JPS6126645A - Heat-resistant resin composition - Google Patents

Abstract

PURPOSE:To provide a composition having excellent thermal stability, hot-water resistance, impact strength and moldability, and useful for the production of various parts, by compounding a specific imidated copolymer and a graft copolymer. CONSTITUTION:The objective composition can be produced by compounding (A) 10-70pts.(wt.) of an imidated copolymer composed of (a) 0-40(wt)% rubbery polymer, (b) 30-80% aromatic vinyl monomer residue, 9c) 20-60% N-phenylmaleimide monomer residue and N-methylmaleimide monomer residue (in total), 9d) 0-20% maleic anhydride monomer residue and (e) 0-30% other vinyl monomer residue, wherein the molar ratio of the N-phenylmaleimide monomer residue to the N-methylmaleimide monomer residue is (97-70)/(3-30), (B) 10-90pts. of a graft copolymer composed of 10-70% rubbery polymer and 30-80% romatic vinyl monomer residue and (C) 0-80pts. of a thermoplastic resin other than the components A and B.

Description

Detailed Description of the Invention (Industrial Application Field) The present invention relates to a thermoplastic resin composition with excellent heat resistance, impact strength, and moldability. It can be preferably used for equipment parts, etc.

(Prior art) A method for producing a copolymer consisting of an aromatic vinyl monomer, maleic anhydride and other vinyl monomers (Japanese Patent Publication No.
-15.829, Japanese Patent Publication No. 45-31.953, and Japanese Patent Publication No. 49-10.156) are known. In addition, maleic anhydride, aromatic vinyl monomer and/or
Alternatively, a method for producing a thermoplastic copolymer with improved impact resistance by craft polymerizing a vinyl monomer copolymerizable with these has also been proposed. (%Kokai No. 48-42.091, JP-A No. 49-28,693, JP-A-53-78.252
No. 53-80.490 1 However, these polymers copolymerized with maleic anhydride have high heat distortion temperatures, but in any case the copolymers decompose in hot water at 19°C. It also has the disadvantage of being easily gelled and foamed by heat, so there are significant restrictions when performing injection or extrusion processing, and if the processed product is brought into contact with water or steam or exposed to high temperatures. The disadvantage was that mechanical properties, particularly impact strength, were reduced.

In order to improve these drawbacks, methods and compositions for producing copolymers in which maleic anhydride is replaced with maleimide derivatives have also been proposed. (U.S. Patent No. 3.651.171, U.S. Patent No. 3.652.726, JP-A-57-98
No. 536) (Problems to be Solved by the Invention) However, although these copolymers or compositions have improved heat stability and hot water resistance, they still have the drawback of being insufficient in impact strength and moldability.

(Means for solving problems) The present invention solves these drawbacks.

By combining the maleimide derivative residues of the imidized copolymer in a specific manner, the present invention attempts to provide a composition that is excellent not only in heat resistance but also in impact strength and moldability.

That is, the present invention includes (AJ acid component rubbery polymer O~40% by weight, aromatic vinyl monomer residue 30~80% by weight, N-phenylmaleimide monomer residue and N-methylmaleimide monomer) The total amount of residues is 20-60% by weight, 0-20M maleic anhydride monomer residues, and 0-20M other vinyl monomer residues.
80 parts by weight, and the molar ratio of N-phenylmaleimide monomer residue to N-methylmaleimide monomer residue is 97 to
10 to 70 parts by weight of an imidized copolymer of 70/3 to 3o and fBl components: 10 to 70 parts by weight of rubbery polymer, 30 to 80 parts by weight of aromatic vinyl monomer residue, / vinyl monomonide mer residues O ~ 40% by weight and other vinyl monomer residues 0 ~
This is a thermoplastic resin composition containing 10 to 90 parts by weight of a 40% by weight kraft copolymer and 0 to 80 parts by weight (C1 component: thermoplastic resin).

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

As for the production method of the component A copolymer, in the first production method, aromatic vinyl monomer, N-
A method of copolymerizing phenylmaleimide monomer, N-methylmaleimide monomer, maleic anhydride and a vinyl monomer mixture copolymerizable with these, as a second production method, in the presence of a rubbery polymer if necessary, A polymer obtained by copolymerizing an aromatic vinyl monomer, maleic anhydride, and a vinyl monomer mixture copolymerizable with these is fully reacted with aniline and methylamine to imide some or all of the acid anhydride groups. The imidized copolymer can be obtained by any of the methods.

The 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, and chlorostyrene; is a substituted monomer,
Among these, styrene is particularly preferred.

Other vinyl monomers include vinyl cyanide monomers such as acrylonitrile, meccrylonitrile, and α-chloroacrylonitrile; acrylic acid ester monomers such as methyl acrylic acid ester and ethyl acrylic ester;
Examples include methacrylic acid ester monomers such as methyl methacrylic acid ester and 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 or suspension state, it is preferable to use a normal reaction vessel, such as an autoclave, and when carried out in a bulk molten state, an extruder equipped with a devolatilization device is used. may also be used. Further, 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. If the temperature is below room temperature, the reaction rate is slow and the reaction takes a long time, making it impractical. On the other hand 3
If the temperature exceeds 50°C, the physical properties will deteriorate due to thermal decomposition of the polymer.

Furthermore, the rubber-like polymers used in the first and second production methods include butadiene polymers, copolymers of butadiene and vinyl monomers copolymerizable, ethylene-propylene copolymers, ethylene-propylene-diene Copolymers, block copolymers of butadiene and aromatic vinyl, acrylic ester polymers, and copolymers of acrylic esters and vinyl monomers copolymerizable therewith are used.

The component A copolymer contains 0 to 40% by weight of a rubbery polymer, preferably 0 to 30% by weight, and 30 to 9% of aromatic vinyl monomer residues.
0% by weight, preferably 40-7% (1% by weight, the total amount of N-phenylmaleimide monomer residues and N-methylmaleimide monomer residues is 20-60% by weight, maleic anhydride monomer It is an imidized copolymer consisting of 0 to 20% by weight of residues and 0 to 30% by weight of vinyl monomer residues copolymerizable with these, and when the amount of rubbery polymer exceeds 40% by weight. Heat resistance, moldability and dimensional stability are impaired.If the amount of aromatic vinyl monomer residue is less than 30% by weight, moldability and dimensional stability will be impaired, and if it exceeds 80% by weight, impact strength will be impaired. If the amount of maleimide derivative residue is less than 20% by weight, the effect of improving heat resistance will not be sufficient, while if it exceeds 60% by weight, the resin composition will become brittle and the moldability will be significantly reduced. In addition, the molar ratio of N-phenylmaleimide monomer residues to N-methylmaleimide monomer residues in the maleimide derivative residues is 97 to 70/
3-30, preferably 95-8075-20. If this ratio exceeds 9773, the impact strength will be insufficient, and if it is less than 70/30, the heat resistance will be poor. In addition, the maleic anhydride monomer residue may be 0% by weight, but 2% by weight may be used.
Up to 0% by weight is permissible. If it exceeds 20% by weight, thermal stability and hot water resistance will deteriorate, which is not preferable.

Next, the method for producing component B will be explained.

The rubbery polymer used for component B is a polymer consisting of butadiene alone or a vinyl monomer copolymerizable with it, ethylene-propylene copolymer, ethylene-propylene-
There are polymers consisting of diene copolymers or acrylic esters alone or vinyl monomers copolymerizable with them.

The aromatic vinyl monomer used for component B includes styrene monomers such as styrene, α-methylstyrene, vinyltoluene, t-butylstyrene, chlorostyrene, and substituted monomers thereof; Styrene and α-
Monomers such as methylstyrene are particularly preferred.

Examples of vinyl cyanide monomers include acrylonitrile, methacrylonitrile, and α-chloroacrylonitrile, with acrylonitrile being particularly preferred. Other vinyl monomers include acrylic esters such as methyl acrylic ester and ethyl acrylic ester, methacrylic esters such as methyl methacrylic ester and ethyl methacrylic ester, and vinyl carboxylic acids such as acrylic acid and methacrylic acid. , acrylamide, methacrylic acid amide, etc.

The method for producing the graft copolymer of component B is as follows: rubbery polymer 10
~70% by weight - a monomer mixture comprising in the presence 30-80% by weight of aromatic vinyl monomers, 0-40% by weight of vinyl cyanide monomers and 0-40% by weight of other vinyl monomers 30
It is obtained by graft copolymerization of ~90% by weight. Polymerization is
Any known polymerization technique can be employed, e.g.
Suspension polymerization, aqueous heterogeneous polymerization such as emulsion polymerization, bulk polymerization,
There are solution polymerization and precipitation polymerization of the produced polymer in a non-solvent. In this case, emulsion polymerization is particularly preferred since it is easy to control the rubber particle size.

Furthermore, thermoplastic resins that can be used as component C include:
For example, a copolymer consisting of 30 to 90% by weight of aromatic vinyl monomer residues, 0 to 40% by weight of vinyl cyanide monomer residues, and 0 to 40% by weight of other vinyl monomer residues, Examples include polycarbonate, polybutylene terephthalate, polyethylene terephthalate, polyarylate, 6.6-nylon, 6-nylon, polyphenylene oxide, polyphenylene sulfide, polyphenylene sulfone, and one or more of these resins can be used.

part, preferably 0 to 60i1 part. A
If the proportion of the components is less than 10 parts by weight, the effect of improving heat resistance will not be sufficient. On the other hand, if the A component exceeds 70 parts by weight, the impact strength will decrease and the moldability will also deteriorate. Further, if the proportion of the B component is less than 10 parts by weight and 1 part by weight, the reinforcing effect of the kraft copolymer against impact will be insufficient, so that satisfactory reconnaissance strength will not be obtained. When the proportion of component B exceeds 90 parts by weight,
Heat resistance and moldability are impaired. Also, the proportion of C component is 8
When the amount exceeds 0 parts by weight, the characteristics of the imidized copolymer, such as heat resistance, deteriorate.

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

There are no particular restrictions on the blending method of the resin composition of the present invention.
Known means can be used.

For example, Banbury mixer, tumbler etc.
Examples include mixers, Henschel mixers, mixing rolls, single-screw or twin-screw extruders, and the like.

As for the mixing form, there are methods of obtaining the composition by ordinary melt mixing, multi-stage melt mixing using a master pellet or the like, solution blending, mixing in a reaction liquid, and the like.

(Example) All parts and parts in the examples are expressed on a weight basis.

(12; Examples 1 to 3 In an autoclave equipped with a stirrer, 60 parts of styrene,
100 parts of methyl ethyl ketone and 10 parts of polybutadiene cut into small pieces were charged, and after stirring at room temperature all day and night to dissolve the rubber, the system was purged with nitrogen gas and the temperature was raised to 85°C.

40 parts of maleic anhydride and 0.0 parts of benzoyl peroxide.
A solution of 0.075 parts of azobisin butyronitrile and 0.075 parts of azobisin butyronitrile dissolved in 250 parts of methyl ethyl ketone was continuously added for 8 hours. After the addition, the opening temperature was further maintained at 85°C for 3 hours. A portion of the viscous reaction solution was sampled and unreacted monomers were determined by gas chromatography. As a result, the polymerization rate was 98% of styrene and 99% of maleic anhydride. To the copolymer solution obtained here, 32.3 parts of Ayu 9, which is 0.85 molar equivalent to maleic anhydride, and 1.9 parts of methylamine, which is 0.15 molar equivalent, were added together with 0.3 parts of triethylamine. The reaction was carried out 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-
Analysis of C-13 revealed that 96 maleic anhydride groups were imidized. This was designated as Polymer A-1.

143 parts of polybutadiene latex (solid content 35 pieces, average particle size 0.35μ, gel content 90 inches) Sodium stearate 1 part, sodium formaldehyde sulfoxylate 0.1 part, tetrasodium ethylenediamine tetraacetic acid 0.03 parts of ferrous sulfate Q, 0.03 parts of ferrous sulfate and 150 parts of water were heated to 65°C, and 50% of a monomer mixture consisting of 30% acrylonitrile and 70% styrene was added to 0° of u,t-dodecyl mercaptan. 2 parts of Φ Yumene hydroperoxide O and 5 parts of After adding an antioxidant to the obtained latex, it is coagulated with calcium chloride, washed with water,
After drying, a graft copolymer was obtained as a white powder, which was designated as Polymer B-1.

The ratio of the imidized copolymer of A-1 as the A component, the kraft copolymer of B-1 as the B component, and the As resin (manufactured by Denki Kagaku Kogyo Co., Ltd., trade name A3-83't) as the C component. This blend was extruded into pellets using an f 30 wmφ screw extruder equipped with a devolatilization device.

Each blend contains 0.2 parts of octadecyl 3-1
3.5-ditertiarybutyl-4-hydroxyphenyl)-propionate and 1 part tristearylphosphite were included. The properties of the composition thus obtained were measured and shown in Table 1.

Comparative Example 1 In the production of component A in Experimental Example 1, 0.85 molar equivalent of aniline and (15) 0.15 molar equivalent of methylamine were used with respect to maleic anhydride, but 1 mol with respect to maleic anhydride was used instead. Polymer A'-1 was obtained by carrying out exactly the same operation as in Experimental Example 1 except that an equivalent amount of aniline was used.The polymerization rate at this time was 97% of styrene, 99% of maleic anhydride, ss, m water. The imidization rate of maleic acid groups to N-phenylmaleimide groups was 94%.This polymer A'-1 was mixed with polymer B-1 and As resin in Experimental Example 3.
Blend in the same manner as above, measure the physical properties of the composition,
The results are shown in Table 1.

Comparison fiI2 Instead of using 0.85 molar equivalent of aniline and 0.15 molar equivalent of methylamine with respect to maleic anhydride in the production of component A of Experimental Example 1, 1 molar equivalent of methylamine with respect to maleic anhydride was used. Polymer A'-2 was obtained by carrying out exactly the same operation as in Experimental Example 1 except that . The polymerization rate at this time was 98% styrene and 99% maleic anhydride.
The imidization rate of maleic anhydride into N-methylmaleimide groups was 98%. This one-part polymer A'-two-part polymer B
-1 and 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.

Table 1 The physical properties were measured by the following method.

(1) Heat resistance vs p = load 5Kf, ASTM
According to D-1525.

(2) Izotsu impact strength: Izotsu with a notch.

According to ASTM D-256.

(3) Fluidity MFI...temperature 250°C, load 5~, A
According to STM D-1238.

(Effects of the Invention) The composition of the present invention shows significant improvements in impact strength and moldability (fluidity) without deteriorating conventional heat resistance.

Claims (1)

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