JPS60177069A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To provide the titled composition of little discoloration by light, outstanding in both heat resistance and molding stability, comprising a polymer prepared by grafting e.g. aromatic vinyl compound to nonconjugated diene rubber and a copolymer derived from unsaturated dicarboxylic anhydride and aromatic vinyl compound, etc. CONSTITUTION:The objective composition comprising (A) 5-75wt% of a polymer prepared by grafting (1) aromatic vinyl and/or unsaturated carboxylic alkyl ester compound(s) (e.g. methyl acrylate) to (2) nonconjugated diene rubber (pref. ethylene-propylene copolymer) and (B) 95-25wt% of a copolymer derived from (1) unsaturated dicarboxylic anhydride, (2) aromatic vinyl compound and, if necessary, (3) another copolymerizable monomer therewith (e.g. acrylonitrile). The compositions of the above components pref. are as follows: component A: nonconjugated diene rubber 5-70wt% compound (1) 30-95wt%, component B: unsaturated dicarboxylic anhydride 0.5-65wt%.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel thermoplastic resin composition that exhibits little light discoloration and excellent heat resistance and molding stability.

Polyphenylene ether (PPO)-based modified materials and ABS-based super heat-resistant materials using α-methylstyrene, which have been widely used for automobile interior materials and office equipment, have a fundamental drawback of poor weather resistance. ing. Furthermore, even if most of the ultraviolet rays are blocked by window glass, such as in automobile interiors and office machines, the visible light that passes through them causes discoloration and deterioration of physical properties, which is a serious defect in so-called light resistance. In order to improve this drawback, it has been proposed to use EPDM-based graph graft polymers on polyphenylene ether-based materials (Japanese Patent Publication No. 47-43174.47-4).
3290), but since PPO itself inherently has poor heat aging resistance and weather resistance, no improvement can be expected. Also, a combination of resins using the same EPDM-based graph graft polymer methyl styrene is also known, but it does not have sufficient heat resistance and has poor molding stability, which poses practical problems.

The present inventors have arrived at the present invention as a result of intensive research aimed at solving these drawbacks.

That is, the present invention provides a graft polymer (A) obtained by graft-polymerizing an aromatic vinyl compound and/or an unsaturated carboxylic acid alkyl ester compound onto a non-conjugated diene rubber, an unsaturated dicarboxylic acid anhydride, an aromatic vinyl, or the like. The object of the present invention is to provide a thermoplastic resin composition which is characterized by being composed of a copolymer (B) comprising other polymerizable monomers, and which exhibits little discoloration due to light resistance and is excellent in heat resistance and molding stability.

The present invention will be explained in more detail below.

The non-conjugated diene rubbery polymer constituting the graft polymer (A) includes ethylene-propylene copolymer, dicyclopentadiene, ethylidene norbornene, 1,4-hexadiene, 1,4-cycloheptadiene, 1.5-7 Ethylene-propylene-nonconjugated diene copolymer such as ethylene-propylene-nonconjugated diene copolymerized with non-conjugated diene such as chlorooctadiene
Acrylic acid esters such as propylene polymers (1), homopolymers such as methyl acrylate, ethyl acrylate, butyl acrylate, and globil acrylate, and copolymers with other copolymerizable compounds such as styrene and acrylonitrile. One or more polymers selected from the group consisting of polymer (11), chlorinated polyethylene 011) and ethylene-vinyl acetate copolymer 1iv), with ethylene-propylene polymers being particularly preferred in terms of physical property balance. preferable.

Examples of the aromatic vinyl compound constituting the graft polymer include styrene, α-methylstyrene, methyl-α-methylstyrene, vinyltoluene, and the like. In addition, unsaturated carboxylic acid alkyl ester compounds include methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, and furthermore, those containing an epoxy group in the molecule. Examples include glycidyl acrylate and glycidyl methacrylate.

There is no particular restriction on the composition ratio of the non-conjugated diene-based rubbery polymer and the compound in graft polymer (A)K, but the non-conjugated diene-based rubbery polymer is 5 to 70% by weight, the compound is 30 to 9% by weight.
Preferably it is 5% by weight.

In addition, there is no particular restriction on the composition ratio of each compound in the compounds constituting the polymer, but the aromatic vinyl compound alone or the aromatic vinyl compound 50 to 80% by weight and the unsaturated carboxylic acid alkyl ester compound 20 to 50% by weight %
It is preferable that

Next, examples of the unsaturated dicarboxylic anhydride constituting the copolymer (B) include maleic anhydride, oxymaleic anhydride, ethoxymaleic anhydride, citraconic anhydride, phthalic anhydride, itaconic anhydride, etc. . Further, examples of the aromatic vinyl compound include styrene, α-methylstyrene, methyl-α-methylstyrene, vinyltoluene, and the like. Furthermore, other polymerizable monomers include the unsaturated carboxylic acid alkyl ester compounds, vinyl cyanide compounds such as acrylonitrile and methacrylonitrile, or C2 to C6 saturated carboxylic acid components.
Vinyl ester M containing, C1 to saturated alcohol component
Acrylic acid and methacrylic esters containing C8,
Examples include ethylenically unsaturated compounds such as maleic esters, vinyl ethers, N-vinyl lactams, and carboxylic acid amides; acrylonitrile in vinyl cyanide compounds; methyl in unsaturated carboxylic acid alkyl ester compounds. Preferred are methacrylate, ethyl methacrylate, and the like.

There is no particular restriction on the composition ratio of each compound constituting the copolymer (B), but it is preferable that the unsaturated carboxylic acid anhydride accounts for 0.5 to 65% by weight, and if it is less than 0.5% by weight, the heat resistance will deteriorate. If the properties exceed 65% by weight, molding stability will deteriorate.

Furthermore, the composition ratio of the aromatic vinyl compound to other polymerizable monomers such as the vinyl cyanide compound and the unsaturated carboxylic acid alkyl ester compound is not particularly limited, but preferably the aromatic vinyl compound is 50 to 100% by weight. and other polymerizable monomers with a market weight of 50 to 0.

Next, there is no particular restriction on the composition ratio of the graft polymer (A) and the copolymer (B), but the preferred composition range is 5 to 75% by weight of the graft polymer (A) and 5 to 75% by weight of the copolymer (B). 95～
It is 25% by weight.

The graft polymer content is less than 5% by weight, i.e. less than 5% by weight of the copolymer (1
If 3) exceeds 95% by weight, the impact resistance will be extremely poor, and if the graft polymer (5) exceeds 75% by weight, the moldability will be poor, flow marks will appear on the surface of the injection molded product, and the heat resistance will deteriorate. The sex is also low.

Examples of methods for producing the graft polymer (A) and copolymer ω) include emulsion polymerization, suspension polymerization, bulk polymerization, solution polymerization, emulsion-suspension polymerization, and bulk-suspension polymerization. The graft polymer (5) and the copolymer (B) can be mixed using a known mixer. In addition, depending on the purpose of mixing, polymers such as polystyrene and styrene-acrylonitrile copolymers, dyes and pigments, stabilizers, plasticizers,
It is also possible to add antistatic agents, ultraviolet absorbers, lubricants, fillers, etc.

EXAMPLES The present invention will be specifically explained below using Examples, but the present invention is not limited to these in any way.

Examples 1 to 5 1) Manufacturing method I of graft polymer (AI-1t)] Iodine number 8.5, Mooney viscosity 61, propylene content 4
500 parts by weight of ethylene-propylene rubber containing dicyclopentadiene as the diene component was dissolved in 2500 parts by weight of n-hexane and 1500 parts by weight of ethylene dichloride, and 450 parts by weight of styrene and 10 parts by weight of benzoyl peroxide were dissolved. Q (The combined solution was brought into contact with a large excess of methanol, the precipitate was separated and dried, and the rubber A styrene kraft polymer (A-1) having a content of 52.6 inches was obtained.

■] Iodine value 85, Mooney viscosity 61. 500 parts by weight of ethylene-propylene rubber containing propylene content 43% by weight and ethylidene norbornene as the diene component, 2500 parts by weight of n-hexane and 15% by weight of ethylene dichloride.
00 parts by weight, 700 parts by weight of styrene, 300 parts by weight of methyl methacrylate and 10 parts by weight of benzoyl peroxide.
After charging parts by weight, polymerization was carried out at 67° C. for 1θ hour under stirring at 60 Or, p, m in a nitrogen atmosphere.

The polymerization solution was brought into contact with a large excess of methanol, and the precipitate precipitated was separated and dried to obtain a styrene-methyl methacrylate graft polymer (A-11) with a rubber content of 35.2 inches.

2) Method for producing copolymer (B-1) ■ 70M parts of styrene, 15 parts by weight of maleic anhydride, 0.05 parts by weight of lauroyl peroxide, and 0.4 parts by weight of L-dodecylmercaptan. and 70°C while purging with nitrogen.
Bulk polymerization was carried out for 5 hours, and then polyvinyl alcohol Q was used as a suspension stabilizer, 14 parts ffi, 4 parts Trose, 0.
0.5 parts by weight of lauroyl peroxide as an initiator and 1 part by weight of acidic sodium sulfite as an aqueous phase polymerization inhibitor were added and polymerized for 3 hours. The particulate polymer was separated, washed and dried to obtain a maleic anhydride-styrene copolymer (B-1).

■] Styrene 70 parts by weight, acrylonitrile 30 ■f
Total: 15 parts by weight of maleic anhydride, 0.05 parts by weight of lauroyl peroxide and 10 parts by weight of t-dodecyl mer
4 parts by weight were added and bulk polymerized at 70°C for 5 hours while purging with nitrogen. Then, 230 parts by weight of water in which 14 parts by weight of polyvinyl alcohol O and 6 parts by weight of Metrose 000 were dissolved as a suspension stabilizer was added and suspended. 05 parts by weight of lauroyl peroxide and 01 parts by weight of acidic sodium sulfite were added as an aqueous phase polymerization inhibitor, and the mixture was polymerized for 3 hours. The particulate polymer is separated, washed and dried to form anhydrous maleic acid/styrene acid.
An acrylonitrile copolymer (B-...) was obtained.

Kraft polymer (A) and copolymer (B) were mixed in a 65 mm screw extruder in the compositions shown in Table 1 to obtain various compositions. Table 1 shows the impact resistance, processability, heat resistance, light resistance, and molding stability of the obtained composition and commercially available modified polyphenylene oxide resins and super heat-resistant ABS resins as comparative products.

Rice Engineering/Noryl PX manufactured by Geneering Plastics Co., Ltd.
1222y Rice 2 Kane Ace MUH manufactured by Kanebuchi Chemical Co., Ltd.
#Patent applicant Sumitomo Naugatuck Co., Ltd.

Claims (1)

[Claims] 1) Non-conjugated diene rubber containing an aromatic vinyl compound and/or
or a graft polymer obtained by graft polymerizing an unsaturated carboxylic acid alkyl ester compound (composed of a copolymer (B) consisting of N, an unsaturated dicarboxylic anhydride, and an aromatic vinyl compound, or these and other polymerizable monomers) 2) The thermoplastic according to claim 1, wherein the graft polymer (A) is 5 to 75% by weight and the copolymer (B) is 95 to 25% by weight. Resin composition. 3) The thermoplastic resin composition according to claim 1, wherein the unsaturated dicarboxylic anhydride in the copolymer/I3) is 0.5 to 65% by weight.