JPH06885B2 - Heat resistant resin composition - Google Patents

Description

TECHNICAL FIELD The present invention relates to a thermoplastic resin composition excellent in heat resistance, impact strength and moldability. The composition of the present invention is used for automobile parts, electric / electronic parts, office work. It can be preferably used for equipment parts and the like.

(Prior Art) Conventionally, a method for producing a copolymer of an aromatic vinyl monomer, maleic anhydride and other vinyl monomers (Japanese Patent Publication No. 40-1).
5,829, Japanese Patent Publication No. 45-31,953, Japanese Patent Publication No. 49-10,156) are known. Also proposed is a method for producing a thermoplastic copolymer having improved impact resistance by graft-polymerizing maleic anhydride, an aromatic vinyl monomer and / or a vinyl monomer copolymerizable therewith with a rubber-like polymer. Has been done. (JP-A-48
-42,091, JP-A-49-28,693, JP-A-53-78,252,
However, the polymers obtained by copolymerizing these maleic anhydrides are
Although it has a high heat distortion temperature, in both cases, the copolymer has the drawbacks of being easily decomposed by hot water and being easily gelled and foamed by heat. There is a serious limitation, and there is a drawback that mechanical properties, particularly impact strength, are deteriorated when the processed product is contacted with water or steam or exposed to high temperature.

For the purpose of improving these drawbacks, a method and a composition for producing a copolymer in which maleic anhydride is replaced with a maleimide derivative have also been proposed. (U.S. Pat. No. 3,651,171, U.S. Pat. No. 3,652,726, JP-A-57-98536) (Problems to be solved by the invention) However, these copolymers or compositions have improved heat stability and hot water resistance. However, it still has the drawback of insufficient impact strength and moldability.

(Means for Solving Problems) The present invention has solved these drawbacks. By combining the maleimide derivative residues of the imidized copolymer in a specific combination, not only heat resistance but also impact strength and moldability can be obtained. It is also intended to provide an excellent composition.

That is, the present invention provides (A) component: aromatic vinyl monomer residue 30 to 80% by weight,
The total amount of N-phenylmaleimide monomer residue and N-methylmaleimide monomer residue is 20 to 60% by weight, maleic anhydride monomer residue is 0 to 20% by weight, and other vinyl monomers Residue 0-30% by weight and rubbery polymer 0-40
An imidized copolymer having a weight ratio of 97-70 / 3-30 and an N-phenylmaleimide monomer residue / N-methylmaleimide monomer residue molar ratio of 97-70 / 3-30. Combined 10 to 70 parts by weight and component (B): 10 to 70% by weight of rubbery polymer, 30 to 80% by weight of aromatic vinyl monomer residue, 0 to 40% by weight of vinyl cyanide monomer residue, and Other vinyl monomer residues 0-4
A thermoplastic resin composition comprising 10 to 90 parts by weight of a graft copolymer of 0% by weight and (C) component: 0 to 80 parts by weight of a thermoplastic resin.

First, a method for producing the imidized copolymer of the component A will be described.

As the method for producing the component A copolymer, the aromatic vinyl monomer, N-
A method of copolymerizing a phenylmaleimide monomer, an N-methylmaleimide monomer, maleic anhydride and a vinyl monomer mixture copolymerizable therewith, and the second production method in the presence of a rubbery polymer if necessary. , An aromatic vinyl monomer, a maleic anhydride and a copolymer of a vinyl monomer mixture copolymerizable therewith, are reacted with aniline and methylamine to form a part or all of the acid anhydride group. Examples thereof include a method of converting to an imide group, and an imidized copolymer can be obtained by any method.

Aromatic vinyl monomers used in the first and second production of the component A copolymer include styrene monomers such as styrene, α-methylstyrene, vinyltoluene, t-butylstyrene, chlorostyrene, and the like. Is a substituted monomer,
Of these, styrene is particularly preferred.

Other vinyl monomers include acrylonitrile, meacrylonitrile, vinyl cyanide monomers such as α-chloroacrylonitrile, acrylic acid ester monomers such as methyl acrylic acid ester, ethyl acrylic acid ester, and methylmethacrylic acid ester. Methacrylic acid ester monomers such as ethyl methacrylic acid ester, vinyl carboxylic acid monomers such as acrylic acid and methacrylic acid, acrylic acid amide, and methacrylic acid amide.

When the imidization reaction of the second production method is carried out in a solution state or a suspension state, it is preferable to use an ordinary reaction vessel, for example, an autoclave, and when it is carried out in a bulk molten state, an extruder equipped with a devolatilization device is used. May be used. A catalyst may be present during imidization, and for example, a tertiary amine or the like is preferably used.

The temperature of the imidization reaction is room temperature to 350 ° C, preferably 100 to 300 ° C. When the temperature is lower than room temperature, the reaction rate is slow and the reaction takes a long time, which is not practical. While 3
If the temperature exceeds 50 ° C, the physical properties of the polymer are deteriorated due to thermal decomposition of the polymer.

Further, as the rubber-like polymer used in the first and second production methods, a butadiene polymer, a copolymer of a vinyl monomer copolymerizable with butadiene, an ethylene-propylene copolymer, an ethylene-propylene-diene Copolymers, block copolymers of butadiene and aromatic vinyl, acrylic acid ester polymers, and copolymers of acrylic acid esters and vinyl monomers copolymerizable therewith are used.

The component A copolymer has an aromatic vinyl monomer residue of 30 to 80.
% By weight, preferably 40 to 70% by weight, the total amount of N-phenylmaleimide monomer residue and N-methylmaleimide monomer residue is 20 to 60% by weight, maleic anhydride monomer residue 0 to An imidized copolymer comprising 20% by weight and 0 to 30% by weight of other vinyl monomer residues and 0 to 40% by weight of a rubbery polymer, preferably 0 to 30% by weight,
When the amount of the rubber-like polymer exceeds 40% by weight, heat resistance, moldability and dimensional stability are impaired. When the amount of the aromatic vinyl monomer residue is less than 30% by weight, moldability and dimensional stability are impaired, and when it exceeds 80% by weight, impact strength and heat resistance are impaired. When the amount of the maleimide derivative residue is less than 20% by weight, the effect of improving the heat resistance is not sufficient, while when it exceeds 60% by weight, the resin composition becomes brittle and the moldability remarkably deteriorates. N- in the maleimide derivative residue
The molar ratio of the phenylmaleimide monomer residue to the N-methylmaleimide monomer residue is 97 to 70/3 to 30, preferably 95 to 80/5 to 20. If this ratio exceeds 97/3, the impact strength will be insufficient, and if it is less than 70/30, the heat resistance will be poor. The maleic anhydride monomer residue may be 0% by weight, but up to 20% by weight is acceptable. If it exceeds 20% by weight, thermal stability and hot water resistance are deteriorated, which is not preferable.

Next, a method for producing the B component will be described.

The rubber-like polymer used as the component B is a polymer composed of a vinyl monomer homopolymerizable with butadiene alone or a copolymer thereof, an ethylene-propylene copolymer, an ethylene-propylene-polymer.
There is a diene copolymer or a polymer comprising an acrylic ester alone or a vinyl monomer copolymerizable therewith.

The aromatic vinyl monomer used as the component B is a styrene monomer such as styrene, α-methylstyrene, vinyltoluene, t-butylstyrene, chlorostyrene, or a substituted monomer thereof. And α-
Monomers such as methylstyrene are particularly preferred.

Examples of the vinyl cyanide monomer include acrylonitrile, methacrylonitrile, α-chloroacrylonitrile, etc., and acrylonitrile is particularly preferable. Other vinyl monomers include acrylic acid esters such as methyl acrylic acid ester and ethyl acrylic acid ester, methacrylic acid esters such as methylmethacrylic acid ester and ethylmethacrylic acid ester, vinylcarboxylic acid such as acrylic acid and methacrylic acid. , Acrylic acid amide, methacrylic acid amide and the like.

The method for producing the graft copolymer of the component B is the rubber-like polymer 10
Graft a monomer mixture consisting of 30-80% by weight of aromatic vinyl monomer, 0-40% by weight of vinyl cyanide monomer and 0-40% by weight of other vinyl monomer in the presence of ~ 70% by weight. Obtained by copolymerization. For the polymerization, any known polymerization technique can be adopted, and examples thereof include aqueous heterogeneous polymerization such as suspension polymerization and emulsion polymerization, bulk polymerization, solution polymerization and precipitation polymerization of the produced polymer in a non-solvent. is there. Emulsion polymerization is particularly preferable here because the rubber particle size can be easily controlled.

Further, as the thermoplastic resin that can be used as the C component,
For example, a copolymer comprising 30 to 90% by weight of an aromatic vinyl monomer residue, 0 to 40% by weight of a vinyl cyanide monomer residue, and 0 to 40% by weight of another vinyl monomer residue, a polycarbonate, Polybutylene terephthalate, polyethylene terephthalate, polyarylate, 6,6-nylon, 6-nylon, polyphenylene oxide, polyphenylene sulfide, polyphenylene sulfone, etc. are used, and one or more of these resins are used. can do.

Further, in the present invention, the proportions of the A component, the B component and the C component are 10 to 70 parts by weight of the A component, preferably 20 to 60 parts by weight, and 10 to 90 parts by weight of the B component, preferably 20 to 60 parts by weight.
Parts by weight, C component 0 to 80 parts by weight, preferably 0 to 60 parts by weight are used. If the proportion of the component A is less than 10 parts by weight, the effect of improving heat resistance is not sufficient. On the other hand, when the amount of the component A exceeds 70 parts by weight, the impact strength decreases and the moldability also deteriorates. When the proportion of B component is less than 10 parts by weight,
Satisfactory impact strength cannot be obtained because the effect of reinforcing the impact of the graft copolymer is insufficient. If the proportion of component B exceeds 90 parts by weight, heat resistance and moldability are impaired. On the other hand, when the ratio of the component C exceeds 80 parts by weight, the characteristics of the imidized copolymer, that is, the heat resistance is deteriorated.

In the present invention, in addition to the components A, B and C, usual additives and reinforcing agents such as stabilizers, lubricants, plasticizers, fillers, colorants, UV absorbers, flame retardants, glass fibers, carbon fibers, etc. It can be blended.

The method for blending the resin composition of the present invention is not particularly limited,
Known means can be used. Examples of the means include a Banbury mixer, a tumbler mixer, a Henschel mixer, a mixing roll, a single-screw or twin-screw extruder, and the like. As a mixing form, there are methods such as ordinary melt mixing, multistage melt kneading using master pellets, solution blending, mixing in a reaction liquid, and the like to obtain the composition.

(Example) All parts and% in the examples are represented by weight.

Examples 1 to 3 Experimental Example 1. Production of component A 60 parts of styrene in an autoclave equipped with a stirrer,
100 parts of methyl ethyl ketone and 10 parts of polybutadiene cut into small pieces were charged and stirred at room temperature for one day to dissolve the rubber, then the system was replaced with nitrogen gas and the temperature was raised to 85 ° C. 40 parts of maleic anhydride and 0.075 parts of benzoyl peroxide, 0.075 of azobisisobutyronitrile
A solution in which 250 parts of methyl ethyl ketone was dissolved was continuously added for 8 hours. Addition temperature is 85 ° C for 3 hours after addition
I kept it. As a result of sampling a part of the viscous reaction liquid and quantifying the unreacted monomer by gas chromatography, the polymerization rate was 98% styrene and 99% maleic anhydride.
It was in%. 32.3 parts of aniline of 0.85 molar equivalent to maleic anhydride was added to the copolymer solution thus obtained, and
1.9 parts of 0.15 molar equivalent of methylamine was added together with 0.3 part of triethylamine, and the mixture was reacted at 140 ° C. for 7 hours. 200 parts of methyl ethyl ketone was added to the reaction solution, cooled to room temperature, poured into 1500 parts of vigorously stirred methanol, precipitated, filtered and dried to obtain an imidized copolymer. C-13
From the NMR analysis, 96% of the maleic anhydride group was imidized. This was designated as Polymer A-1.

Experimental Example 2. Production of B component 143 parts of polybutadiene latex (solid content 35%, average particle size 0.35μ, gel content 90%), sodium stearate 1 part, sodium formaldehyde sulfoxylate
0.1 part, tetrasodium ethylenediamine tetraacetyl acid 0.03 part, ferrous sulfate 0.003 part and water
Heat 150 parts to 65 ° C and add acrylonitrile 30 to it.
% And 50 parts of styrene, 50 parts of a monomer mixture,
0.2 parts of t-dodecyl mercaptan and 0.15 part of kyumen hydroperoxide were continuously added over 4 hours, and after the addition, polymerization was carried out at 65 ° C. for 2 hours. The polymerization rate was 97% styrene, 96 acrylonitrile by gas chromatography analysis.
It was in%. After adding an antioxidant to the obtained latex, it was coagulated with calcium chloride, washed with water and dried to obtain a graft copolymer as a white powder, which was designated as Polymer B-1.

Experimental Example 3. Evaluation of physical properties of resin composition As component A, imidized copolymer of A-1, component B-1 of graft copolymer, component C is AS resin (manufactured by Denki Kagaku Kogyo Co., Ltd., product The name AS-S) was blended in various proportions, and the blended product was extruded and pelletized by a 30 mmφ devolatilizing screen extruder. The blends each contained 0.2 part of octadecyl 3- (3,5-di-sialybutyl-4-hydroxyphenyl) -propionate and 1 part of tristearyl phosphite. The physical properties of the composition thus obtained were measured and are shown in Table 1.

Comparative Example 1 In the production of the component A of Experimental Example 1, with respect to maleic anhydride
Polymer A'was carried out in exactly the same manner as in Experimental Example 1 except that 0.85 molar equivalent of aniline and 0.15 molar equivalent of methylamine were used instead of 1 molar equivalent of aniline with respect to maleic anhydride. -1 was obtained. The polymerization rate at this time was 97% styrene and 99% maleic anhydride, and the imidation rate of the maleic anhydride group to the N-phenylmaleimide group was 94%. This polymer A'-1 was replaced with polymer B-
1 and AS resin were blended in the same manner as in Experimental Example 3,
The physical properties of the composition were measured, and the results are shown in Table 1.

Comparative Example 2 In the production of the component A of Experimental Example 1, with respect to maleic anhydride
The same procedure as in Example 1 was repeated except that 0.85 molar equivalent of aniline and 0.15 molar equivalent of methylamine were used instead of 1 molar equivalent of methylamine to maleic anhydride. A'-2 was obtained. At this time, the polymerization rate was 98% styrene and 99% maleic anhydride, and the imidation rate of maleic anhydride to the N-methylmaleimide group was 98%. The polymer A'-2 was blended with the polymer B-1 and the AS resin in the same manner as in Experimental Example 3 and the physical properties of the composition were measured. The results are shown in Table 1.

The physical properties were measured by the following methods.

(1) Heat resistance VSP: Load 5 kg, according to ASTM D-1525.

(2) Izod impact strength: Izod with notches. ASTM
According to D-256.

(3) Fluidity MFI ... Temperature 250 ° C, load 5kg, ASTM D-
According to 1238.

(Effects of the Invention) The composition of the present invention is remarkably improved in impact strength and moldability (fluidity) without lowering the conventional heat resistance.

Claims (1)

[Claims] 1. Component (A): aromatic vinyl monomer residue 30 to
80% by weight, the total amount of N-phenylmaleimide monomer residue and N-methylmaleimide monomer residue is 20-60.
An imidized copolymer containing 0 to 20% by weight of maleic anhydride monomer residues, 0 to 30% by weight of other vinyl monomer residues and 0 to 40% by weight of a rubber-like polymer, and N
-10-70 parts by weight of an imidized copolymer in which the molar ratio of the phenylmaleimide monomer residue and the N-methylmaleimide monomer residue is 97-70 / 3-30, and the component (B): rubber-like Polymer 10 to 70% by weight, aromatic vinyl monomer residue 30 to 80% by weight, vinyl cyanide monomer residue 0 to 40% by weight and other vinyl monomer residue 0 to 4
10 to 90 parts by weight of a graft copolymer consisting of 0% by weight and (C) component: thermoplastic resin other than (A) component and (B) component
A thermoplastic resin composition containing 80 to 80 parts by weight.