JPS6351182B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a thermoplastic resin composition, and its purpose is to improve the melt processability of aromatic polyamide-imide resin. Polyimide resins represented by the U.S. DuPont trademark "Vespel SP" and the U.S. company trademark "Polyimide 2080" have excellent heat resistance, mechanical strength, chemical resistance, and electrical properties, but lack melt processability. On the other hand, aromatic polyamide-imide resin, represented by the American Amoco trademark "Torlon", has both polyimide bonds and polyamide bonds in the polymer main chain, so it is difficult to melt mold. Furthermore, as it has excellent heat resistance, mechanical strength, chemical resistance, and electrical properties similar to polyimide resin, it is possible to supply high-performance industrial material parts with a highly productive molding method. , is attracting attention from various quarters. However, aromatic polyamide-imide resin also has a considerably higher melt viscosity than general-purpose thermoplastic molding materials, making it difficult to melt blend and melt mold, making it particularly difficult to obtain molded products using injection molding machines. In this case, the mold temperature is over 200℃, the injection pressure is 1000-2000Kg/ ^cm2 , and the conditions are extremely narrow and strictly controlled (e.g. resin residence time, resin temperature, screw shape, mold structure, etc.). ), and the melting properties and other properties are still insufficient to achieve sufficient molding productivity. The inventors of the present invention have conducted intensive studies with the aim of making aromatic polyamide-imide resins flow well when melted. As a result, we have discovered that polyarylene polyether polysulfone resins (hereinafter referred to as aromatic polysulfone resins) have a specific melt flow rate and decomposition temperature. abbreviated)
was found to be effective as a fluidization promoter for aromatic polyamideimide resins, and the present invention was achieved. That is, the present invention is based on the general formula (In the formula, Ar is a trivalent aromatic group containing at least one 6-membered carbon ring, and R is a divalent aromatic residue having 6 to 27 carbon atoms.) The main structural unit is the repeating unit represented by Aromatic polyamideimide resin with 50-99.9 parts by weight and temperature 350℃, load
Melt flow rate under operating conditions of 2160g is
The present invention provides a resin composition comprising 0.1 to 50 parts by weight of an aromatic polysulfone resin having characteristics of 0.1 g/10 minutes or more and a decomposition temperature of 350° C. or more. The aromatic polyamideimide resin used in the present invention has the general formula 50 with the repeating unit expressed as the main constituent unit
~100 mol% (preferably 70-100 mol%),
Other aromatic polymers which may contain less than 50 mol% (preferably 30 mol%) of other bonding units, such as polyamide and/or polyimide units having the general formula () or (): be. Some of the imide bonds in this structure () and () are the amic acid bonds as their ring-closing precursors. This also includes those that remain in this state. here
Ar is a trivalent aromatic residue containing at least one carbon 6-membered ring, of which the divalent one means that two carbonyl groups are bonded to adjacent carbon atoms in the benzene ring of the Ar group. Characterized by. for example,

【formula】

【formula】

【formula】

【formula】

It is possible to specifically enumerate structures such as:
Ar' is a divalent aromatic residue or aliphatic group containing at least one carbon 6-membered ring, for example,

【formula】 【formula】

【formula】

【formula】

【formula】

[Formula] - (CH ₂ ) ₄ -, - (CH ₂ ) ₃ -, etc. Ar'' is an aromatic group in which a tetravalent carbonyl group containing at least one 6-membered carbon ring is linked, two of which are each bonded to adjacent carbon atoms in the benzene ring of the Ar'' group. characterized by, for example,

【formula】

[Formula] etc. R is a divalent aromatic residue having 6 to 27 carbon atoms, and specific examples include

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

[Formula] etc. The aromatic polyamideimide resin with the structural unit formula ( ) used in the present invention is dimethylformamide,
Dimethylacetamide, N-methylpyrrolidone,
In polar organic solvents such as cresol

【formula】

【formula】

It can be produced by reacting a combination of the following. In addition, the introduction of structural units () polyamide units and/or () polyimide units that can be partially copolymerized into the structural unit () as the main component as required is the production of polyamide-imide of the structural unit (). When the raw material

[expression] or

[Formula] one Department

【formula】

【formula】

【formula】 or

This is achieved by substituting with [Formula] and reacting. Among them, a typical aromatic polyamide-imide resin is sold by Amoco Corporation in the United States. It has a molecular structure of These manufacturing methods are disclosed in detail in British Patent No. 1056564 and US Patent No. 3661832 filed by Standard Oil. Other methods for producing aromatic polyamide-imide resins are also disclosed in U.S. Patent No. 3,669,937 (Bayer AG), French Patent No. 2,096,454 (Celarac Fabrics AG), French Patent No. 1,515,066 (DuPont AG), No. 45-18316 (Hitachi Chemical), British Patent No. 1181446 (Hitachi Chemical), French Patent No.
No. 2086324 (General Electric Company), Special Publication
No. 45-35072 (Nitto Denko Corporation), U.S. Patent No. 3625911
(Mobil Oil), British Patent No. 1277834 (Lone Poulenc), British Patent No. 1032649 (Westinghouse), and Special Publication No. 49-4077 (Toray Industries). The aromatic polysulfone resin used as a fluidization promoter in the present invention has an arylene bond (aromatic core bond),
Among linear polymers containing ether bonds and sulfone bonds as essential bonding units, those with a melt flow rate of 0.1 (preferably 0.5) g/10 minutes or more under operating conditions of a temperature of 350°C and a load of 2160 g are particularly preferred. , and has the characteristics of a decomposition temperature of 350°C or higher. However, the melt flow rate and decomposition temperature defined in the present invention are based on the following measurement method. That is, the melt flow rate was performed by using a melt indexer manufactured by Toyo Seiki Seisakusho Co., Ltd., and placing a sample that had been dried to an absolutely dry state in advance in a cylinder heated to 350°C for 8 minutes, and then applying a load of 2160 g. The orifice in the center of the die (inner diameter 2.1
mmφ, length 8 mm) and measure the amount of polymer discharged in 10 minutes. In addition, the decomposition temperature is determined by Rigaku Denki.
Using a thermogravimeter manufactured by Co., Ltd., the sample, which had been dried to an absolutely dry state, was kept in a nitrogen atmosphere and its weight was continuously measured while heating at a rate of 10°C/min. The temperature at which the weight % weight loss is reduced is read and taken as the decomposition temperature. If an aromatic polysulfone resin with a melt flow rate lower than 0.1 g/10 min under operating conditions of temperature 350°C and load 2160 g is used, the melt viscosity of the fluidizing agent itself will be too high, making it difficult to use aromatic polyamideimide resin. It is unsuitable because it becomes difficult to fluidize. In addition, aromatic polysulfone resins with a decomposition temperature lower than 350°C have too low thermal stability and tend to thermally decompose when melt-mixed with aromatic polyamide-imide resin, making stable mixing operations difficult. It's inappropriate. Representative examples of suitable aromatic polysulfone resins that meet the definition as a fluidization promoter of the present invention include those having the following structural formula. These aromatic polysulfones can be easily produced by the methods described in, for example, Japanese Patent Publication No. 10067-1970, Japanese Patent Publication No. 7799-1979, and Japanese Patent Publication No. 617-1974, and can be used to create the desired melt blend. to 1
The species and/or two or more species can be arbitrarily selected. The proportion of aromatic polysulfone resin as a good fluidizing agent in the total composition of the present invention is 0.1, corresponding to 50 to 99.9 parts by weight of aromatic polyamideimide resin.
~50 parts by weight is suitable. Since the aromatic polysulfone resin has a good fluidizing effect even when added in a small amount, the lower limit can be set to a relatively small value of 0.1 parts by weight. The amount is preferably 0.5 parts by weight or more. Furthermore, since the compatibility between the aromatic polysulfone resin and the aromatic polyamide-imide resin is not necessarily good, if the content of the aromatic polysulfone resin in the entire composition is too large, the physical properties and chemical resistance of the polyamide-imide resin may deteriorate. This is not desirable because it will not be possible to maintain the Therefore, there is an upper limit to the content of the aromatic polysulfone resin, and the appropriate amount is 50 parts by weight (preferably 40 parts by weight) or less. The following fillers may be added to the composition of the present invention in an amount of less than 10% by weight. Examples of the fillers include (a) wear resistance improvers: graphite, carbon random, silica powder, molybdenum disulfide, fluorine resin, etc., (b) reinforcing agents: glass fiber, carbon fiber, boron fiber,
Silicon carbide fibers, carbon whiskers, asbestos fibers, asbestos, metal fibers, etc. (c) Flame retardant improvers:
Antimony trioxide, magnesium carbonate, calcium carbonate, etc., (d) Electrical property improvers: clay, mica, etc., (e) Tracking resistance improvers: asbestos, silica,
graphite, etc., (f) acid resistance improvers: barium sulfate, silica, etc., (g) thermal conductivity improvers: iron, zinc,
Metal powders such as aluminum and copper, (h)Others: glass beads, glass bulbs, glass balloons, calcium carbonate, alumina, talc, diatomaceous earth, clay, kaolin, clay, calcium sulfite, hydrated alumina, mica, asbestos, various Examples include synthetic and natural compounds that are stable at temperatures above 350°C, such as metal oxides and inorganic pigments. When mixing and preparing the composition of the present invention,
Equipment used for melt blending conventional rubbers or plastics can be utilized, such as hot rolls, Banbury mixers, Brabenders, extruders, and the like. The mixing operation is continued until a homogeneous blend is obtained. The mixing temperature is set above the temperature at which the blended system can melt and below the temperature at which the blended system begins to decompose;
The temperature is selected from the range of 250 to 400°C, preferably 300 to 380°C. In mixing and preparing the composition of the present invention, the aromatic polyamide-imide resin and the aromatic polysulfone resin can be separately supplied to a melt kneader, and these raw materials can be mixed in advance in a mortar, a Henschel mixer, etc. Alternatively, the mixture may be premixed using a ball mill, ribbon blender, etc., and then supplied to a melt kneader. The composition of the present invention forms a homogeneous melt blend and can be subjected to injection molding or extrusion molding, which is a highly productive molding method, but it can also be applied to other compression molding, sintering molding, etc. I have no reservations. Furthermore, when manufacturing molded articles using an injection molding machine, extrusion molding machine, etc. equipped with a screw cylinder with excellent melt blending performance, it is not always necessary to separately prepare a uniform melt blend composition in advance. Aromatic polyamideimide resin and aromatic polysulfone resin may be directly fed separately or simply by dry blending them to a screw hopper to produce a molded article with a uniform composition in one step. is also possible. The molded article obtained by melt molding the composition of the present invention has excellent properties such as heat resistance, mechanical properties, electrical properties, sliding properties, and solvent resistance properties, and can be used for many purposes. be able to. For example, it is useful for automobile parts, electric/electronic parts, water supply and distribution equipment parts, office machine parts, aircraft parts, special machine parts, etc. Hereinafter, the present invention will be further explained in detail by giving Examples. Note that the values of %, ratio, and parts shown in this example mean % by weight, weight ratio, and parts by weight, respectively, unless otherwise specified. Examples 1 to 4 and Comparative Reference Examples 1 to 2 Polyamideimide Resin powder (Amoco “Torlon 4000T”) and formula The first was an aromatic polysulfone resin (UCC "Udel P-1700") having a decomposition temperature of 464°C and a melt flow rate of 8.1 g/10 min.
After dry blending with the composition shown in the table, the pellets were fed to a Brabender Plastograph extruder and extruded while being melted and kneaded at a processing temperature of 360° C. and a screw rotation speed of 25 rpm, which was repeated twice to obtain uniform melt-blended pellets. Next, the flow characteristics of the composition obtained above and the homogeneous melt blend pellets were evaluated at a temperature of 320 to 350°C and a pressure of 20 to 20°C.
Compression molding at 100Kg/ ^cm2 (the higher the aromatic polysulfone resin content, the lower the temperature and pressure),
When molded test pieces were prepared and their physical properties were measured, the results shown in Table 1 below were obtained.

[Table] As can be seen from the results in Table 1, in Examples 1 to 4, the flow characteristics were improved compared to Comparative Example 1 in which no aromatic polysulfone resin was added, and good fluidization was achieved. Furthermore, as the amount of added aromatic polysulfone resin increases in the order of Examples 1, 2, 3, and 4, the flow characteristics improve and the melt moldability improves, but this also increases the bending stress, isot impact strength, and thermal strength of the molded product. Deformation temperature decreases. As shown in Comparative Example 2, if the amount of aromatic polysulfone resin added is increased to an extreme amount of 60%, it is not preferable because the bending stress, Izot impact strength and heat distortion temperature are significantly reduced. Example 5 Aromatic polyamideimide Resin pellets (Amoco “Torlon 4203”) 80
After dry blending 20 parts of the same aromatic polysulfone resin used in Example 1 and 2 parts of tetrafluoroethylene resin (Asahi Glass Co., Ltd. "Aflon Polymist F-5"), a screwdriver with a compression ratio of 2.0/1 was used. 40mmφ extruder equipped with (processing temperature 340-360℃)
An extrusion operation was performed while melting and kneading to obtain uniformly blended pellets. Flow characteristics of this blended pellet (load 21600g, temperature 350℃, ASTM D-1238)
The elevated flow rate was 0.83 g/10 minutes, and the flow characteristics were greatly improved compared to 0.12 g/10 minutes when aromatic polysulfone resin was not blended. Next, the three-way homogeneous blended pellets obtained above were put into an injection molding machine (barrel temperature 350-370℃, mold temperature 210℃, mold temperature 210℃,
A molded test piece was prepared under an injection pressure of 350 kg/cm ² ) and its physical properties were measured, and it was found to have an excellent balance of physical properties as shown in Table 2 below.

[Table] Example 6 Polyamideimide 85 parts of resin powder (Amoco “Torlon 4000T”) and formula Decomposition temperature 451℃, melt flow rate indicated by
Aromatic polysulfone resin (ICI “Polyethersulfone 200P”) with characteristics of 13.0g/10min15
After dry blending, the mixture was melt-kneaded in the same manner as in Example 1 to obtain homogeneous melt-blended pellets. Subsequently, the homogeneous blend pellets obtained were compression molded at a temperature of 340℃ and a pressure of 30Kg/ ^cm2 , and the elevated flow rate, which is a guideline for physical properties and moldability, was measured, and the results are shown in Table 3 below. It was found to have an excellent balance of physical properties and flow characteristics.

【table】

Claims (1)

[Claims] 1. General formula (In the formula, Ar is a trivalent aromatic group containing at least one carbon 6-membered ring, and R is a divalent aromatic residue having 6 to 27 carbon atoms.) The repeating unit represented by the following is the main structural unit: Aromatic polyamide-imide resin having 50 to 99.9 parts by weight, a polyarylene polyether polysulfone resin having a melt flow rate of 0.1 g/10 minutes or more under operating conditions of a temperature of 350°C and a load of 2160 g, and a decomposition temperature of 350°C or more. A resin composition consisting of 0.1 to 50 parts by weight.