JP3513543B2 - Thermoplastic resin composition - Google Patents

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention provides a molded article having excellent impact resistance, heat distortion resistance, and chemical resistance, and having an excellent surface appearance, and at the same time, it has excellent heat resistance. It relates to a plastic resin composition.

[0002]

2. Description of the Related Art A resin composed of ABS resin and polycarbonate resin is a thermoplastic resin having excellent heat resistance, impact resistance and moldability, and is widely used in machines, automobiles, home appliances, office automation equipment and electric and electronic parts. It is used. In recent years, a maleimide resin / polycarbonate resin alloy using a maleimide resin instead of the ABS resin is becoming popular because it is superior in heat distortion resistance to the ABS resin / polycarbonate resin alloy. However, the impact resistance of these resins tends to be lower than that of ABS resin / polycarbonate alloy. JP-A-6-1164
No. 69 discloses a method of blending an ethylene / carbon monoxide / (meth) acrylic acid alkyl ester copolymer with a maleimide resin, but this method still has insufficient impact resistance. On the other hand, in Japanese Patent Laid-Open No. 4-1257, ABS
Ethylene based resin alloy / polycarbonate resin alloy
A method of blending a carbon monoxide / (meth) acrylic acid alkyl ester copolymer has been proposed, but this method is inferior in heat deformation resistance to a maleimide resin / polycarbonate resin alloy.

[0003]

The present invention provides a thermoplastic resin composition having improved impact resistance, chemical resistance, molding processability, etc., without impairing the heat resistance of the maleimide resin / polycarbonate resin alloy. It is provided.

[0004]

Means for Solving the Problems As a result of intensive studies for solving the above problems, the present inventors have found that (A) a specific maleimide resin and (B) a thermoplastic resin composed of a polycarbonate resin. , (C) ethylene, carbon monoxide,
Thermoplastics that provide excellent impact resistance, heat distortion resistance, chemical resistance, molding processability, and excellent surface appearance by blending (meth) acrylic acid alkyl ester copolymer It was found that a resin composition can be obtained, and the present invention has been completed.

That is, the present invention relates to (A) a maleimide resin 90-1 containing 5 to 60% by weight of a maleimide monomer residue.
0% by weight, and (B) polycarbonate resin 10 to 90
With respect to 100 parts by weight of the thermoplastic resin composed of 10% by weight,
(C) A thermoplastic resin composition characterized in that 0.5 to 50 parts by weight of ethylene / carbon monoxide / (meth) acrylic acid alkyl ester copolymer is added.

The maleimide resin (A) used in the present invention contains 5 to 60% by weight of a maleimide monomer and comprises an aromatic vinyl monomer and another vinyl monomer. Are preferred, and those comprising a maleimide-based monomer, an aromatic vinyl-based monomer, another vinyl-based monomer, and a rubber-like elastic material are more preferred.

The maleimide type monomers include maleimide, N-methylmaleimide, N-ethylmaleimide, N
Examples include -phenylmaleimide and derivatives thereof, N-cyclohexylmaleimide and derivatives thereof, and the like. Examples of the aromatic vinyl-based monomer include styrene, methylstyrene, chlorostyrene, α-methylstyrene and the like. Other vinyl monomers include acrylonitrile,
Vinyl cyanide monomers such as methacrylonitrile; (meth) acrylic acid alkyl esters such as methyl methacrylate, ethyl methacrylate, butyl methacrylate, methyl acrylate, ethyl acrylate, butyl acrylate; maleic anhydride, ( Examples thereof include unsaturated carboxylic acids such as (meth) acrylic acid. As the rubber-like elastic body, one having a glass transition temperature of 0 ° C. or lower, preferably −30 ° C. or lower is used. Specifically, polybutadiene rubber, styrene-
Butadiene rubber (SBR), acrylonitrile-butadiene rubber (NBR), butyl acrylate-butadiene rubber, styrene-butadiene-styrene rubber (SBS)
And the like; acrylic rubbers such as polybutyl acrylate; polyolefinic rubbers such as ethylene-propylene-non-conjugated diene rubber (EPDM). The above maleimide-based monomer, aromatic vinyl-based monomer,
The other vinyl-based monomers and rubber-like elastic materials are used alone or in combination of two or more.

The composition of the (A) maleimide resin used in the present invention has a maleimide monomer residue content of 5 to 60% by weight, preferably 5 to 55% by weight, more preferably 5 to 5% by weight.
It is 0% by weight. When the maleimide-based monomer residue is less than 5% by weight or more than 60% by weight, impact resistance, heat distortion resistance,
Molding processability and the like are reduced, which is not preferable. Aromatic vinyl monomer residue is 95-40% by weight, preferably 95-
It is 45% by weight, more preferably 95 to 50% by weight.
If the aromatic vinyl monomer residue is less than 40% by weight or more than 95% by weight, molding processability, impact resistance, heat distortion resistance, etc. are deteriorated, which is not preferable. The content of the other vinyl monomer residue is preferably 30% by weight or less, more preferably 25% by weight or less. If it exceeds 30% by weight, moldability,
It is not preferable because the thermal stability is lowered and the molded product is colored. The rubber-like elastic body is preferably 35% by weight or less, more preferably 25% by weight or less. 35% by weight
If it exceeds, rigidity, surface hardness, moldability, chemical resistance, etc. are deteriorated, which is not preferable.

The intrinsic viscosity (30 ° C.) of the methylethylketone-soluble component of the (A) maleimide resin used in the present invention is
N, N'-dimethylformamide solution) is preferably 0.25 to 1.5 dl / g, more preferably 0.5 to 1.5 dl / g.
It is in the range of 0.8 dl / g. If it is less than 0.25 dl / g or exceeds 1.5 dl / g, impact resistance, chemical resistance, rigidity, and moldability are deteriorated, which is not preferable.

The method for producing the (A) maleimide resin used in the present invention is not particularly limited, and emulsion polymerization, suspension polymerization, bulk polymerization, emulsion-bulk polymerization, emulsion-suspension polymerization, bulk-suspension polymerization. Examples include turbid polymerization. Further, if desired, products produced by different production methods can be arbitrarily mixed and used. Furthermore, JP-A-63-15
As shown in No. 9458, a copolymer is obtained by using maleic anhydride in place of the maleimide-based monomer during polymerization,
Then, it can also be produced by a method of imidization with methylamine, aniline or the like.

As a more specific method for producing the (A) maleimide-based resin, for example, a maleimide-based monomer, an aromatic vinyl-based monomer and, if necessary, another vinyl-based monomer (A-a) React the polymer with, if necessary, a rubber-like elastic material and two or more monomers selected from the group consisting of an aromatic vinyl-based monomer, a maleimide-based monomer, and optionally another vinyl-based monomer. The (Ab) graft copolymer thus prepared can be used.

The polycarbonate resin (B) used in the present invention is a thermoplastic aromatic polycarbonate,
Aromatic polycarbonates produced by the reaction of dihydric phenol compounds with phosgene or carbonic acid diesters are preferred. The molecular weight is not particularly limited, but a molecular weight of 40,000 or less is preferable from the viewpoint of fluidity, and a molecular weight of 15,000 or more is preferable from the viewpoint of impact resistance and chemical resistance.

Bisphenols are preferred as the dihydric phenol compound, and particularly 2,2-bis (4-hydroxyphenyl) propane, so-called bisphenol A, and bisphenol A partially substituted with other functional groups are used. preferable. The bisphenol A can be replaced with a fixed amount or the whole amount of the bisphenol A by another divalent phenol compound. As divalent phenol compounds other than bisphenol A, hydroquinone, 4,4-dihydroxydiphenyl, bis (4-hydroxyphenyl) cycloalkane,
Bis (4-hydroxyphenyl) sulfide, bis (4
Examples thereof include compounds such as -hydroxyphenyl) sulfone and bis (4-hydroxyphenyl) ketone. It may be a homopolymer composed of these dihydric phenols, a copolymer composed of two or more kinds, or a blend thereof.

Further, in order to improve the flame retardancy, it is possible to use a polymer in which a phosphorus compound is copolymerized or end-capped. Further, in order to enhance the weather resistance, a polymer obtained by copolymerizing a dihydric phenol having a benzotriazole group can also be used.

The (C) ethylene / carbon monoxide / (meth) acrylic acid alkyl ester copolymer used in the present invention is a copolymer of ethylene, carbon monoxide and a (meth) acrylic acid alkyl ester. The alkyl group of the (meth) acrylic acid alkyl ester is linear or branched, and its carbon number is preferably 1 to 18, and methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec -Butyl group, t-butyl group, isobutyl group,
Hexyl group, 2-ethylhexyl group, octyl group and the like are exemplified, and among them, those having 2 to 8 carbon atoms are more preferable. Those having more than 18 carbon atoms are not preferable in terms of economy.

The composition of the (C) ethylene / carbon monoxide / (meth) acrylic acid alkyl ester copolymer used in the present invention has an ethylene residue of preferably 30 to 90% by weight, more preferably 40 to 80% by weight. %, Carbon monoxide residue is preferably 1 to 40% by weight, more preferably 5 to 30
% By weight, the (meth) acrylic acid alkyl ester residue is preferably 5 to 60% by weight, more preferably 20 to 50% by weight, and it is also possible to copolymerize other compounds, if necessary. . If the composition is out of the above range, the impact resistance and the molding processability are largely deteriorated, and further peeling occurs in the molded product, which is not preferable.

The (C) ethylene / carbon monoxide / (meth) acrylic acid alkyl ester copolymer used in the present invention is described in, for example, JP-A Nos. 4-1255 and 4-1256.
And the method described in JP-A-4-1257 and the like. Further, the copolymer (C) may be a graft copolymer obtained by grafting a polyamide oligomer. The graft copolymer is disclosed in JP-A-2-7382.
No. 8 and those described in JP-A-2-245033 can be used. The (C) ethylene / carbon monoxide / (meth) acrylic acid alkyl ester copolymer used in the present invention has a melt index (1
90 ° C., 2.16 Kg), preferably 1-200 g / 1
It is 0 minutes, more preferably 5 to 150 g / 10 minutes.

In the thermoplastic resin composition of the present invention, the respective compounding ratios of (A) maleimide resin, (B) polycarbonate resin, (C) ethylene / carbon monoxide / (meth) acrylic acid alkyl ester copolymer. Is
For 100 parts by weight of a thermoplastic resin composed of (A) 90 to 10% by weight and (B) 10 to 90% by weight, (C) 0.
5 to 50 parts by weight. Preferably, (A) 80-20
1 to 40 parts by weight with respect to 100 parts by weight of the thermoplastic resin composed of 20% to 80% by weight of (B). With respect to 100 parts by weight of the mixture of (A) and (B),
When (C) is less than 0.5 part by weight, the effect of improving impact resistance and molding processability is small, and when (C) exceeds 50 parts by weight, molding process becomes difficult. Also, a mixture of (A) and (B) 100
If the content of (A) is less than 10% by weight, the heat distortion resistance and impact resistance are deteriorated, and if it exceeds 90% by weight, peeling occurs in the molded product.

The thermoplastic resin composition of the present invention comprises (A),
It can be obtained by mixing and melting (B) and (C) by an arbitrary method, but the operation is not particularly limited.
For example, mixing with a Henschel mixer, a single screw extruder, 2
It can be produced by melt-kneading using a shaft extruder, a kneader or the like.

During mixing, the components (A), (B), (C)
Besides, one kind or two or more kinds of arbitrary thermoplastic resins may be kneaded at the same time within a range not impairing the object of the present invention.

If necessary, generally well known antioxidants, heat stabilizers, lubricants, plasticizers, flame retardants, flame retardant auxiliaries,
Additives such as ultraviolet absorbers, pigments, antistatic agents, nucleating agents, dispersants, and compatibilizers can be used alone or in combination of two or more. Also, as other additional components, organic
Inorganic fillers / reinforcing agents such as glass fiber, mica, talc, wollastonite, potassium titanate, calcium carbonate, silica and the like can be used alone or in combination of two or more.

The method of molding the thermoplastic resin composition produced by the present invention is not particularly limited, and molding methods generally used for thermoplastic resins, that is, injection molding, blow molding, extrusion molding, and sheets are used. Forming, roll forming,
A molding method such as press molding or laminated molding can be applied.

[0023]

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

Examples 1 to 10, Comparative Examples 1 to 11 (A) Maleimide Resins The following (A-a1), (A-a2), (A-a3) and (A-b) are used, and 5 types are used. Maleimide resins A1 to A5
Was prepared and used. (A-a1) N-phenylmaleimide residue 47% by weight,
Styrene residue 50% by weight, maleic anhydride residue 3% by weight
Copolymer (intrinsic viscosity 0.62 dl / g) (A-a2) N-phenylmaleimide residue 16% by weight,
Copolymer consisting of 60% by weight of styrene residue, 1% by weight of α-methylstyrene residue, and 23% by weight of acrylonitrile residue (intrinsic viscosity 0.58 dl / g) (A-a3) 71% by weight of styrene residue, acrylonitrile Copolymer consisting of 29% by weight of residue (intrinsic viscosity 0.54
dl / g) (Ab) 60% by weight of polybutadiene rubber having an average particle diameter of 0.35 μm, 21% by weight of grafted branch styrene residue, 10% by weight of grafted branch acrylonitrile residue, 7% by weight of ungrafted polymer styrene residue, Graft copolymer consisting of 2% by weight of acrylonitrile residue (graft ratio 52
%, Intrinsic viscosity 0.65 dl / g)

A1: (A-a1) is used. A2: (A-a2) and (A-b) are mixed in a weight ratio of 3: 1. A3: (A-a1) and (A-). a3) and (A-b) are mixed in a weight ratio of 1: 3: 1. A4: (A-a1), (A-a3) and (A-b) are used in a weight ratio of 16 :. Use a mixture of 3: 1 A5: Use a mixture of (A-a3) and (Ab) in a weight ratio of 3: 1.

(B) Polycarbonate resin TAFRON FN-2500A (viscosity average molecular weight of about 2350)
0) (made by Idemitsu Petrochemical Co., Ltd.)

(C) Ethylene / carbon monoxide / (meth) acrylic acid alkyl ester copolymer Elvalloy HP441 (melt index: 8 g / 1
0 minutes) (Mitsui DuPont Polychemical Co., Ltd.)

(D) Low density polyethylene Moretec 0168N (made by Idemitsu Petrochemical Co., Ltd.) is used

The above (A), (B) and (C) or (D)
Are mixed in the proportions shown in Table 1, hindered phenolic antioxidants and phosphite stabilizers are further added, and the mixture is stirred with a super mixer, and then TEX44 of Japan Steel Works, Ltd.
With a twin-screw extruder, melt extrusion was performed at a barrel setting temperature of 260 ° C. to obtain a resin composition.

The obtained resin composition was dried at 110 ° C. for 5 hours using a hot air dryer, and then J150E- manufactured by Japan Steel Works Ltd.
Using a P injection molding machine, molding was carried out at a cylinder temperature of 280 ° C. and a mold temperature of 70 ° C., a test piece was obtained, and physical properties were measured by the following methods. The measurement results are shown in Table 1.

The impact resistance was evaluated by the IZOD test (kgcm / cm) according to ASTM D-256 at 1/8 "notch and 23 ° C. The heat distortion resistance was ASTM.
According to D-648, H of 18.6 kg / cm ² load
It was evaluated by DT (° C). As for the moldability, the fluidity was evaluated at a temperature of 250 ° C. by using a mosquito coiled spiral mold having a thickness of 3 mm (mm). For chemical resistance, a test piece with a thickness of 3 mm was fixed on an arc-shaped jig with a strain of 1%, and the fragrance of automobile fragrance New Honey Kiss Lime (SOFT99 Corporation) was applied to the entire surface of the test piece. The time until the cracks were generated on the surface was measured (minutes, but when the cracks did not occur within one week, it was indicated as ◯).

[0032]

[Table 1]

Comparative Example 1 is Example 1, Comparative Example 2 is Example 2, Comparative Example 3 is Examples 3-5, and Comparative Example 4 is Example 6.
7 to 7, Comparative Example 5 to Examples 8 to 9 and Comparative Example 6 to Example 10, respectively, in Comparative Example, (C) ethylene / carbon monoxide / (meth) acrylic acid alkyl ester copolymer was used. Since it is not compounded, it is inferior in impact resistance, chemical resistance, and moldability as compared with the corresponding examples. In Comparative Example 7, the amount of the ethylene / carbon monoxide / (meth) acrylic acid alkyl ester copolymer (C) is out of the range of the present invention, so that the molding process becomes difficult. Comparative Example 8 is inferior in impact resistance and heat distortion resistance as compared with Examples 2, 4 and 10 because it does not contain (B) a polycarbonate resin. In Comparative Example 9, since the (A) maleimide-based resin was not mixed, peeling of the surface of the obtained molded body was observed. In Comparative Example 10, (C) ethylene / carbon monoxide /
Since (D) low-density polyethylene was used instead of the (meth) acrylic acid alkyl ester copolymer, peeling of the surface of the obtained molded product was observed. In Comparative Example 11, as compared with Examples 4, 6, and 8, the amount of the maleimide-based monomer in the (A) maleimide-based resin is outside the range of the present invention.
Inferior in heat distortion resistance. From these results, it is understood that the thermoplastic resin composition of the present invention has a good balance of impact resistance, heat distortion resistance, chemical resistance, and moldability.

[0034]

The resin composition of the present invention has a good balance of impact resistance, heat distortion resistance, chemical resistance and molding processability, and is industrially extremely useful.

─────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP 61-250048 (JP, A) JP 6-116469 (JP, A) JP 4-1257 (JP, A) (58) Field (Int.Cl. ⁷ , DB name) C08L 35/00-35/08 C08L 25/00-25/18 C08L 51/04 C08L 69/00 C08L 73/00

Claims (3)

(57) [Claims] 1. The amount of (A) maleimide-based monomer residue is 5 to 6
90 to 10% by weight of a maleimide resin containing 0% by weight,
(B) 0.5 to 50 parts by weight of (C) ethylene / carbon monoxide / alkyl (meth) acrylate copolymer with respect to 100 parts by weight of a thermoplastic resin composed of 10 to 90% by weight of a polycarbonate resin. A thermoplastic resin composition characterized by being added. 2. The (A) maleimide resin comprises 5 to 60% by weight of maleimide monomer residues, 95 to 40% by weight of aromatic vinyl monomer residues, and other vinyl monomer residues. Groups 0-3
0% to 35% by weight of rubber-like elastic material, and the intrinsic viscosity of the methyl ethyl ketone soluble component is 0.25 to 1.5.
The thermoplastic resin composition according to claim 1, which has a dl / g range. 3. (C) Ethylene / carbon monoxide / (meth)
The acrylic acid alkyl ester copolymer has an ethylene residue of 30 to 90% by weight, a carbon monoxide residue of 1 to 40% by weight,
The thermoplastic resin composition according to claim 1 or 2, wherein the (meth) acrylic acid alkyl ester residue is 5 to 60% by weight.