JPS5883056A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To provide the titled compsn. having excellent melt flow characteristics and resistance to heat, impact and weather, by mixing polyglutarimide with a graft copolymer consisting of an ethylene/propylene/non-conjugated diene copolymer rubber and a vinyl monomer. CONSTITUTION:The titled compsn. is obtd by mixing 10-90ptw.wt. polglutarimide (A) with 10-90pts.wt. graft copolymer (B) obtd. by polymerizing 90- 30pts.wt. at least one vinyl monomer selected from an arom. vinyl monomer a (meth)acrylate ester and a vinyl cyanide in the presence of 10-70pts.wt. ethylene/propylene/non-conjugated diene rubber polymer, in such a proportion that the sum of conponents A and B is 100pts.wt.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides heat resistance, impact resistance, solution flowability and weather resistance.
This invention relates to an excellent thermoplastic resin composition.

Polyglutarimide is a resin with a high heat deformation temperature, but on the other hand, it has poor mechanical properties such as porosity and temperature during bath molding.
Due to its poor fluidity in molds, its use as a thermoplastic molding material has been limited.

A method for modifying polyglutarimide resin intended for thermoplastic molding materials is disclosed in Karikai No. 52-65989 (Rohm, & Haas) (as described here, acrylonitrile/L). It is difficult to obtain the impact strength of alkyl acrylate rubbers such as methacrylate lL'a methyl/getadiene/styrene (MBSJ) copolymers or alkyl acrylate rubbers such as polybutyl acrylate. Impact modifiers based on diene rubbers such as copolymers and MBS copolymers contain double bonds in the rubber, so they are susceptible to deterioration from elements such as hydrogen, ozone, and ultraviolet rays. Even if the wfI ball strength of the polyglutarimide resin is increased by mixing these impact-modified nodes, it is not possible to obtain an impact-resistant resin with good weather resistance.

On the other hand, acrylic rubber such as polybutyl acrylate rubber does not contain unsaturated bonds, so by mixing it as an impact modifier, it can be expected to obtain a polyglutarimide resin composition with excellent weather resistance. The resin composition has insufficient impact strength and has low practical value as a heat-resistant and impact-resistant resin.

In this way, it is not possible to obtain a resin with sufficiently high impact strength by mixing only the above VI impact modifier with polyglutarimide, so as a method to further improve the impact strength, (1) polyglutarimide 1 A method of mixing both a multistage polymer based on a getadiene rubber or an alkyl acrylate rubber and a polycarbonate (as disclosed in JP-A-55-80459) and (2) a method of mixing a multistage polymer based on a getadiene rubber and a polycarbonate. A method (Japanese Unexamined Patent Publication No. 55-152740) has been proposed in which two types of impact modifiers, which are multistage polymers based on rukyl acrylate rubber, are mixed. Although the strength increases, since polycarbonate is an essential component, the fluidity deteriorates, making it unattractive as a thermoplastic molding resin.Furthermore, method (2) above does not sufficiently increase impact strength, and uses butadiene-based rubber. Since it contains an impact modifier used as a paste, its weather resistance is also poor, making it impossible to obtain a desirable resin composition.

Therefore, the present inventors aimed to obtain a polyglutarimide resin composition that maintains the high heat distortion temperature of polyglutarimide, has excellent impact resistance and fluidity during melt molding, and has good weather resistance. As a result of intensive studies, we found that by mixing a graft copolymer based on ethylene-propylene-nonconjugated diene copolymer rubber with polyglutarimide, we could improve heat resistance, fore-impact resistance, melt flowability, and weather resistance. It has been discovered that a thermoplastic resin composition with excellent properties can be obtained, and the present invention has been achieved.

That is, the present invention has (magnetic polyglutarimide and o: 1
B + aromatic bi=/kMj41 in the presence of 10 to 70 M parts of ethylene-propylene-nonconjugated diene copolymer rubber, (meth)acrylic sapon ester yarn monomer and V annated vinyl 7y monofilament. (B) a graft copolymer obtained by polymerizing 90 to 50 coulometric parts of at least one vinyl yarn monomer selected from the group consisting of
is 20 to 10, and (A) + (E) is 10
The object of the present invention is to provide a thermoplastic resin composition which is blended in a proportion of 0 parts by weight.

(A) Polyg p-p imide used in the present invention is the following formula (
It is a polymer or copolymer containing a cyclic imide unit represented by 1).

3 RI R In the formula, R1, R, and R3 each represent hydrogen or a substituted or unsubstituted alkyl group or aryl group having 1 to 20 prime numbers.

Any chemical w containing the above cyclic imide unit
Although the present invention can be applied even to a polyglutaramide having a four-structure structure, usually R in the above-mentioned cyclic imide unit is
Those in which 1 and R2 are hydrogen or methyl and R3 is hydrogen, methyl, ethyl, propyl, butyl or phenyl are generally used.

The method for producing polyglutarimide is not particularly limited, but for example, polymethyl methacrylate described in Karikai Publication No. 52-65989 is reacted with ammonia or a primary amine such as methylamine or ethylamine in an extruder. Methods that form glutarimide rings are useful.

In the present invention 1, the (B) graft copolymer to be mixed with (A) polyglutarimide refers to styrene in the presence of ethylene-glopyrene-nonconjugated diene co-polymer rubber (hereinafter abbreviated as iGPDM). , aromatic vinyl compounds such as a-methylstyrene, etc. It is obtained by polymerizing one type of EPDM.Ethylene/propylene (mole ratio) is 20/80 to 90.
/10. It is desirable that the composition has a non-conjugated diene content of 1 to 20 mol % and a Mooney viscosity of 20 to 100.

As the non-conjugated diene, cyclic dienes such as norbornenes and fuclopentadienes, and chain dienes such as 1,4-hexadiene are used. Among these non-conjugated dienes, 5-ethylidene-2-norbornene, synclopentadiene and 1,4-hexadiene are commonly used.

In the Bl graft copolymer used in the present invention, E
The composition of the monomer mixture (graft component) to be polymerized in the presence of PDM is i.
, (meta)acrytvm: r-stellar single body θ ~ 10
0 foot weight% and vinyl cyanide monomer 0-40 heavy weight%
It is preferable that it is in the range of . If the composition of the graft component is within the above range, +A) polyglutamate F and +B) the graft copolymer exhibit good compatibility, resulting in good impact strength, heat resistance, fluidity and weather resistance. A resin composition can be obtained.

Also, in the presence of 10 to 70 parts by weight, preferably 15 to 60 parts by weight of the Bl graft copolymer EPDM, 30 to 90 parts by weight, preferably 40 to 90 parts by weight of a monomer or monomer mixture having the above composition. It is necessary that the composition consists of 85 parts by weight of the polymer.

If EPDM is less than 10 M parts, the impact strength of the resin composition is insufficient, and if it exceeds 70 parts by weight,
This is not preferred because the compatibility between the graft copolymer and polyglutarimide deteriorates, making it impossible to obtain a resin composition with excellent impact resistance.

Although various methods have been proposed for producing graft copolymers based on EPDM, there are no particular restrictions on the method for producing and recycling the fBl graft copolymer used in the present invention. The two-step polymerization method in which the first step is fEl liquid pre-glat polymerization described in Publication No. 24596, the #I liquid storm method using a non-rat-combining bath strategy described in Japanese Patent Publication No. 18118-1983, etc. Tokuko Showa 49-1454
9.9 Emulsification Summer Law and Special Publication 1977-
It can be produced by the suspension polymerization method described in Publication No. 528559 and the like.

The blending ratio of the resin composition in this study is (A) 10 to 90 coulometric parts of polyglypimide, preferably 40 to 80 coulometric parts.
parts by weight and (B) 90 to 10 parts by weight, particularly preferably 60 to 20 parts by weight (with the exception of Al +
(Bl is 100 parts by weight). Only when mixed at a blending ratio within this range, a resin composition excellent in all of heat resistance, impact resistance, fluidity, and weather resistance can be obtained.

Outside this composition range, the heat resistance of the resulting resin composition will be
aft wl One or more of sphericity and fluidity (or axial properties are poor, and a desirable resin composition cannot be obtained).

The b11 fat composition of the present invention is obtained by further mixing (A) polyglutarimide and (Bll graft electrolyte), as well as (co)plates and resins of each building according to the purpose.
It is also possible to further improve the physical property balance of heat resistance, impact resistance, and melt flowability, or to impart other desirable properties. For example, impact strength and fluidity can be improved by mixing polystyrene, styrene/acrylonitrile copolymer (8AN4at resin), styrene/methacrylic-methyl copolymer, styrene/methacrylate/I//acrylonitrile copolymer, etc. can be improved. α-methylstyrene/acrylonitrile co-m combination,
α-methyl resin/styrene/acrylonitrile copolymer α-methyl resin/methacrylic acid
α-methylstyrene copolymers such as JV/acrylonitrile copolymers, styrene/maleic anhydride copolymers,
Mixing maleic anhydride based copolymer such as styrene/maleic anhydride/acrylonitrile copolymer, styrene/maleimide copolymer, maleimide copolymer such as methacrylate/l'l&methy)V/maleimide copolymer, etc. It is possible to improve impact strength and melt fluidity while maintaining high thermal stability. Also, styrene/maleic anhydride/getadiene copolymer, styrene/maleic anhydride/acrylonitrile/L//getadiene copolymer, acrylonitri/L//maleic anhydride/styrene copolymer (ABS resin), methacrylate !l/l' acid methi)
By mixing rubber modified/kuma copolymers such as V/getadiene/styrenic copolymer (MBS resin) and rubber reinforced polystyrene (H-PST resin), impact strength can be significantly increased while imparting the desired properties. In addition, desirable properties can be imparted by mixing various resins to suit various purposes.

The thermoplastic resin composition 1 of the present invention may be improved in thermal stability by adding an antioxidant such as a normal hindered phenol antioxidant, a phosphorus antioxidant, or a sulfur antioxidant. It is also possible to add a lubricant to improve the fluidity. Also, depending on the purpose, fibrous reinforcing agents such as glass fibers, mechanical fillers, colorants, and pigments can be added. The resin composition V of the invention can be made flame retardant by mixing a general halogenated organic compound flame release agent such as tetrabromobisphenol A1 decaglomobiphenyl ether and brominated polycarbonate with antimony oxide. .

The method for producing the thermoplastic resin composition of the present invention is not limited; for example, +A) polyglutarimide, (Bl graft copolymer and one or more other polymers as necessary) may be mixed in advance, or may not be mixed. A method is adopted in which the materials are supplied to a dilution machine in a desired ratio and then melted and mixed.

As explained above, the thermoplastic resin composition of the present invention has an excellent balance of heat resistance represented by heat distortion temperature, mechanical properties represented by impact resistance, and fluidity during melt molding. Since it also has excellent weather resistance, it is expected to be used in a variety of applications that take advantage of these properties.

Hereinafter, the present invention will be further illustrated by Reference Examples and Examples. In addition, in the examples, the thermal teardrop temperature is ASTM D-6.
48-56, Izot impact degree is ASTM D-25
6-56Method At. Bath viscosity is measured using a Kaika type flow tester and the resin temperature is 260°C.
It was measured with The number of copies indicates the heavy lid part.

Example 1 (Preparation of (A) polyglutarimide, (B) graft copolymer and (C) vinyl co-electropolymer)
Pellets of polyglutarimide polymethyl methacrylate were charged into an extruder together with ammonia or ethylamine or ethylamine, and extrusion was carried out at a resin temperature of 280°C while degassing the gas generated from the exhaust port attached to the extruder. Table 1
Five shelves of polyglutarimide as shown in Figure 1 were prepared.

Table 1 (B) Mikata EPT manufactured by Mikata Petrochemical Industry Co., Ltd. as the graft copolymer KPDM
4 Q 70 (iodine value: 24, Mooney viscosity: 65
, non-conjugated diene component: 5-ethylidene-2-) Polymerization of a monoelectrolyte mixture is carried out in the presence of EPDM according to the composition, and a graft copolymer (S
-1 to B-6) were prepared.

For comparison, a graft copolymer (B-
7 and B-8) were prepared in the same machine.

Table 2 (CJ vinyl/L/based copolymers) Copolymers (C-1) to (c-
4) was prepared.

Copolymer (C-1): styrene/acrylonitrile = 7
0150 Copolymer CC-23: Styrene/methacrylate/I
//Acrylonitrile = 30/60/10 Copolymer (c-5): α-methylstyrene/styrene/
Acrylonitrile = 70/l O/20 Copolymer (C-4): Styrene/maleic anhydride = 7
8/2 2 Example 1 Polyglutarimide prepared in Reference Example 1 (A-1 to A-
5), graft copolymers (B-1 to B-8) and copolymers (C-1 to C-4) were blended in the proportions shown in Table 5, and the physical properties of the test pieces obtained by molding were evaluated. The measured results are shown in Table 5.

In addition, a 1/2 inch rii, y piece with a notch was irradiated with a Sunshine Weatherometer for 400 hours, and irradiated with M+
The weather resistance was evaluated by comparing the Izot impact strength of J. The results are shown in Table 51.

As is clear from the results in Table 5, the composition of the present invention (K-
1 to 2-12) have a well-balanced and excellent heat resistance, melt flowability, impact resistance, and weather resistance, and these properties can be improved by combining with other vinyl copolymers (C1) Further improvement (K-7 to -12).

On the other hand, when a graft copolymer containing poly-tadiene as a paste was combined (K-15), the weather resistance was extremely poor;
Melt fluidity is also insufficient.

In addition, when a graft copolymer containing acrylic rubber as a paste is blended (K-14), the weather resistance is satisfactory, but the impact strength is extremely low, so that it cannot withstand even one practical use.

Claims (1)

[Claims] (A) In the presence of polyglutarimide and (Bl ethylene-globylene-nonconjugated diene copolymer rubber 10 to 70 parts by weight) an aromatic vinyl monomer, a (meth)acrylic acid ester monomer, and At least one vinyl monomer selected from the group consisting of vinyl cyanide monomers 90
A graft copolymer obtained by polymerizing ~30 parts of (A)
A thermoplastic resin composition comprising 10 to 90 parts by weight of (B), 90 to 10 parts by weight of (A) + fB), and 100 parts by weight of (A) + fB).