JPS6181451A - Heat-resistant thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To obtain a composition having remarkably improved impact strength, keeping excellent mechanical strength and heat-resistance of the base resin, by compounding a thermoplastic resin containing a polymer having imide group at the side chain with a higher alcohol fatty acid ester. CONSTITUTION:The objective composition can be produced by compounding (A) 80-99.9pts.wt. of a thermoplastic resin containing a polymer having imide group at the side chain with (B) 0.1-20pts.wt. of a higher alcohol fatty acid ester. The component A is an imidated copolymer composed of (i) 0-30 (wt)% rubbery polymer, (ii) 30-90% aromatic vinyl monomer residue, (iii) 10-70% unsaturated dicarboxylic acid imide derivative residue and (iv) 0-30% vinyl monomer residue copolymerizable therewith. The component B is preferably an ester of a 8-30C higher alcohol and lauric acid, palmitic acid, etc.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a heat-resistant thermoplastic resin composition containing a polymer having a side chain busy imide group having excellent impact strength. It can be preferably used for automobile parts, electrical parts, thunderbolt parts, office equipment parts, heating appliances, etc.

(Prior Art) Methods for producing polymers having imide groups in their side chains have been known. (U.S.P. 3,840,499, U.S.P.
3,998,907). Also known are compositions in which impact resistance is improved by blending rubber grafts or polycarbonate with polymers having imide groups in their side chains. (USF
3,652,726, USP & 642,949, Special Publication No. 49-12.576).

(Problems to be Solved by the Invention) These polymers having side tin imide groups have high heat resistance but poor impact resistance. Compositions blended with rubber grafts or polycarbonate have improved impact resistance to some extent, but still have the drawback of being insufficient.

(Means for Solving the Problems) The present inventor conducted intensive studies to improve the above-mentioned drawbacks of polymers having imide groups in side chains and compositions containing the same, and found that certain fatty acid esters, i.e., higher By adding a fatty acid ester of alcohol, we succeeded for the first time in obtaining a thermoplastic resin with significantly improved impact resistance without sacrificing mechanical properties or heat resistance.

The present invention consists of a high grade thermoplastic resin containing a polymer having an imide group in its side chain.

In the present invention, the polymer having an imide group in the side chain is 1) a copolymer in which an aromatic vinyl monochord and an unsaturated dicarboxylic acid anhydride are combined in the presence or absence of a rubber-like monomer. imidized association, 1)) an aromatic vinyl monomer, an unsaturated dicarzanoic anhydride, and a vinyl monomer that can be combined with 1)) in the presence or absence of a rubbery polymer; A copolymer imidized conjugate, l1)
) A polymer obtained by imidizing a copolymer made of an olefin and an unsaturated dicarmenic acid in the presence or absence of a rubbery polymer. Iv) Acrylic acid in the presence or absence of a rubbery polymer. and/or a polymer obtained by imidizing a copolymer obtained by polymerizing a monomer that is copolymerizable with methacrylic acid, ■)
V+) Aromatic vinyl monomer, maleimide and/or N-substituted maleimide polymerized in the presence or absence of a rubbery polymer; Vinyl monomer, maleimide and/or N-
There are polymers obtained by polymerizing substituted maleimides and vinyl monomers that can be combined with these maleimides.

Further, in the present invention, the thermoplastic resin containing a polymer having an imide group in a side chain includes polymers having an imide group in a side chain as exemplified in 1) to vi)K above. and/or α-
Methyl styrene copolymer, v+ii) methyl methacrylate-butadiene-styrene copolymer, 1x) acrylonitrile-ethylene/propylene-styrene copolymer,
×) Acrylonitrile-acrylic is mousstyrene copolymer, ×1) Acrylonitrile-styrene and/or α
-Methylstyrene copolymer, X1i) Rubber-modified styrene copolymer, Vlil) Styrene-butatsuene block copolymer, XV) Polycargonate, XV) Polyamide, Kari1) Thermoplastic polyurethane, Kari10 Borif 22 xiii) polyester, polysulfone, XX) polyphenylene/sulfide, xx1)
1f of polymers selected from polyetherimide, etc.! The thermoplastic resins blended above are exemplified.

Of course, the thermoplastic resin containing a polymer having an imide group in its side chain also includes a polymer alone having an imide group in its side chain.

In the present invention, the higher alcohol fatty acid ester added to the thermoplastic resin containing a polymer having an imide group in the side chain includes a higher alcohol having 8 to 30 carbon atoms, lauric acid, palmitic acid, stearic acid, isostearic acid,
Esters with fatty acids such as 12-hydroxystearic acid, ricinoleic acid, isooctanoic acid, persatic acid, callic acid, dimer acid, oleic acid and behenic acid are preferred. Preferred higher alcohols that form co-esters with fatty acids include decyl alcohol, dodecanol, myristyl alcohol, cecyl alcohol,
Stearyl alcohol, oleyl alcohol, C5yH
zs(C+oH!+)CHCH! OH,CttHts(
CttHts)CHCHIOH1C+sH*t(CI.

Horse, )CHCH,OH,C,,H,,(C,,I(t
s) CHCH,0H1C1~1゜Summer dry~1)(C1~
IHI~t+) CHClbOH, etc.

The higher alcohol fatty acid ester used in the present invention contains 80 to 99.9 parts by weight of a thermoplastic resin containing a polymer having an imide group in its side chain, and more preferably 0.1 to 20 parts by weight. It is a 0.5-10M scenic area. When the amount of higher alcohol fatty acid ester is less than 0.1]j Kurabe, the impact resistance of the composition is insufficiently improved.

On the other hand, if the amount of the higher alcohol fatty acid ester exceeds 20 parts by weight, the heat deformation resistance of the composition will be significantly reduced, and the mechanical strength will also be reduced.

The composition of the present invention is a mixture of a thermoplastic resin containing a polymer having an imide group on the side and a higher alcohol fatty acid ester, but there are no particular restrictions on the mixing method, and known means can be used. Take it. Examples of the means include a vanopary mixer, a tumbler mixer, a mixing roll, a single-shaft or twin-screw extruder, and the like. Examples of the mixing form include normal melt mixing, multistage melt mixing using master pellets, etc., and blending of solutions.

The composition of the present invention may further include antioxidants, poor solvents, ultraviolet absorbers, plasticizers, lubricants, glass fibers, carbon fibers,
It is also possible to add fillers such as calcium carbonate, mica, and carden black, colorants, antistatic agents, metal powder, and the like.

(Example) The present invention will be further explained below with reference to Examples.

Note that all parts and percentages in the examples are expressed on a weight basis.

Stirring (100 parts of styrene, 50 parts of methyl ethyl ketone, cut into small pieces) in an autoclave equipped with a 71° C.
After 24 parts of liptadiene rubber (NF35AS, manufactured by Asahi Kasei Corporation) was charged and the inside of the system was replaced with nitrogen gas, the mixture was stirred at room temperature all day and night to dissolve the rubber. After the temperature was set at 80° C., a solution of 67 parts of maleic anhydride and 0.3 parts of benzoyl peroxide dissolved in 400 parts of methyl ethyl ketone was continuously added over 8 hours. After heating, the temperature was kept at 80°C for an additional 3.5 hours. A portion of the viscous reaction solution was sampled and unreacted monomers were determined by gas chromatography, and the polymerization rate and maleic anhydride content in the polymer were calculated, and it was found that styrene was polymerized. rate of 98%, polymerization rate of maleic anhydride of 99%, content of maleic anhydride in the co-monomer of 35.2
%Met. Next, 63 parts of aniline (per 100% mole of added maleic anhydride) and 2 parts of triethylamine were added to one combined solution.
1 part Irganox 1076 (Ciba Geigy) as an antioxidant. : was added, the temperature was raised to 140°C, and the reaction was carried out for 7 hours to perform an imidization reaction. Reaction solution ke IQO℃
The reaction solution was purged into a Steffleske tube. Further, vacuum drying was performed at 180℃ for 3 hours (・,
After dissolution #, pulverization treatment is performed.

A yellowish white powder, Co-1 (combined Af), was obtained. Analysis of the C-C-13 portion showed that the conversion of acid anhydride groups to imide groups was 98%.

This copolymer was designated as Polymer A.

Experimental example - 1 part of styrene instead of 100 parts of styrene in (1)
00 parts and acrylonitrile 17 parts, 67 parts of maleic anhydride was changed to 50 parts, 63 parts of aniline was replaced with 47 parts, and the same procedure as in Experimental Example-(1) was carried out to produce an imidized 1 coalescence. I got it. This is called 1 combination B. The average polymerization rate at this time was 95%, and the conversion rate to imide groups was 98%.
%Met.

Experimental Example (3) In the absence of a rubbery polymer, the same procedure as in Experimental Example (1) was performed except that the polybutadiene of aromatic Experimental Example (1) was not used, and the imidized polymer was I got it. This will be referred to as Polymer C.

The average polymerization rate at this time was 99%, and the conversion rate to imide groups was 98%.

Polybutanoene rubber (Asahi Kasei Tsuen NF35AS) 2
4 parts to 100 parts of styrene and 50 parts of methyl ethyl ketone.
The autoclave was kept at 80'C, and the solution in which N-phenylmaleimide 100B and benzoyl peroxide 0.3 parts were dissolved in 400 parts of methyl ethyl ketone was continuously added over a period of 8 hours. Further, the mixture was kept at 80° C. for 3.5 hours to carry out polymerization. 1. Vacuum dry the combined liquid and crush it! l
l! ? A powdered copolymer was obtained. This is called a polymer. Note that the average conversion rate at this time was 95%.

? 2280 parts of liptadiene latin (solid content 50%, average particle size 0.35μ, glu content 90%), 1 part sodium stearate, sodium formal, 0.1 part 7' human sulfoxylate, tetrasonium ethylenediamine 90.03 parts of tetraacetic acid, 0.003 parts of ferrous t1itc acid, and 200 parts of water were charged into an autoclave purged with nitrogen gas. After heating the temperature to 65℃,
60 parts of a monomer mixture consisting of 30% acrylonitrile and 70% styrene, 0.3 t-dodecylmercaptan
1 part and 0.2 parts of cumene hydrochloride oxide were added continuously over 4 hours, and after the addition was completed, polymerization was carried out at 65°C for 2 hours. The polymerization rate was 96%. After adding an antioxidant to the obtained latex, it was salted out with Lucium chloride, washed with water, and dried to obtain a white powdery polymer. This is ABS
is displayed.

Example-1 70 parts of polymer A obtained in Experimental Example (1), 70 parts of Polymer A obtained in Experimental Example (31
AB S 30 m and carbon number 24-2 obtained in
Alcohol (CI4-8. Alcohol) 3 parts of tostearic acid ester compound were mixed in a Henshil mixer, and then extruded and pelletized in a vented extruder. The blend contained 0.2 part of the antioxidant Irganox 1076 (manufactured by Ciba Geigy). Thereafter, 0.2% of Irganox 1076 was added to the compositions of all Examples and Comparative Examples.
Part of the content was included. The physical properties of the composition thus obtained are shown in Table 1. Note that ctn~ used here,
6 alcohol is HI 5OCOL manufactured by Ito Oil Co., Ltd.
It is 246.

Examples-2 to 18 and Comparative Examples-1 to 4 Imidized polymers of Polymers A, B, C, and D and Experimental Example (5
) and acrylonitrile-styrene copolymer (AS-H: manufactured by Denki Kagaku Co., Ltd., hereinafter referred to as As), polycargonate (Panrai) K-1300: manufactured by Yodai Kasei Co., Ltd., hereinafter referred to as PC and needle A ready-made product was prepared by mixing each moderately rho primary alcohol/fatty acid ester with a thermoplastic resin containing the respective compounds (shown below), and the physical properties of each were measured and shown in the first column.

The physical properties were measured by the following method.

(1) Impact resistance...notched isot strength, A
According to 8TM-D-256.

(2) Vicat softening point...Load h5#, A S T
According to M-D-1525.

(3) Mechanical strength...bending strength, ASTM-
According to D-760.

(Effects of the Invention) Table 1 shows that the composition of the present invention has significantly improved impact resistance without impairing mechanical strength and heat resistance, compared to compositions containing no higher alcohol fatty acid ester. It will be done.

Claims (2)

[Claims] (1) A thermoplastic resin composition characterized by containing 80 to 99.9 parts by weight of a thermoplastic resin containing a polymer having an imide group in its side chain and 0.1 to 20 parts by weight of higher alcohol fatty acid ester. thing. (2) The polymer having an imide group in the side chain is a rubbery polymer with 0
-30% by weight, 30-90% by weight of aromatic vinyl monomer residues, 10-70% by weight of unsaturated dicarboxylic acid imide derivative residues, and 0-30% by weight of vinyl monomer residues copolymerizable with these.
The composition according to claim 1, which is an imidized copolymer comprising 30% by weight.