JPS6172048A - Resin composition having excellent heat-resistance and heat-stability - Google Patents

Abstract

PURPOSE:To provide a composition composed of a specific maleimide copolymer and a specific unsaturated dicarboxylic acid anhydride copolymer, and having excellent heat-resistance, thermal stability, and affinity with glass fiber, etc. CONSTITUTION:The objective composition can be prepared by compounding (A) 10-98pts.wt. of a maleimide copolymer composed of 2-70(wt)% maleimide compound, 98-30% aromatic vinyl compound and/or unsaturated carboxylic acid alkyl ester compound and 0-50% vinyl cyanide compound with (B) 90-2pts.wt. of an unsaturated dicarboxylic acid anhydride copolymer composed of 0.5-40% unsaturated dicarboxylic acid anhydride, 99.5-60% aromatic vinyl compound and/or unsaturated carboxylic acid alkyl ester compound and/or unsaturated carboxylic acid alkyl ester compound and 0-50% vinyl cyanide compound. The intrinsic viscosity of each component is preferably 0.3-1.5 to obtain a composition having balanced mechanical property and moldability.

Description

DETAILED DESCRIPTION OF THE INVENTION CI) Object of the Invention The present invention relates to a resin composition having excellent heat resistance and thermal stability. More specifically, the present invention relates to a resin composition comprising a 7-reimide copolymer and an unsaturated dicarboxylic anhydride copolymer, which has excellent heat resistance and thermal stability, and also has excellent affinity with glass fibers and the like.

Copolymers made of maleic anhydride, an unsaturated dicarboxylic acid anhydride, and styrene have long been known as polymers with excellent heat resistance, and various polymerization methods and polymer blends made using such polymers have been proposed. . Furthermore, a glass fiber reinforced resin composition made by mixing glass fibers has also been proposed in Japanese Patent Publication No. 54-19906.

However, it has the problem that its anhydrous properties significantly reduce the styrene and oleic acid properties.

The present inventors conducted intensive research to improve the thermal stability of maleic anhydride copolymers, and as a result, mixed a specific maleimide copolymer with a specific unsaturated dicarboxylic anhydride copolymer. It has been discovered that if the composition is thermally stable, it has excellent heat resistance. Furthermore, when the composition of the present invention contains metal fibers, glass fibers, and other various inorganic fillers, it has excellent impact resistance and rigidity, and also has various metals,
Excellent adhesion to other inorganic materials and organic polymeric materials containing polar groups.

That is, the present invention provides a maleimide compound consisting of 2 to 70% by weight of a flamide compound, 98 to 30% by weight of an aromatic vinyl compound and/or an unsaturated carboxylic acid alkyl ester compound, and θ to 50% by weight of a vinyl cyanide compound. Copolymer (A) and unsaturated dicarboxylic anhydride 0°5-4
0% by weight, an unsaturated dicarboxylic acid anhydride copolymer (B) consisting of a hereditary vinyl compound and/or an unsaturated carboxylic acid alkyl ester compound in an amount of 995 to 60M, and a vinyl cyanide compound O to 50% by weight. The present invention provides a resin composition having excellent heat resistance and thermal stability.

[]] Structure of the Invention 0 Maleimide Copolymer The maleimide copolymer used in the present invention includes a maleimide compound of 2 to 70 times, an aromatic vinyl compound and/or an unsaturated carboxylic acid alkyl ester compound of 98 to 30 times. Weight % and vinyl cyanide compound O~5
It consists of 0% by weight.

If the amount of the maleimide compound exceeds 2N, the final composition will have poor heat resistance, and if it exceeds 70% by weight, the mechanical strength will be poor and the moldability will be poor, which is not preferable.

If the aromatic vinyl compound and/or unsaturated carboxylic acid alkyl ester compound exceeds 98% by weight, the final composition will have poor heat resistance, and if it is less than 30% by weight, it will have poor mechanical strength, which is not preferred.

Furthermore, if the vinyl cyanide compound exceeds 50% by weight, the thermal stability and mechanical strength of the final composition will deteriorate, which is not preferred.

In particular, it is preferred that the maleimide compound be present in an amount of 5 to 60% by weight, the aromatic vinyl compound and/or the unsaturated carboxylic acid alkyl ester compound be contained in an amount of 95 to 40% by weight, and the vinyl cyanide compound be contained in an amount of 0 to 40% by weight.

Maleimide compounds include maleimide, N-alkyl-substituted maleimide, N-aryl-substituted maleimide and their non-rogen compounds; aromatic vinyl compounds include:
Styrene, α-methylstyrene, P-methylstyrene,
P-t-methylstyrene, dimethylstyrene, etc. may be mentioned. , hydroxyethyl methacrylate, hydroxypropyl methacrylate, etc.0 As vinyl cyanide compounds, acryl nitrile,
Methacrylate trile and the like can be mentioned.

The maleimide copolymer can be obtained by the known milk polymerization method, bulk polymerization method, suspension polymerization method, solution polymerization method, or a combination thereof.

The maleimide copolymers include not only copolymers obtained using the above-mentioned maleimide compounds as starting materials, but also anhydride copolymers obtained using unsaturated dicarboxylic acid anhydrides such as maleic anhydride. Also included are maleimide-based copolymers obtained by maleimide-coating a polymer with ammonia and/or a primary amine.

0 Unsaturated dicarboxylic anhydride copolymer The unsaturated dicarboxylic anhydride copolymer used in the present invention contains 0.5 to 40% by weight of an unsaturated dicarboxylic anhydride, an aromatic vinyl compound, and/or an aromatic vinyl compound. Or, if the unsaturated dicarboxylic acid anhydride is less than 0.5% by weight, the mechanical strength of the final composition will deteriorate. If the content exceeds 40% by weight, the thermal stability will be poor, which is not preferable. If the cyanide vinyl compound exceeds 50% by weight, the thermal stability and mechanical strength will be poor, which is not preferable.

Preferably, the amount of unsaturated dicarboxylic acid anhydride is 1 to 30% by weight, and the amount of vinyl cyanide compound is 0 to 40'TL.

Examples of the unsaturated dicarboxylic anhydride include maleic anhydride, itaconic anhydride, citraconic anhydride, acunitic anhydride, and the like.

Aromatic vinyl compounds include styrene, α-methylstyrene, P-methylstyrene, pt-butylstyrene, dimethylstyrene, methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, hydroxyethyl Examples of vinyl cyanide compounds include acrylate, hydroxyethyl methacrylate, hydroxyethyl acrylate, and the like.

The unsaturated dicarboxylic anhydride copolymer can be obtained by known bulk polymerization methods, solution polymerization methods, bulk-suspension polymerization methods, and the like.

0 Composition The resin composition of the present invention comprises the above-mentioned maleimide copolymer (
It consists of At and an unsaturated dicarboxylic acid anhydride copolymer (B), and there is no particular restriction on the composition ratio (weight ratio), but the copolymer (A) 10 to 98 parts by weight, the copolymer (B) )90
It is preferably 2 parts by weight (per 100 parts by weight of the total amount of (A) and (B)).

If the copolymer (N) is less than 10 parts by weight, the composition tends to have poor thermal stability, and if it exceeds 98 parts by weight, the mechanical strength tends to be poor.

In particular, maleimide copolymer (A) 20 to 90% by weight,
Unsaturated carboxylic acid anhydride copolymer (B) 80-10
Preferably, it is % by weight.

There is no particular restriction on the intrinsic viscosity of the above-mentioned copolymers (A) and (B), which are essential components in the resin composition of the present invention. Polymers (A) and (B) each have an intrinsic viscosity of 0
．． It is preferable that it is 3-1.5.

There are no restrictions on the respective forms when mixing the maleimide copolymer (B) and the unsaturated dicarboxylic anhydride copolymer (B), and the state of the reaction solution after the polymerization is completed. Alternatively, it may be in the form of a powder or pellet.

Further, there is no restriction on the mixing method, and a known method using a Banbury mixer 1 extruder or the like may be used.

In addition, when mixing, well-known additives such as antioxidants, antistatic agents, ultraviolet absorbers, lubricants, dyes and pigments, metal fibers, glass fibers, other inorganic fillers, and other thermoplastic resins are appropriately blended. can do.

When metal fibers or glass fibers are blended, a composition with excellent impact resistance, stiffness, heat resistance, and thermal stability is obtained; when other thermoplastic resins are blended, a composition with excellent impact resistance, flexibility, heat resistance, and thermal stability is obtained. A composition with excellent properties can be obtained.

The metal fibers and glass fibers may have surfaces treated with epoxy resin, aminosilane, etc.

Other thermoplastic resins that can be blended into the composition of the present invention include ABS resin, ABS resin, ACS resin, AAS resin,
Examples include MBS resin, polycarbonate resin, saturated polyester, polyamide, polyacetal, polysulfone, polyphenylene oxide, and the like.

Examples will be described below, but the present invention is not limited to these in any way.

Note that ``parts'' and ``parts'' refer to parts by weight.

Example-1 and Comparative Example-1 Maleimide copolymer shown in Reference Example-1 and Reference Example-2
Single products of unsaturated dicarboxylic acid anhydride copolymers and mixtures thereof shown in
A test piece was prepared by molding at 70°C, and its physical properties were measured.

The measurement results are shown in Table 3.

Reference Example-1 Various maleimide copolymers (A)-1 to CA)-7 shown in Table 1 were produced by known emulsion polymerization or solution polymerization methods.
was synthesized.

Table 1 Note 1) Dimethylformamide solution, measured at 30°C.

2) E: Emulsion polymerization method S: Solution type method Reference example-2 Various maleic anhydride copolymers (B)-1 to ( B
)-6 was synthesized.

Table 2 Note 1) Same as Table 1.

2) B: Bulk polymerization method B-8: Bulk-turbidity polymerization method 3rd
Table Example-2 and Comparative Example-2 Reference Example-Maleimide copolymer shown in IK and Reference Example-2
A total of 80 parts of the maleic anhydride copolymer shown above was mixed with 20 parts of aminosilane-treated glass fibers (average line 10μ, length 3mm),
The mixture was kneaded in a 40° diameter extruder with a vent, and then pelletized.

This pellet was molded at 220 to 270°C using a small-sized injection molding machine to prepare a test piece, and its physical properties were measured.

The results are shown in Table 4.

Table 4 [Part 1 Effects of the Invention The resin composition of the present invention has remarkable heat resistance and thermal stability (foaming and silver streak resistance) compared to the Flaimide copolymer alone and the unsaturated dicarboxylic anhydride copolymer alone. ), and by incorporating glass fiber etc., the impact resistance and rigidity are also significantly improved.

Claims (1)

[Claims] 1) Maleimide copolymer (A) consisting of 2 to 70% by weight of a maleimide compound, 98 to 30% by weight of an aromatic vinyl compound and/or an unsaturated carboxylic acid alkyl ester compound, and 0 to 50% by weight of a vinyl cyanide compound. and 0.5 to 40% by weight of an unsaturated dicarboxylic anhydride, 99.5 to 60% by weight of an aromatic vinyl compound and/or an unsaturated carboxylic acid alkyl ester compound, and 0 to 50% by weight of a vinyl cyanide compound. A resin composition having excellent heat resistance and thermal stability, comprising a saturated dicarboxylic anhydride copolymer (B).