JPS5884855A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To obtain titled composition of simultaneously improved inpact resistance and melt fluidify with retaining the original heat distortion temperature, comprising polyglutarimide and a rubbery polymer-based specific graft copolymer. CONSTITUTION:The objective composition comprising (A) 10-90 (pref. 30-80) pts.wt. of polyglutarimide and (B) 90-10 (pref. 70-20) pts.wt. of a graft copolymer prepared by the polymerization of (i) 95-20pts.wt. of a vinyl monomer mixture containing, at least, an aromatic vinyl monomer and maleic anhydride in the presence of (ii) 5-80pts.wt. of a rubbery polymer so that the amount of the component (A) plus (B) equals 100pts.wt. Additional incorporation of a graft copolymer prepared from a vinyl monomer (e.g. styrene) in the presence of a rubbery polymer, an aromatic vinyl monomer/maleic anhydride copolymer, etc. would lead to further improvement for the present purpose.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides a thermoplastic gruel composition which has a low thermal deformation degree and excellent thermal resistance and melt flowability.

In recent years, borig-p-p-imide, which has been proposed as a new imide polymer with excellent heat resistance, for example in JP-A No. 52-65989 @IL, has a high heat distortion temperature, but has a typical 4JIl impact resistance. Unfortunately, its use as a molding material is quite limited due to its poor mechanical properties and poor fluidity during melt molding.

In the past, 41 methods have been studied to improve the shortcomings of polyglutarimide, and for polyglutarimide, (1) acrylonitrile/getadiene/styrene-based CABS system) has been used to improve the so-called 1m14 strength. A method using a polymer, methacrylate A' [methyl/butadiene/styrene (MBEI) copolymer or alkyl rea acrylate rubber (Japanese Unexamined Patent Publication No. 1982-65989'), <2) getadiene rubber or I Method of using polycarbonate and a multi-stage electric combination based on Rekyl acrylate rubber (II? 1986-AO4S9
No. 1 and (6) Multi-stage electrolyte composite based on butadiene rubber τ and multi-#! based on fullkyl acrylate rubber t-base! Method of using i-ri combination (Unexamined Japanese Patent Publication No. 55-152
No. 740), etc. have been proposed. however,
The strength obtained by method (1) above is still insufficient, but in order to obtain a higher strength, it is necessary to mix many modifiers, resulting in heat Either or both of the deformation temperature and melt fluidity must be made significantly magnetic.Also, in methods (2) and (6) above,
The i-strength is improved to some extent. However, there is a problem in that the bath fluidity of the composition is rather deteriorated.

Therefore, the inventors of the present invention have conducted careful studies with the aim of maintaining polyglutarimide's high heat distortion temperature and improving its trade resistance and bath melt fluidity at the same time. The present invention has been achieved by discovering that the above object can be effectively achieved by blending a specific graft copolymer based on Electropolymer t.That is, the present invention is based on (A) polyglutarimide and (
B) In the presence of 5 to 80 parts by weight of a rubbery polymer, polymerize 95 to 203 parts of a mixture of 95 to 203 parts of violet to Vinino containing an aromatic vinyl group electrolyte and maleic anhydride as essential components. Naru Craft Kyodo) Go □1 tau, (A) is 10-90
Ayodobe, (B) is 90 to 10 parts by weight, and (A)
+ (B) is blended in a proportion of 100 parts by weight.

Merely blending ordinary valence 4 modifiers such as polymers does not provide sufficient valence 4 modification effect, and a resin composition with high heat distortion temperature and excellent VC in both impact resistance and solution flowability is obtained. It is not possible. However, the above (A) polyglutarimide and C
B> By mixing a graft copolymer with a sulco, it is possible to obtain a resin composition which has markedly improved impact resistance and melt flowability while maintaining a high heat distortion temperature. Although the reason for this effect of the present invention is not clear, it is probably due to (B)
A copolymer containing an aromatic vinyl monomer and anhydrous maleic monomer as essential components, which are the graft components of the graft copolymer, has excellent compatibility with (A) polyglutarimide, and is highly compatible with the copolymer. This is thought to be because the polymer itself has a high heat distortion temperature and good melt fluidity.

The polyglutarimide used in the present invention has the following formula (
It is an R6 body or copolymer containing a cyclic imide unit represented by I).

However, R1, R, and Rs in the formula each represent hydrogen or a substituted or unsubstituted alkyl group or aryl group having 1 to 20 carbon atoms.O If it contains the above cyclic imide unit, any chemical 4
Although polyglutarimides of PL. is hydrogen, methyl group, ethyl group, propyl group, ethyl group or phenyl group, which are generally used. In addition, the method for preparing polyglutarimide is, but not limited to, for example, polymethacrylate/L/serial methyl described in JP-A No. 52-65989 and ammonia or a primary amine such as methylamine or ethylamine using an extruder. The CB) gelabut copolymer used in the present invention is a method in which a glutarimide ring is formed by reacting an aromatic vinyl group with an anhydride arene group in the presence of a rubbery polymer. It is made by polymerizing vinyl thread as an essential component.

Here, as the rubber-like one-coat, polygetadiene rubber, acrylonitrile/butadiene co-electrolyte rubber (NBR),
y. Diene-based rubbers such as carbon/getadiene coelectrolyte rubber (SBR), acrylic rubbers such as polybutyl acrylate and polypropyl acrylate, and ethylene/propylene/non-conjugated diene rubber (]lCpDM) can be used. . In addition, the vinyl monomer mixture to be graft copolymerized with this rubbery polymer contains an aromatic vinyl monomer and maleic anhydride as essential components, but it also contains vinyl monomers that can be copolymerized with these. Regarding the preparation method of this vinyl monomer mixture for 3M combination, it is possible to further increase the effect of the wood and give characteristics to the composition according to the purpose by using a page body.
There is no particular restriction, and the mixture may be charged all at once with the rubbery polymer before the start of polymerization, or may be divided into portions and continuously charged during polymerization. Alternatively, polymerization can be carried out while continuously charging maleic anhydride into a solution of a rubbery polymer in an aromatic vinyl monomer or a mixture of an aromatic vinyl monomer and other vinyl monomers. In addition to the 0 or more methods that can be used, various methods are possible for charging the vinyl monomer mixture, and there are no particular restrictions, but the total composition of all vinyl monomers charged during polymerization can be 20-95% by weight of aromatic vinyl monomer, 5-50% by weight of maleic anhydride, and 0-50% by weight of other copolymerizable vinyl monomers.
is appropriate. If the composition is other than this, there will be adverse effects such as a decrease in the impact strength and heat distortion temperature of the resulting composition.
-Methylstyrene and mixtures thereof, other vinyl monomers include acrylonitrium, methacrylate/I/
#Methyl.

ArcryA/methyl acid, maleimide, etc., and a mixture thereof are shown, but are not limited to these. .

(b) Rubbery polymer and vinyl in graft copolymer
The proportion of the rubber-like electrolyte mixture is 5 to 80 parts by weight, preferably 15 to 65 parts by weight, and vinyl chloride.
It is necessary to polymerize from 95 to 20 parts by weight, particularly preferably from 85 to 35 parts by weight (100 g parts in total) of the thread monopolymer mixture. When the proportion of the rubber-like polymer is less than 5 parts by weight, not only the double-sided resistance is insufficient, but also the thermal deformation 4 is reduced, and when it exceeds 80 parts by weight, the mechanical properties obtained are poor. This is not preferable because it does not have the effect of improving impact resistance.

(B) There are no particular restrictions on the polymerization method for the graft copolymer, including bulk polymerization, solution polymerization, suspension polymerization, emulsion polymerization, and JJL-111! Polymerization can be carried out by ordinary polymerization methods such as l-polymerization method. For example,
49, JP-A-53-804'90, a method of polymerizing while charging maleic anhydride into a rubbery polymer/styrene/methyl ethyl ketone solution at a controlled rate; As shown in JP-A No. 55-48213, a method of polymerizing without adding maleic anhydride/acrylonitrile (maleic anhydride/acrylonitrile) to methyl ethyl ketone/toluene (41) of rubbery polymer/styrene/acrylonitrile, etc. It can be polymerized in various ways.

In the present invention, the blending ratio of (~polyglutarimide and (B) graft copolymer) is 10 to 90 parts by weight of (A), particularly preferably 30 to 80 parts by weight, and 90 to 10 parts by weight, particularly Preferably 70 to 20] t11k part ((gradient + (
c) is 100 parts by weight). If the blending ratio is other than this, the impact strength and thermal deformation tIA degree will be low, and a desirable resin composition cannot be obtained.

Kinei Akira's resin composition further contains aromatic vinyl monomers such as nistyrene and α-methylstyrene, methacrylic A'M methip, acrylic A/#! in the presence of a rubbery polymer. Mechiμ
A graft copolymer formed by combining at least one vinyl monomer selected from the group consisting of (meth)acrylic ester monomers such as and cyanide vinyl μ series monomers such as acrylonitrile. By mixing the coalescence, the resistance l
It is also possible to further improve l11m properties. In addition, styrene/maleic anhydride copolymer, d-methylstyrene/
Anhydrous V-in acupuncture copolymer, styrene/Anhydrous Vomaray 7/
Acrylonitrile copolymers and aromatic vinyl group-based polymers such as styrene/maleic anhydride/methacrylate A/-methyl coelectronic polymers, α-methylstyrene/acrylonitrile copolymers, α-methylstyrene/acrylonitrile copolymers, α -Methylstyrene/styrene/acrylonitrile copolymer and α-
By mixing α-methylstyrene copolymers such as methylstyrene/methacrylate/V/acrylonitrile copolymer, it is possible to further improve impact resistance and molten flammability while maintaining a high heat distortion temperature. ° You can also. Furthermore, by mixing styrene/acrylonitrile μ copolymer, styrene/methacrylic tvdl meth 1v/acrylonitrile copolymer, etc., it is possible to improve the balance of melt fluidity and lid resistance. In addition, it is also possible to obtain a gruel Jj'd composition having the characteristics of a porridge by mixing a supplementary (co)polymer or resin ha.Thermoplastic abrasive composition of the present invention On the normal thermoplastic painting side,
For hindered phenol-based antioxidants and phosphorus-based antioxidants, antioxidants such as antioxidants and sulfur-based antioxidants are added to improve mechanical stability, and lubricants are added to further improve fluidity. You can also make it better. Depending on the purpose, fibrous reinforcing agents such as glass fibers, inorganic fillers, layer colorants, and pigments can also be blended. Furthermore, by mixing a general halogenated organic compound-based flame precipitating agent such as tetraglomobinphenol/l/A, decabromobiphenyl ether, or brominated polycarbonate with antimony oxide, the resin composition of the present invention can be made into four-flame. It is possible.

The present invention will be further explained below with reference to Reference Examples and Examples. In addition, in one example of actual performance, the degree of thermal deformation is ASTM D
-648-56, Izot-4 strength is ASTM D
-j56-56 Measured according to Method A ◎ Melt viscosity was measured at resin temperature 2 using Koka type flow tester.
11111 at 60°C. The number of copies is based on N plates.

Reference example 1 Polyglutarimide (he), graft copolymer LB),
Graft copolymer (Cl and vinyl A/based copolymer <D
) a141III (1) Pellets of polymethacrylic A/II methyl (~ polymethacrylic A/II methyl) are charged into an extruder together with 1 ammonia or methylamine or ethylamine, and while degassing the generated gas from the exhaust port attached to the extruder 1λ, Extrusion was carried out with tree layer 7I!28C1 to prepare 5ai polyglutarimide shown in coating 1.

Table 1.

(2)-Graft copolymer (B) A vinyl-based electrolyte containing carbon dioxide and anhydrous maleic acid as essential components was polymerized in the presence of each of the polymers and polymers shown in Table 2. A graft copolymer having the following composition was prepared. In addition, Table 2. Medium PBD is polygetadiene rubber, a styrene/getadiene copolymer rubber consisting of 725% by weight of SBR and 75% of getadiene.
nPDM is an ethylene/propylene 15-ethylidene-2-turbornene terpolymer rubber with an iodine value of 25 and a Mooney viscosity of 60 (ethylene/propylene = 68,5/
Table 2 Graft Copolymer C
B) (6) Graft copolymer (C) Polymerization of a vinyl spinning wheel in the presence of a rubbery electropolymer τ
A graft copolymer (c
) 84 pieces of 3 m were manufactured.

Table 5 Graft co-electropolymer (C) (4) Seven types of vinyl copolymers (→ vinyl co-electropolymer ψ having the composition shown in Table 4) were prepared.

Table 4 Vinyl copolymer (→ Example 1 In polyglutarimide and graft copolymer 1116 in Reference Example 1), graft copolymer (C) and vinyl copolymer (D) in Table 5. The mixtures were blended in the following proportions and subjected to an extruder to be melt-mixed and pelletized at 250C. Then 2601:
A test piece was molded under the conditions of mold IML at 7°C.

Table 5 Table 5 (continued) The following is clear from Table 5.

Graft copolymer containing polyglutarimide, aromatic vinyl group-type violet and maleic anhydride as essential components■)
By blending these, a resin composition with excellent heat deformation -k, impact resistance and bath melt flowability can be obtained. (
, L1-7) Furthermore, by blending together with a graft copolymer (C1) containing styrene, acrylonitrile, methyl methacrylate, etc. as a graft component, -'411
It is also possible to further improve the 8Ii degree. (8-11
) Also, by blending copolymers such as styrene/male 4y acid anhydride copolymer, α-notip styrene copolymer, and styrene/acrylonitrile copolymer, heat distortion temperature and resistance to - It is also possible to achieve a balance between impact resistance and melt flow properties. (1) - 19) On the other hand, if a graft copolymer (Q) without maleic anhydride is mixed with polyglutarimide, the vfJ
It is not possible to obtain a desirable resin composition due to the poor 4 properties and high wave properties. (]KanezO~22) Patent applicant Taku V Co., Ltd.

Claims (1)

[Claims] (gradient polygluta p-imide and p) rubbery polymers 5 to 8
Vinyl monomer mixture 9 containing an aromatic vinyl monomer and maleic anhydride as essential components in the presence of 0 parts by weight
A graft copolymer obtained by polymerizing 5 to 20 parts by weight of (A
A thermoplastic 11!