JPH0481623B2 - - Google Patents

Description

[Detailed description of the invention]

"Industrial Application Field" The present invention relates to a thermoplastic resin composition having excellent heat resistance and impact resistance. ``Prior Technology'' Office equipment and electrical equipment such as word processors, personal computers, TV sets, and tape recorders generate internal heat and are not used in locations where they are exposed to external shocks or high temperatures. Therefore, molding is required using a thermoplastic resin having heat resistance and impact resistance. As such thermoplastic resin compositions having heat resistance and impact resistance, modified polyphenylene ethers, polycarbonates, nylon resins, compositions of ABS resins and N-phenylmaleimide-styrene copolymers, etc. are used. ing. "Problems to be Solved by the Invention" However, compared to general molding resins such as ABS resin, modified polyphenylene ether, polycarbonate, etc. are relatively expensive, and
There was a problem that the moldability was poor due to the high melt viscosity. In addition, ABS resin and N-phenylmaleimide-styrene copolymer compositions are relatively inexpensive and have good moldability (Japanese Patent Application No. 10730/1989).
(Specification), when the content of ABS resin is increased to improve impact resistance, heat resistance decreases, and conversely, when the content of N-phenylmaleimide-styrene copolymer is increased, Heat resistance improves, but
It was difficult to obtain a balance in physical properties because impact resistance and moldability decreased. The present inventors have conducted extensive research with the aim of providing a thermoplastic resin composition that does not have such problems, has excellent heat resistance and impact resistance, and has good moldability. This invention has been achieved. "Means for Solving the Problems" The above object of the present invention is to combine the following three components (A), (B) and (C) with 6 to 55% by weight of component (A) and 6 to 55% by weight of component (B). 20 to 65 parts by weight of a composition containing 0 to 33% by weight and 3 to 46% by weight of component (C) and having a melt flow rate of 3 to 25, and
This can be achieved by a heat-resistant and impact-resistant resin composition containing polycarbonate in a total amount of 100 parts by weight. (A) 90-50% aromatic vinyl monomer residues, 10-50 maleimide and/or N-aromatic maleimide residues
%, and a copolymer consisting of 0 to 30% of vinyl monomer residues copolymerizable with these. (B) A copolymer consisting of 90-40% aromatic vinyl monomer residues and 10-60% unsaturated nitrile residues. (C) 40-85% by weight of aromatic vinyl monomer, unsaturated nitrile in the presence of 5-75 parts by weight of rubbery polymer.
Polymerization using a monomer mixture consisting of 15 to 45% by weight and 0 to 30% by weight of a vinyl monomer copolymerizable with these in an amount such that the total amount with the above rubbery polymer is 100 parts by weight. A copolymer obtained by The aromatic vinyl monomers used and contained in the above three components (A), (B), and (C) are styrene, but α-methylstyrene, p- Methylstyrene, t-butylstyrene, halogenated styrene or mixtures thereof can also be used. As the N-aromatic maleimide contained in component (A), N-phenylmaleimide is generally used, but N-alkyl-substituted phenyls such as N-tolylmaleimides and N-p-ter.butylmaleimide Maleimides, N-naphthylmaleimide, etc., or
Mixtures of these may also be used. N-aromatic maleimide and maleimide can be used as a mixture in any ratio, but from the viewpoint of compatibility with other resins, the content of maleimide residue is lower than that of maleimide residue and N-aromatic maleimide. It is preferably within 10% of the total amount with residues. Generally, heat resistance improves as the content of maleimide residues increases. Aromatic vinyl monomer and maleimide derivative used in component (A) and "vinyl monomer copolymerizable"
Common examples include acrylonitrile, methacrylonitrile, acrylic esters, methacrylic esters, maleic anhydride, or mixtures thereof. The maleimide derivative residue content of component (A) is 10 to 50
% is suitable. The maleimide derivative residue content is
If it is less than 10%, the heat resistance of the composition obtained by blending will not be sufficient, while if it exceeds 50%, its fluidity will be significantly reduced, which is not preferable. In this specification, the residue content is expressed as a ratio of the number of molecules of each residue contained in the copolymer. In addition, if the content of "copolymerizable vinyl monomer" residue exceeds 30%, other components or
This is not preferable because the compatibility with the resin decreases. Component (A) is a pre-prepared copolymer containing a desired amount of maleic anhydride residues, such as a styrene-maleic anhydride copolymer, a desired primary amine, and, if necessary, It may be produced by imidization with ammonia, or by copolymerization of a desired maleimide monomer and an aromatic vinyl monomer, or by copolymerization of these monomers with an unsaturated nitrile monomer, etc. May be manufactured. The polymerization method is generally emulsion polymerization, bulk polymerization, bulk-suspension polymerization, suspension polymerization, or the like. The unsaturated nitrile monomer contained in both components (B) and (C) is generally acrylonitrile, but methacrylonitrile or a mixture thereof can also be used. It is appropriate that the unsaturated nitrile monomer residue contained in component (B) be 10 to 60%; if it is outside this range, the compatibility with component (A) will deteriorate and the resulting composition This is not preferable because it reduces the heat resistance and impact resistance of the product. Component (B) is produced by bulk polymerization, bulk-suspension polymerization, suspension polymerization, emulsion polymerization, etc. Furthermore, when unsaturated nitrile is used as a "copolymerizable vinyl monomer" during the production of component (A), component (A) can be produced simultaneously. The "copolymerizable vinyl monomer" used in the production of component (C) is generally acrylic esters, methacrylic esters, or mixtures thereof. In addition, as the rubbery polymer used for the copolymer (C) component, polybutadiene, styrene-
Butadiene copolymer rubber, acrylonitrile-butadiene copolymer rubber, acrylic ester rubber,
Commonly used are ethylene-propylene rubber, ethylene-propylene-nonconjugated diene rubber, or mixtures thereof. Acrylonitrile and methacrylonitrile are used as the unsaturated nitrile. Component (C) is obtained by adding and polymerizing a monomer mixture to 5 to 75 parts by weight of a rubbery polymer so that the total amount becomes 100 parts by weight. As for the polymerization method,
Emulsion polymerization, bulk-suspension polymerization, bulk polymerization, etc.
The normal method is fine. The appropriate content of the rubbery polymer in component (C) is 5 to 75 parts by weight; if it is less than 5 parts by weight, sufficient impact resistance cannot be obtained, and if it exceeds 75 parts by weight, the copolymer This is not preferable because it becomes difficult to mix with combined (A) and (B). Furthermore, if the blending ratio of each monomer in the monomer mixture is outside the above range, chemical resistance, compatibility, etc. will deteriorate, which is not preferable. The above components (A), (B), and (C) are blended using a Banbury mixer, an extruder, or the like. The appropriate blending ratio is 6 to 55% by weight of component (A), 0 to 33% by weight of component (B), and 3 to 46% by weight of component (C), which is outside the above range. However, the balance between heat resistance and impact resistance is not good and is not suitable. Furthermore, the melt flow rate (MFR) of the composition obtained by blending each component (A), (B), and (C) is
3 to 25 is appropriate, and if the MFR is less than 3,
The impact resistance of the obtained composition decreases, and if it exceeds 25, the impact resistance and heat resistance of the obtained composition decrease, which is not preferable. In addition, in this specification, MFR is JIS
This is a value measured based on method A described in K7210 under conditions of a measurement temperature of 240°C, a load of 10 kg, and a time of 10 minutes. A composition formed by blending each component (A), (B) and (C)
MFR can be adjusted by the degree of polymerization of each component and the blending ratio of each component. Generally, as component (A) increases, MFR decreases, and each component (B) and (C)
In particular, as component (B) increases, MFR increases. The polycarbonate used in the production of the composition according to the present invention is not particularly limited to aromatic type, aliphatic type, or a mixture of both, but polycarbonate using bisphenol-A as the bisphenol component is used. Bis(4-hydroxyphenyl)-2,2
-Propane carbonate is common. In addition, the polycarbonate to be used preferably has a relatively low viscosity, for example, a flow value (unit: 10 ^-2 ml/sec) of 2.5 to 10, particularly one with a flow value of 4 to 8, from the viewpoint of moldability, ease of kneading, etc. Preferably. In addition,
"Flow value" is a value measured based on JIS K6719. The blending ratio of polycarbonate and each component (A), (B), and (C) is 20% of the composition consisting of each component (A), (B), and (C).
It is appropriate to mix up to 65 parts by weight, preferably 30 to 55 parts by weight, and polycarbonate in a total amount of 100 parts by weight. If the polycarbonate content is less than 35 parts by weight, the impact resistance (particularly the falling weight impact strength (FDI)) will be significantly reduced, which is not preferable. Even if the content of polycarbonate exceeds 80 parts by weight, there is no significant deterioration in physical properties and there is no particular disadvantage, but the resulting composition becomes expensive and uneconomical. The blending is preferably carried out by melt-kneading using a Banbury mixer, an extruder, or the like. Note that it is best to mix the components (A), (B), and (C) in a predetermined ratio in advance, melt and knead them using an extruder, etc., and then blend the pelletized composition with the polycarbonate. is easy and preferable, but (A), (B), (C)
Each component and polycarbonate may be kneaded simultaneously. "Effects of the Invention" The composition according to the present invention has good impact resistance, especially FDI
It has excellent heat resistance and good moldability, so it can be used to mold casings for electrical and office equipment and other products that require high physical properties and have complex shapes. It can be applied. "Example" In each of the following Examples and Comparative Examples, the polycarbonate used was polybis(4-hydroxyphenyl)-2, which has a flow value of 7.0×10 ^-2 ml/sec,
2-Propane carbonate (Mitsubishi Chemical Industries, Ltd.)
NOVAREX 7022A) was used. Each component (A), (B), and (C) was prepared according to each production example described below. The physical properties of the obtained composition were measured by the following method. Tensile strength, elongation: JIS K6871 Vikatsu softening point: JIS K6870 Load: 5Kg Melt flow rate: JIS K6870 (load: 10Kg, temperature: 240°C) Izotsu impact strength: JIS K6871 Notched falling weight impact strength (FDI): Effects Technology, USA
ETI-8200/ETI-300 manufactured by Inc. was used. Diameter 1/
A predetermined weight is fixed to a falling weight with a 2" spherical tip, and it is dropped from a certain height onto the center of a plate-shaped molded product with a thickness of 2.5 mm, and the energy required until the plate-shaped molded product breaks is measured. [Production of components (A) and (B)] Production example 1 69 kg of styrene and maleic anhydride in a 300 polymerization can.
Charge 1.9Kg and 95℃ while stirring and purging with nitrogen.
The temperature rose to . To this system, 10 kg of maleic anhydride kept at 70°C was continuously added at a constant addition rate, and bulk polymerization was carried out at 95°C for 460 minutes. When the continuous addition was completed, the polymerization rate was 44% by weight, and the maleic anhydride residue in the resulting polymer was 31% by mole. After adding 21 kg of acrylonitrile to this system over a period of 20 minutes, the temperature of the system was maintained at 90°C and an additional 20 kg of acrylonitrile was added.
Stir for a minute. At this point, the concentration of maleic anhydride in the monomer was 0.1% or less. Add 30g of polyvinyl alcohol suspending agent to this system.
70 kg of water containing 30 g of a polyacrylic acid ester suspending agent and 300 g of sodium sulfate was added to form a suspension. This suspension system was heated to 110℃, and at 110℃ it was heated to 120℃.
After stripping for a minute, 8 kg of acrylonitrile was added. After raising the temperature to 150°C over 60 minutes, stripping was performed again at this temperature for 120 minutes. Further, 7 kg of aniline and 2 kg of 25% aqueous ammonia were added, and an imidization reaction was carried out at 155°C for 120 minutes. The obtained bead-like polymer was washed with water, dried, and pelletized using an extruder. As a result of analysis of this pellet, 27 mol% of N-phenylmaleimide residues, 4 mol% of maleimide residues, and 69 mol% of styrene residues were found.
Component (A) consists of 76% by mole, 41% by mole of acrylonitrile residue, and 59% by mole of styrene residue.
It was found that it was a mixture of 24% by weight of component (B). The obtained composition is hereinafter referred to as "AB-1". Production Examples 2 to 8 Add 100 parts of ion-exchanged water (parts by weight, same below) to a flask polymerization tank equipped with a reflux condenser and a stirrer.
0.05 part of polyvinyl alcohol, 2 parts of acrylic acid
Dissolve 0.1 part of ethylhexyl acrylate copolymer, further dissolve N-phenylmaleimide, styrene, acrylonitrile, and terpinolene as a chain transfer agent in the proportions shown in Table 1. Lonitrile 0.15
2.5 hours at a polymerization tank temperature of 60°C while stirring under a nitrogen stream.
Suspension polymerization was further carried out at 80°C for 2 hours. The slurry was filtered through a cloth, dehydrated, and dried to obtain a granular copolymer composition. The resulting compositions are hereinafter referred to as "AB-2".
~It's called "AB-8." The ratio of component (A) to component (B) is (A)/(B) = 56/44 (weight ratio) for AB-2 to AB-4, and (A) for AB-5 to AB-8. /(B)=40/60
(weight ratio).

[Table] Unit: parts by weight
[Production of component (C)] Production Examples 9 to 10 Two types of graft copolymers having the composition, content, particle size, and styrene/acrylonitrile ratio of the rubbery polymers shown in Table 2 were subjected to a conventional emulsion polymerization method. Manufactured by.

[Manufacture of composition consisting of components (A), (B) and (C)]

Production Example 11 The components (A), (B), and (C) above were mixed in the ratios shown in Table 3, pelletized using an extruder, and the melt flow rate (MFR) was measured. The obtained compositions are designated as "D-1" to "D-9".

[Table] Examples 1 to 13, Comparative Examples 1 to 5 Compositions D-1 to D-9 listed in Table 3 and polycarbonate were blended at the ratio (weight ratio) listed in Table 4, and kneaded using an extruder. , pelletized. The physical properties of the obtained composition are listed in Table 4.

【table】

[Table] As is clear from Table 4, the composition according to the present invention has good heat resistance and moldability (evaluated by MFR), and exhibits excellent impact resistance, especially FDI.
Furthermore, the decrease in FDI at low temperatures is extremely small.

Claims (1)

[Scope of Claims] 1 The following three components (A), (B) and (C), wherein component (A) is 6 to 55
A composition containing component (B) in an amount of 0 to 33% by weight and component (C) in an amount of 3 to 46% by weight, and having a melt flow rate of 3 to 25. 20 to 65 parts by weight of a heat-resistant, impact-resistant resin composition, and polycarbonate in a total amount of 100 parts by weight. (A) 90-50% aromatic vinyl monomer residues, 10-50 maleimide and/or N-aromatic maleimide residues
%, and a copolymer consisting of 0 to 30% of vinyl monomer residues copolymerizable with these. (B) A copolymer consisting of 90-40% aromatic vinyl monomer residues and 10-60% unsaturated nitrile residues. (C) 40-85% by weight of aromatic vinyl monomer, unsaturated nitrile in the presence of 5-75 parts by weight of rubbery polymer.
Polymerization using a monomer mixture consisting of 15 to 45% by weight and 0 to 30% by weight of a vinyl monomer copolymerizable with these in an amount such that the total amount with the above rubbery polymer is 100 parts by weight. A copolymer obtained by