JPS60177067A - Heat-resistant resin composition of both outstanding high-temperature rigidity and falling ball impact strength - Google Patents

Abstract

PURPOSE:To provide the titled composition comprising a graft polymer derived from rubbery polymer and e.g. aromatic vinyl compound and a copolymer derived from maleimide, aromatic vinyl compound, etc. CONSTITUTION:The objective composition comprising (A) 10-90wt% of a graft polymer with a graft rate 20-150% and weight-average particle size 0.05-3mu, prepared by grafting (1) a compound selected from aromatic vinyl compounds, unsaturated nitrile compounds and unsaturated carboxylic alkyl ester compounds to (2) a rubbery polymer with a gel content 20-95wt% and (B) 90-10wt% of a copolymer with an intrinsic viscosity 0.4-1.3 derived from (1) 1-75wt% of maleimide and/or its derivative. (2) 99-25wt% of aromatic vinyl compound, and (3) 0-50wt% of unsaturated nitrile and/or unsaturated carboxylic alkyl ester compound(s).

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a heat-resistant resin composition having excellent high-temperature rigidity and falling ball impact strength.

Regarding rubber-reinforced styrene resins such as ABS resins, research on improving heat resistance has been conducted for a long time, and numerous documents can be found.

For example, there is a technology to introduce maleimide or its copolymer into ABS resin (USP 3642949゜U
S P 3652726 etc.) 0 Maleimide modified ABS resin is unmodified ABS resin and α
-It has a higher heat distortion temperature than methylstyrene-modified ABS resin, but when it is actually used as a molded product, this heat distortion temperature does not necessarily match the heat resistance of the molded product. . Also, like the α-methylstyrene-modified AB8 resin, it does not have the excellent impact resistance characteristic of ABS resins, and even if the rubber content is simply increased, the practical falling ball impact strength is still low.

As a result of intensive study in view of such problems, the present inventors found that
The present invention was achieved based on the discovery that a heat-resistant resin composition with excellent practical performance such as high-temperature rigidity and falling ball impact strength can be obtained by combining a specific graft polymer and a copolymer.

That is, the present invention comprises a rubbery polymer having a gel content of 20 to 95, and two or more compounds selected from the group consisting of an aromatic vinyl compound, an unsaturated nitrile compound, and an unsaturated carboxylic acid alkyl ester compound. Polymerized graft ratio of 20 to 150% and weight average particle diameter of 0.05 to 3
μ graft polymer (A) 10 to 90% by weight, maleimide and/or its derivative 1 to 75% by weight, aromatic vinyl compound 99 to 25% by weight, and unsaturated nitrile compound and/or unsaturated carboxylic acid alkyl ester compound Intrinsic viscosity 0.4-1.0-50% by weight.
The present invention provides a heat-resistant resin composition having excellent high-temperature rigidity and falling ball impact strength, characterized in that the copolymer (B) of No. 3 has a weight ratio of 90 to 1O.

The present invention will be explained in more detail below.

The rubbery polymer constituting the graft polymer used in the present invention is a rubbery polymer with a gel content of 20 to 95 inches, and is polybutadiene.

Conjugated diene rubber such as styrene-butadiene rubber, acrylonitrile-butadiene rubber, ethylene-propylene rubber, ethylene-propylene rubber such as 1V conjugated diene rubber, acrylic rubber such as butyl acrylate rubber I, chlorinated polyethylene, ethylene-acetic acid Vinyl rubber etc. are exemplified. The gel content of the rubbery polymer can be adjusted as appropriate by changing polymerization conditions such as the initiator and polymerization temperature, and by using a crosslinking agent.

Gel content is generally measured under dimethylformamide conditions at 30°C. The rubbery polymer used in the present invention preferably has a gel content of 50 to 95%.

A graft polymer can be obtained by polymerizing a rubbery polymer and a compound, but the grafting ratio of the graft polymer (
A specific graft polymer in which the weight of the compound grafted onto the rubbery polymer/the weight of the rubbery polymer is 20 to 150%, and the weight average particle diameter of the kraft is 0.05 to 3μ. . For graft polymers outside of this range, high temperature stiffness is an object of the present invention.

A composition with excellent falling ball impact strength and heat resistance cannot be obtained.

Grafting rate depends on polymerization temperature and compound addition rate.

It can be adjusted as appropriate by increasing or decreasing the amount of polymerization aid.

Further, the weight average particle diameter of the graft polymer can be calculated from an electron micrograph or the like. The particle size of the graft polymer generally depends on the particle size in the polymerization system of the rubbery polymer used, and is usually the same as or slightly larger than the particle size in the polymerization system. In particular, a graft polymer having a weight average particle size of 0.1 to 2 μ and a graft ratio of 20 to 10% is preferred.

Examples of the aromatic vinyl compound constituting the graft polymer and copolymer include styrene, α-methylstyrene, nuclear-substituted methylstyrene, and chlorostyrene.

Examples of unsaturated nitrile compounds include acrylonitrile, methacrylonitrile, fumaronitrile, and maleonitrile. In addition, examples of unsaturated carboxylic acid alkyl ester compounds include methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate,
There is no particular restriction on the ratio of the compound to the rubbery polymer constituting the 0-kraft polymer, exemplified by hydroxyethyl methacrylate, but the rubbery polymer may be 5 to 80% by weight.
, preferably 95 to 20% by weight of the compound. In addition, there is no particular restriction on the ratio of each compound in the compounds used for polymerization, but aromatic vinyl compounds 50 to 80% by weight, unsaturated nitrile compounds and/or unsaturated carboxylic acid alkyl ester compounds 50 to 20% by weight. is preferable, particularly 50 to 80% by weight of methyl ref, 50 to 20% by weight of acrylonitrile and/or methyl methacrylate.
Preferred examples of imides and/or derivatives thereof include maleimide, methylmaleimide, ethylmaleimide, ethylmaleimide, diphenylmaleimide, chlorphenylmaleimide, etc. One or more types of these may be used.

Particularly preferred is a mixture of N-phenylmaleimide and other maleimides in which N-phenylmaleimide accounts for 100 to 50% by weight.

The copolymer is a copolymer consisting of 1 to 75% by weight of the above-mentioned maleimide and/or its derivative, 99 to 25% by weight of an aromatic vinyl compound, and 0 to 50% by weight of an unsaturated nitrile compound and/or an unsaturated carboxylic acid alkyl ester compound. It is a polymer, and the intrinsic viscosity of the copolymer is 0.4 to 1.
．． It is 3. Note that the intrinsic viscosity is the viscosity measured in dimethylformamide at 30°C.

The copolymer used in the present invention has the above-mentioned specific composition and has a specific intrinsic viscosity. Outside this range, a composition excellent in high-temperature rigidity, falling ball impact strength, and heat resistance, which are the objects of the present invention, cannot be obtained.

There are no restrictions on the form in which the graft polymer and copolymer are mixed, and they may be in a latex state, or may be in a powdered or granular state such as powder, pellets, or beads. Also, there is no limit to the mixing method; 2 loaves of bread, 8 pieces of bread, 78□ yew.

One example is crab.

In addition, when mixing, use known dyes, pigments, and antioxidants.

It is also possible to add plasticizers, antistatic agents, ultraviolet absorbers, lubricants, flame retardants, etc.

Furthermore, the composition of the present invention is applied to polycarbonate.

It is also possible to mix with other thermoplastics such as polysulfones, polyesters, polyamides, polyphenylene oxides.

The present invention will be specifically explained below using Examples, but the present invention is not limited by these in any way.

Example 1 Graft polymers (A-1 to A-5) When polymerizing polybutadiene, styrene, and acrylonitrile based on a known emulsion graft polymerization method, polybutadiene latexes having different gel contents and average particle diameters were used, and Graft polymers (A-1 to A-4) having different graft ratios were obtained by adjusting the amounts of the initiator and chain transfer agent. After polymerization, it was subjected to salting-drying treatment and recovered in powder form.

In addition, a graft polymer (A-5) was obtained based on a known bulk-suspension polymerization method. After polymerization, the polymer was filtered and dried and recovered in the form of beads.

Table 1 shows the charging composition, the grafting ratio and weight average particle diameter of the obtained kraft polymer.

Table 1 Copolymers (B-1 to 9) N-phenylmaleimide, ortho-chlorophenylmaleimide, styrene, acrylonitrile, and methyl methacrylate were polymerized by a known emulsion polymerization method. In addition,
The intrinsic viscosity was adjusted by increasing or decreasing the amount of chain transfer agent. After polymerization, the copolymer was salted and dried and recovered in powder form. Table 2 shows the composition and intrinsic viscosity of the copolymer.

The various graft polymers and copolymers obtained by the above methods were kneaded in a Banbury mixer and then granulated through an extruder. Table 3 shows the composition and physical properties of the resulting compositions.

*1 One end of a test piece (ASTM-1 type dumbbell) with an open deformation thickness of μ inches is fixed horizontally with a clamp, and the other end is the free end. The test piece with one end fixed is left in an oven at 110°C, and after 2 hours, the amount of deflection (in ) of the free end is measured.

*2 3mm thick flat plate with or without flow mark (vertical 100 runs, width 70
wn) was injection molded, and the state of occurrence of flow marks on the flat plate surface was observed with the naked eye, and it was determined to be Q-xx according to the degree of occurrence of flow marks.

○: No Δ: Slight flow mark ×: Flow mark present A sample of 3 g x 70 mm x 4 = 4 mm was molded and compared with an unretained product, and the degree of thermal coloring (discoloration) was visually determined.

O: No discoloration △: Slight discoloration is observed ×: Significant discoloration patent applicant Sumitomo Naugatuck Co., Ltd.

Claims (1)

[Claims] 1. Made by polymerizing a rubbery polymer with a gel content of 20 to 95% and two or more compounds selected from the group consisting of aromatic vinyl compounds, unsaturated nitrile compounds, and unsaturated carboxylic acid alkyl ester compounds. Graft rate 20~
10 to 90% by weight of graft polymer (4) with a weight average particle size of 150 mm and a weight average particle size of 0.05 to 3μ, 1 to 75% by weight of maleimide and/or its rust conductor, 99 to 25% by weight of an aromatic vinyl compound, and Saturated nitrile compounds and/or unsaturated carboxylic acid alkyl ester compounds 0
-50% by weight of a copolymer (B) having an intrinsic viscosity of 0.4 to 1.3; and 90 to 10% by weight of a heat-resistant resin composition having high rigidity and excellent falling ball impact strength.