JPS59184254A - Polyaryl ketone resin composition - Google Patents

Abstract

PURPOSE:To provide a polyaryl ketone resin compsn. having excellent heat resistance, by blending an arom. thermoplastic resin having amide and/or imide groups. CONSTITUTION:40-99pts.wt. crystalline polyaryl ketone resin (A) mainly composed of a repeating unit of formula I (wherein Z, Z', Z'' are each a bivalent arom. residue contg. at lest one six-membered carbon ring ; Q is O, CO or a direct bond ; n is 0-3), such as a polyether ether ketone resin composed of a repeating unit of formula II, and 1-60pts.wt. arom. thermoplastic resin (B) having amide and/or imide groups, such as Torlon 4203L (a product of Amoco Chemicals) or ULTEM-1000 (a product of G.E. Co.) are melt-mixed together at 340-400 deg.C by using a heated roll or Banbury mixer.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a polyarylketone resin composition with excellent heat resistance.

Imperial Chemical Industries Poly,
Crystalline polyarylketone resins, such as ether ether ketone resins, are used as engineering resins with excellent heat resistance, flame retardance, hydrolysis resistance, and chemical resistance, and are used as insulation coatings for electric wires and cables, aircraft parts, electrical equipment, etc. It is attracting attention for applications such as electronic components. In these applications, molded products are often used at high temperatures, so the resin material is required to have even better heat resistance.

Crystalline polyarylketone resin is originally a highly crystalline polymer, but the glass transition temperature of the resin itself is approximately 140 to 170.
℃, so its heat resistance is not at all sufficient, and the reality is that it is desired to further improve its heat resistance, especially when it is applied to the above-mentioned uses.

As a result of intensive studies aimed at improving the heat resistance of crystalline polyarylketone resins, the present inventors found that melt compounding of a specific aromatic thermoplastic resin containing an amide group and/or an imide group has improved mechanical properties. The inventors have discovered that this is extremely effective in improving heat resistance as well as improving heat resistance, and have arrived at the present invention.

MoQ-Z″:F-+ (where z, z′, z″ are divalent aromatic residues containing at least one carbon 6-membered ring, Q
40 to 99 parts by weight of a crystalline polyalketone resin whose main structural unit is a repeating unit of O, Co, or a direct bond, and n is an integer of O to 6, and an amide group and/or imide Aromatic thermoplastic resin containing group 1
The present invention provides a polyarylketone resin composition obtained by heat-melting and mixing up to 40 parts by weight.

The crystalline polyarylketone resin 1 used in the present invention has the general formula +O-Z -0-, 'Z' (-Q -
It is a polymer represented by Z″Y. Here, Z1Z′, Z
'', Q is O, CO or a direct bond, and n
represents an integer from 0 to B.

In particular, it is polyetheretherketone resin (hereinafter abbreviated as P, BEK resin), which is a typical crystalline polyarylketone resin.
It is commercially available from Industries, Inc. The manufacturing method is disclosed in European Patent No. 1.879 and the corresponding Japanese Patent Application Laid-Open No. 54-90296, and is carried out at 150-400°C in a diphenylsulfone solvent.
It is produced by reacting 4,4'-difluorobenzophenone and no-hydroquinone under temperature conditions of .

In addition to the aryl ketone structural unit as a main component, other conjugated units can be partially introduced into the crystalline polyaryl ketone resin used in the present invention, if necessary. A method for producing these copolymers is described in British Patent No. 141'4.
It is disclosed in the specification of No. 421, Japanese Patent Application Laid-Open No. 52-38000, etc.

The aromatic thermoplastic polymer containing an amide group and/or (d-imide group) used in the present invention has an amide group and/'! It is a thermoplastic resin with a glass transition temperature of 150°C (preferably 170°C) or higher containing
Examples include noetherimide resins and amorphous aromatic boronamide resins.

These resins will be explained in more detail below.

Polyamide-imide resin used as one of the aromatic thermoplastic polymers of the present invention (hereinafter abbreviated as FAI resin)
is the general formula % Formula % Let's use the repeating unit as the main constituent unit O ~ 1
00 (preferably 50 to 100) mole, and the following (n) in an amount less than 70 (preferably 50) mole
Among the aromatic polymers which can have the general formula (Ill), they have thermoplastic properties.

Some of the imide bonds in structures (1) and (lit) are broken into the amic acid bond 1 \O-OH as its ring-closing precursor. Here, Ar is a hexavalent aromatic group containing at least one 6-membered carbon ring, of which two carbonyl groups are bonded to adjacent carbon atoms in the benzene ring of the Ar group. For example, structures such as can be specifically listed.

Ar is a divalent compound containing at least one carbon 6-membered ring (in the formula Y
is 0, s, co1so2, SO1 (indicates an alkyl group having 1 to 6 carbon atoms), and the like. "Ar" is an aromatic group in which at least one tetravalent carbonyl group containing a 6-membered carbon side is connected, and it is characterized by the fact that two of these groups are bonded to adjacent carbon atoms in the benzene ring of the Ar1 group. For example, R is a divalent aromatic and/or alicyclic residue, and specific examples include the following.

These PAI resins can be manufactured by adding polar compounds such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone, and cresol. In addition, the introduction of the structural unit (n) polyamide unit and/or (III) polyimide unit which can be partially copolymerized to the structural unit (1) as the main component as necessary is the introduction of the structural unit (1) as the main component. This is achieved by substituting and reacting PAI resin during ice making.

Among them, a typical FAI resin is sold by Amoco Corporation in the United States and has the same molecular structure. The manufacturing method for these is covered by British Patent No. 1, 056.564, which was filed by Tandert Oil Company.
No. 661,832, and the like.

The aromatic polyetherimide resin (hereinafter referred to as PEI resin) used as one of the aromatic thermoplastic polymers of the present invention has a repeating unit represented by the general formula as a main unit, and has an ether bond and an imide bond. It is an aromatic polymer composed of two bonding units as essential bonding units. Ar1Ar' and R here
is the same as shown in formulas (1) and (II) above. Typical examples include those with the following structural formula.

The amorphous aromatic polyamide resin (hereinafter abbreviated as PA resin) used as one of the aromatic thermoplastic polymers of the present invention has an aromatic structure whose main constituent unit is a repeating unit expressed by the general formula %. group polymer (R and A r' here are both (n)
The glass transition temperature is 150°C or higher and has thermoplastic properties. A typical example thereof is one having the following structural formula.

The composition of the present invention comprises crystalline polyarylketone resin 40
-99 (preferably 50-95 parts by weight of aromatic thermoplastic resin containing an amide group and/or imide group (hereinafter abbreviated as heat-resistant thermoplastic resin)) 1-60 (preferably 5-5.0) It is prepared by heating and melting mixing parts by weight.If the amount of the heat-resistant thermoplastic resin is less than 1 part by weight, the effect of improving the heat distortion temperature of the crystalline polyaryl ketone resin will be small, which is not preferable. If the amount is more than 100%, the heat distortion temperature is saturated at the upper limit, so it is unnecessary in terms of improving heat resistance.

The composition of the present invention may further contain 70% by weight of at least one filler, if necessary. Examples of the fillers used include (a) wear resistance improvers: graphite, carborundum, silica powder, molybdenum disulfide, fluororesin, etc., (1) reinforcing agents: glass fiber, carbon fiber, boron fiber, silicon carbide fiber,
Carbon whiskers, asbestos fibers, asbestos, metal fibers, etc. (C) Flame retardant improvers such as antimony dioxide, magnesium carbonate, calcium carbonate, etc. (d) Electrical property improvers: clay, mica, etc., (C) Tracking resistance (f) Acid resistance improvers: Barium sulfate, silica, calcium metasilicate, etc. (g) Thermal conductivity improvers: Metal powders such as diiron, zinc, aluminum, copper, etc. (11) Other synthetic and natural compounds that are stable at temperatures above 350°C, such as Nigaras beads, glass spheres, calcium carbonate, alumina, talc, diatomaceous earth, water-containing alumina, mica, mineral balloons, asbestos, various metal oxides, and inorganic pigments. There are many types.

In preparing the composition of the present invention by heating and melt-blending, equipment used for melt-blending ordinary rubber or plastics, such as a hot roll, a Panbury mixer, a Brabender, an extruder, etc., may be used. I can do it. The mixing operation is continued until a homogeneous formulation is obtained.

The mixing temperature is 640 to 400 (preferably Kero, 50 to R8
0)°C is appropriate. crystalline polyarylketone resin,
The heat-resistant thermoplastic resin and the fillers that can be added as needed can be separately fed to a melt mixer, or these raw materials can be mixed in advance in a mortar, Henschel mill, ball mill, ribbon blender, etc. This can also be done by pre-mixing the mixture using a machine and then supplying it to the melt mixer. In addition, when melt-mixing a six-component system, in addition to the method of performing six-part melt blending of the crystalline polyaryl ketone resin, heat-resistant thermoplastic resin, and fillers, there is also a method of melt-blending the crystalline polyaryl ketone resin, heat-resistant thermoplastic resin, and fillers. It is also possible to utilize a two-stage blending method in which the two are melt-blended to produce a master pellet, and then the master pellet and the heat-resistant thermoplastic resin are melt-blended.

Although the composition of the present invention forms a homogeneous melt blend and can be subjected to injection molding or extrusion molding, it has no difficulty in being applied to other compression molding, sintering molding, and the like.

When the molded article obtained by molding the composition of the present invention is heat-treated at a temperature below the melting point of the crystalline polyaryl carbonate resin, the effect of further improving heat resistance can be obtained.

The molded article obtained by molding the composition of the present invention has excellent properties such as surface thermal properties, mechanical properties, electrical properties, sliding properties, and solvent resistance properties, and can be used for many purposes. can do.

For example, compositions useful for automobile parts, electric/electronic parts, water supply and distribution equipment parts, sliding members, etc. can be designed and formulated.

Hereinafter, the present invention will be further explained in detail by giving Examples.

It should be noted that the values of ratio, ratio, and parts shown in the present examples indicate parts by weight, weight ratio, and parts by weight, respectively, unless otherwise specified.

Examples 1 to 4 and Comparative Examples 1 to 2 PE'''EK resin (manufactured by Imperial Chemical Industries, glass transition temperature 146°C, 1 (manufactured by Amoco, "Torlon 4203L") was triblended with the composition shown in Table 1. After that, it is fed to a Brabender Plastograph Extruder and the processing temperature is 350 to 3'60.
The mixture was melt-kneaded at 50° C. and a screw rotation speed of 50 rpm to obtain uniform melt-blended pellets.

Next, the homogeneous melt blend pellets obtained above were heated to a temperature of 666.
After compression molding was performed at a temperature of 100 kg/ffl at a pressure of 100 kg/ffl to prepare a molded test piece, the physical properties were measured and the results shown in Table 1 were obtained.

As can be seen from the results in Table 1, in the case of Examples 1 to 4, P
A) The effect of improving heat distortion temperature is remarkable compared to Comparative Example 1 in which no resin is added.

When the amount of PA■ resin added increased in the order of Examples 1, 2, 6, and 4, the heat distortion temperature and bending stress improved in accordance with the amount added.

Stream side 5 70 parts of PEEK resin (manufactured by Imperial Chemical Industries) and PEI resin (manufactured by General Electric Company) with the formula ``U''
After tri-blending 30 parts of I tem-1000″) with a ribbon blender, a 40 mmφ extruder equipped with a screw with a compression ratio of 2.6 (processing temperature 340-360°C
) and melted and kneaded to obtain uniformly blended pellets.

Next, the uniformly mixed pellets obtained above were placed in an injection molding machine (barrel temperature 640-370°C, injection pressure 1,000 Ky/c).
I? When the heat distortion temperature and mechanical properties were measured, the results shown in Table 2 were obtained.

Table 2 As is clear from the results in Table 2, the physical properties of Example 5 showed an excellent improvement effect, especially in terms of heat resistance, compared to the working distance value of Comparative Example 1 of PEEK resin alone. .

Example 6 Polyarylketone resin (heat distortion temperature 156°C) 80
It was synthesized by solution polymerization from an equimolar mixture of 4.4'-2,2-propylbis(p-phenyleneoxy)dianili/ and isophthalic acid dichloride, and had a logarithmic viscosity of 1.32 (solvent: N - Methylpyrrolidone, polymer concentration: 0.5 g/”s measurement temperature 2
After tri-blending 20 parts of a PA resin having a characteristic of 30° C.), the mixture was passed through the same Brabender extruder as in Example 1 to obtain a uniformly blended beret.

Next, the above uniformly mixed pellets were mixed at a temperature of 380°C and a pressure of 5DK.
When a physical property test piece was prepared by compression molding at y/cyl and the heat distortion temperature was measured, it showed a high value of 203°C.

Example 7 Logarithmic viscosity o65 (solvent 2N-methylpyrrolidone, polymer concentration: 0.5 g/dl, measurement temperature: 60
°C) 50 parts and the same crystalline polyarylketone resin as Example 6 (heat distortion temperature = 156 °C, melting point: 340 °C)
After tri-blending 50 parts, the mixture was melt-kneaded in the same manner as in Example 1 to obtain uniformly blended pellets.

Next, the homogeneously blended pellets were compression molded to prepare physical property test pieces, and when the heat distortion temperature was measured, it showed a high value of 225°C.

Example 8 shows a relative viscosity of 1.20 (solvent: chloroform,
Polymer concentration: Q, 5 g/di, measurement temperature: 30
A crystalline polyarylketone copolymer resin 9 having a heat distortion temperature of 157°C and having a heat distortion temperature of 157°C.
After tri-blending 0 parts, it was applied to a Brabengoo extruder and melted and mixed to obtain uniformly blended pellets.

Next, the uniformly mixed pellets were mixed at a temperature of 370°C and a pressure of 50K.
A physical property test piece was prepared by compression molding at g/cffl, and the heat distortion temperature was measured, which was as high as 209°C.

20 parts of PA resin having a relative viscosity of 2.05 (polymer concentration 20.5 coefficient solvent: 98% concentrated sulfuric acid, measurement temperature: 60°C) and the same PEEK as in Example 1.
After tri-blending 80 parts of the resin, the mixture was placed in a Brabender extruder and melt-kneaded to obtain uniformly blended pellets.

Next, the above uniformly mixed pellets were mixed at a temperature of 380°C and a pressure of 50K.
When a physical property test piece was prepared by compression molding at g/ffl and the heat distortion temperature was measured, it was found to be as high as 185°C.

Patent applicant: Higashi Shishiki Kaisha 4

Claims (1)

[Claims] 1 General formula, -(-0-Z-C-Z'(-Q-Z''+-)
(In the formula, z, z', 7.// is a divalent aromatic residue containing at least one carbon 6-membered ring, Q is 0, Co1 or a direct bond, and n is 0 to 6 40 to 99 parts by weight of a crystalline polyarylketone resin whose main structural unit is a repeating unit of A polyarylketone resin composition.