JPS6028863B2 - Resin composition with excellent heat aging resistance - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a resin composition that has excellent impact resistance and heat resistance, as well as excellent heat aging resistance.

Polysulfone resins are used in various fields as engineering plastics that have better heat resistance than before. Among heat-resistant polymers, polysulfone resin is particularly characterized by excellent heat aging resistance. Therefore, compared to other heat-resistant polymers, it has the advantage of being able to be used continuously for long periods of time at temperatures close to the heat distortion temperature (high continuous use temperature). However, polysulfone resin has low mechanical properties, especially impact strength, and is expensive, so its use is subject to various restrictions.

Polysulfone resins are mixed with ABS resins to improve their impact strength and reduce costs.

(Special Publication No. 46-37890 Special Publication No. 49-27668) A
Mixing with Shigeru Resin improves impact strength and reduces costs, but on the other hand, the continuous use temperature drops to near the continuous use temperature of A Shigeru Resin, and the characteristics of polysulfone resin are completely lost. . The present inventor has arrived at the present invention as a result of intensive research to improve the drawbacks of the prior art.

That is, the present invention provides 90 to 1% by weight of polysulfone resin wind.
and a rubber copolymer mainly composed of ethylene and propylene, and one or more monomers selected from at least two groups of aromatic vinyl monomers, vinyl cyanide monomers, and other polymerizable monomers. Graft polymer (b-1) obtained by graft polymerization of The present invention relates to a resin composition consisting of a copolymer (b-2) consisting of the monomers (B'10 to 9% by weight) and having excellent heat aging resistance.

Furthermore, the resin composition of the present invention has excellent impact resistance and heat resistance.

Furthermore, the price reduction effect is also recognized. Next, the content of the present invention will be explained in more detail.

Polysulfone resins are defined as linear polyarylene compounds in which arylene units are interposed with ether and sulfone linkages.

For example, those prepared from 2,2-bis-(4-hydroxyphenyl)propane and 4,4'-dichlorodiphenyl sulfone, and the bisphenol of 4,4'-dichlorodiphenyl sulfone and penzophenone, or the bisphenol of acetophenone. It is produced from phenol or 4,4'-dihydroxyphenyl sulfone. The rubber copolymer mainly composed of ethylene and propylene constituting the graft polymer includes not only ethylene-propylene rubber consisting only of ethylene and propylene, but also ethylene-propylene rubber as a third component such as dicyclobentadiene, ethylidene norbornene, etc. Also included are ethylene-propylene terpolymers containing 1,4-hexadiene, 1,5-hexadiene, 1,4-cycloheptadiene, 1,5-cyclooctadiene, and mixtures thereof.

The molar ratio of ethylene and propylene in the rubber copolymer is 5:
The ratio is preferably in the range of 1 to 1:3.

Further, in the case of an ethylene-propylene terpolymer, the proportion of unsaturated groups preferably has an iodine value in the range of 4 to 50.

Examples of the aromatic vinyl monomer constituting the graft polymer and copolymer include styrene, Q-methylstyrene, Q-chlorostyrene, and dimethylstyrene, with styrene being preferred.

Examples of the vinyl cyanide monomer include acrylonitrile and methacrylonitrile, with acrylonitrile being preferred.

Other polymerizable monomers include methacrylic acid ester, acrylic acid ester, carboxylic acid hydroxyalkyl ester, vinyl chloride, vinyl acetate, etc., but methacrylic acid Particularly preferred are esters, acrylic acid esters, and hydroxyalkyl carboxylic acid esters.

One or more monomers selected from at least two groups among these aromatic vinyl monomers, vinyl cyanide monomers, and other polymer monomers are used to form graft polymers and copolymers. Used as a monomer.

The monomers constituting the graft polymer and the monomers constituting the copolymer may have the same composition or different compositions.

The weight ratio of the monomer and the rubber copolymer constituting the graft weight body is not particularly limited, but is preferably 95-4% by weight of the monomer and 5-6% by weight of the rubber copolymer.
It is.

Graft polymers and copolymers are produced by known methods such as bulk polymerization, bulk-suspension polymerization, suspension polymerization, solution polymerization, emulsion polymerization, and emulsion-suspension polymerization.

In the present invention, a resin composition comprising a graft polymer and a copolymer is used.

Particularly preferred are 10 to 9% by weight of the graft polymer and 90 to 1% by weight of the copolymer. If the resin composition {B) is the graft polymer (b-1) alone, the miscibility with the polysulfone resin is poor, the impact strength and tensile strength vary widely, and furthermore, there is delamination on the surface of the molded product, which is not preferable.

Impact strength and tensile strength after heat aging also vary greatly, and elongation is unmeasurable (1%
(below). Therefore, judging from the viewpoint of heat aging resistance, it is difficult to say that the composition is excellent. Moreover, when the copolymer (b-2) alone is used, the final composition (polysulfone resin-
Copolymer) has poor impact strength and appearance (layer delamination),
Furthermore, heat resistance also decreases.

The impact strength and tensile strength after heat aging are also significantly inferior, and the heat aging resistance is not improved. In this way, the grafted polymer (b
-1) or copolymer (b-2) alone cannot provide a resin composition with excellent heat aging resistance, which is the objective of the present invention.

In industrial parts that require long-term high-temperature properties, such as maintaining impact strength under high temperatures and minimizing creep deformation, large variations in physical properties such as impact strength can be a fatal flaw in the material.

Therefore, both graft polymers and copolymers are required. In addition, the intrinsic viscosity of the copolymer (b-2) (30
00, dimethylformamide) is preferably 0.5 to 1.3.

A copolymer with an intrinsic viscosity of less than 0.5 has a large difference in melt viscosity from the polysulfone resin, and tends to cause delamination and a decrease in impact strength. Furthermore, a copolymer with an intrinsic viscosity exceeding 1.3 has poor processability, poor appearance of the molded product, and tends to leave residual strain, making it undesirable for long-term deterioration. Furthermore, the resin composition of the present invention contains 90 to 10% by weight of polysulfone resin and the resin composition {B) 1
It consists of 0 to 9% by weight.

Is polysulfone resin particularly bad? 0 to 15% by weight and resin composition 'B} 30 to 85% by weight.
When the polysulfone resin exceeds 90% by weight, heat aging resistance is good, but no improvement in impact resistance is observed.

Moreover, no effect of price reduction can be expected. On the other hand, if the polysulfone resin content is less than 1% by weight, the heat resistance will be significantly reduced.

Moreover, it is meaningless from the point of view of improving the continuous use temperature. Polysulfone resin and resin composition {B'
The mixing can be carried out using a known method such as a Banbury mixer or an extruder.

It is also possible to add stabilizers, plasticizers, antistatic agents, pastes, beam pigments, fillers, ultraviolet absorbers, etc. during mixing. Next, the present invention will be explained in detail with reference to examples.

Example Bakelite polysulfone resin "P-170" manufactured by Union Carbide, a graft polymer and a copolymer were mixed in a Banbury mixer based on the composition ratio shown in Table 1, and then granulated in a vented extruder.

The evaluation results of the obtained resin composition are shown in Table-2. o Resin composition number 1 ■-1) Graft polymer (solution polymerization method): 60% by weight ethylene-propylene-ethylidene norbornene rubber copolymer (iodine value 8.5, Mooney viscosity 61, propylene content 43) %) 18% by weight, a graft polymer consisting of 55% by weight of styrene and 20% by weight of acrylonitrile■
-2) Copolymer (suspension polymerization method): 40% by weight styrene 7
Copolymer consisting of 30% by weight of acrylonitrile and 30% by weight Intrinsic viscosity (3000, DMF): 0.6 o Resin composition (B}-2 ■-1) Graft polymer (bulk polymerization method): 8% by weight Ethylene leaf.

Ropylene-dicyclobentadiene rubber copolymer (iodine value 10, Mooney viscosity 65, propylene content 40%) 2
-2) Copolymer (emulsion polymerization method): 2% by weight, 3% by weight of styrene, Q-Copolymer consisting of 40% by weight of methylstyrene and 3% by weight of acrylonitrile.

Intrinsic viscosity (30%, DMF): 0.8 o Resin composition leg-3 ■-1) Graft polymer (solution polymerization method): 6% by weight Graft used in resin composition {B}-1 Same as polymer ■-2) Copolymer (suspension polymerization method): Copolymer consisting of 4% by weight styrene 7% by weight and 3% by weight acrylonitrile Intrinsic viscosity (300○, DMF): 1.2 o Resin composition side-4 ■-1) Graft polymer (solution polymerization method); 6% by weight resin composition Same as the graft polymer used in leg 1-2) Copolymer (suspension polymerization method) legal): 4% by weight
*Intrinsic viscosity of a copolymer consisting of 7% by weight of styrene and 3% by weight of acrylonitrile (30 qo, DMF): 0.3 Table 11 Table 2 *1 Impact strength. Elongation and tensile strength vary.

*2 Growth rate is 1% or less as measured by measuring equipment. *1 Impact strength, elongation, and tensile strength vary because a homogeneous mixture cannot be obtained.

*2 Growth rate is 1% or less as measured by measuring equipment.

[Brief explanation of the drawing]

FIG. 1 shows the relationship between deterioration time and impact strength at 130 oo for sample numbers 2, 10 and 11. Figure 1

Claims (1)

[Scope of Claims] 1. 90 to 10% by weight of polysulfone resin (A), a rubber copolymer mainly composed of ethylene and propylene, and aromatic vinyl monomers, vinyl cyanide monomers, and other polymerizable monomers. A graft polymer obtained by graft polymerizing one or more monomers selected from at least two groups of monomers (
b-1) and one or more monomers selected from at least two groups of aromatic vinyl monomers, vinyl cyanide monomers, and other polymerizable monomers (b-1)
2) A resin composition having excellent heat aging resistance, comprising 10 to 90% by weight of the resin composition (B). 2. The resin composition according to claim 1, wherein the polysulfone resin (A) is 70 to 15% by weight and the resin composition (B) is 30 to 85% by weight. 3 Resin composition (B) is graft polymer (b-1) 10
Claim 1 or 2, which is a composition comprising ~90% by weight and 90-10% by weight of copolymer (b-2)
The resin composition described in . 4. The resin composition according to claim 1, 2, or 3, wherein the copolymer (b-2) has an intrinsic viscosity (30°C, dimethylformamide) of 0.5 to 1.3.