JPH0453853A - New thermoplastic resin composition - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a thermoplastic resin composition having excellent mechanical properties such as Izot impact strength, tensile strength and elongation.

[Conventional technology] Polyolefin resin has excellent impact resistance, chemical resistance, cost, etc., and vinyl aromatic hydrocarbon resin has excellent rigidity, heat resistance,
Blends of polyolefin resins with vinyl aromatic hydrocarbon resins are being considered because of their superior cost and other advantages. However, compositions of simple polyolefin resins and vinyl aromatic hydrocarbon resins have inherently poor compatibility, and as a result, impact strength, tensile strength, elongation, etc. are significantly reduced, and they are far from practical.

[Problem to be solved by the invention]

The object of the present invention is to improve such compatibility and provide a thermoplastic resin material consisting of a polyolefin resin and a vinyl aromatic hydrocarbon resin, which has particularly excellent mechanical properties such as impact strength, tensile strength, and elongation. There is uni.

[Means for Solving the Problems] As a result of intensive studies to solve the above problems, the present inventors have developed a modified polyolefin modified with an epoxy group-containing vinyl monomer and a carboquinol compound having an unsaturated bond or its anhydride. The inventors have discovered that a thermoplastic resin composition having excellent compatibility with the vinyl aromatic hydrocarbon resin and excellent mechanical properties can be obtained, and the present invention has been achieved.

That is, the present invention provides: (8) 5 to 95 parts by weight of a resin consisting of 5 to 100% by weight of a modified polyolefin resin modified with an epoxy group-containing vinyl monomer and 95 to 0% by weight of a polyolefin resin, and (B) an unsaturated bond. Carboxymo containing 5 to 100% by weight of a modified vinyl aromatic hydrocarbon resin modified with its anhydride and 95% by weight of a vinyl aromatic hydrocarbon resin.
This is a thermoplastic resin composition containing 95 to 5 parts by weight of a resin consisting of 0 to 0% by weight.

Examples of the polyolefin resin used in the present invention include polypropylene, polyethylene, propylene-ethylene copolymer, ethylene-propylene-dicyclopenkdiene copolymer, ethylene-propylene-ethylidene norbornene copolymer, poly(4-methyl- Penten-1)
Examples include.

The epoxy group-containing vinyl monomer constituting the modified polyolefin resin of the present invention is specifically defined as: macrycidyl methacrylate, glycidyl acrylate, 1,2-epoxy-5-hexene, or the following structural formula (wherein, the total is glycidyl acrylate). C6-C having at least one Kin group
24 aromatic hydrocarbon group, R represents a hydrogen atom or a methyl group) 0HzC=C-C-N-CHz-Ar. For example, an aromatic hydrocarbon having at least one phenolic hydroxyl group and N-methylol acrylamide, or N-methylol methacrylamide, or N-methylol acrylamide, or N-
It can be easily obtained by condensing an alkyl ether derivative of methylolmethacrylamide with an acid catalyst and then glycidylating the phenolic hydroxyl group. Specifically, N-
C4-(2,3-epoxypropoxy)-3,5-dimethylbenzylcoacrylamide, N-C4-(2,3-
epoxypropoxy) 3.5 dimethylhenzylcomethacrylamide, N-[4-(2,3-epoxypropoxy)-3-methylhenzylcomethacrylamide, and the like.

Examples of organic peroxides include methyl ethyl ketone peroxide and cyclohexanone peroxide as ketone peroxide types, lauroyl peroxide and penduyl peroxide as dianrubroxide types, and cumene hydroperoxide and t- Butyl hydroperoxide, dicumyl peroxide, 2,5-dimethyl-2,5-
di(t-butylperoxy) to beef san, di-t-butyl peroxide, 2,5-dimethyl-2,5-di(t-
butylperoxy)hexyne and 3,1,3-bis-
(butylberoquinoisopropyl)henzen, 2,2-di(t-butylperoxy)butane as a peroxyketal type, t-butylberoquinohenzoate as an alkyl perester type, and t as a percarbonate type. -Butylperoquine isopropyl carbonate and the like.

A suitable composition of each component of the modified polyolefin resin is 0.01 to 20 parts by weight, preferably 0.1 parts by weight of the epoxy group-containing vinyl monomer per 100 parts by weight of the polyolefin resin.
~10 parts by weight, and 0.01 to 5 parts by weight of organic peroxide,
Preferably it is 0.03 to 1 part by weight. If the amount of the epoxy group-containing vinyl monomer and organic peroxide added is less than the above range, a sufficient modification effect cannot be obtained, and if it is more than the above range, coloring of the resin and a decrease in molecular weight occur, which is not preferable.

There are no particular limitations on the method for producing the modified polyolefin resin of the present invention. For example, the polyolefin resin, the epoxy group-containing vinyl monomer, and the organic peroxide are reacted in an organic solvent at the decomposition temperature of the organic peroxide while stirring. Manufactured by Alternatively, it is produced by uniformly mixing a polyolefin resin, an epoxy group-containing vinyl monomer, and an organic peroxide using a high-speed stirrer or the like, and then melt-kneading the mixture using a single-screw or multi-screw extruder with sufficient kneading capacity. Reaction temperature in extruder is 150-250'C1 Reaction time is 10 seconds-
30 minutes is preferable. From the viewpoint of economy, it is preferable to produce by melt-kneading using an extruder.

Specific examples of the vinyl aromatic hydrocarbon resin used in the present invention include polystyrene, high impact polystyrene, acrylonitrile-styrene resin, ABS resin, and the like.

Specifically, the carboxyful compound having an unsaturated bond or a collection thereof according to the present invention includes α, β-unsaturated dicarboxylic acids such as maleic acid and itaconic acid, and their acid anhydrides, acrylic acid, and methacrylic acid. amide compounds of unsaturated monocarboxylic acids such as acrylamide and methacrylamide, and compounds having the following structural formula (where n is an integer of 1 to 3).

H, C= C)l-4-C112-C)l 2-+-f
-CH= CH-CH-CH2O Or, specifically, 1,8-hesadienyl-scunninoquan hydride, 1,9-decadienyl-scunninoquan hydride, 1-scunninoquan These include hydride-1,5-hexadiene, 1-succininocouanhydride-1,9-decadiene, and the like.

The organic peroxide used for modifying the vinyl aromatic hydrocarbon resin is the same as the organic peroxide described above.

A suitable composition of each of the above components is 0.01 to 20% by weight, preferably 0.1 to 10% by weight of a carboxyl compound having an unsaturated bond or an anhydride thereof, based on 100% by weight of the vinyl aromatic hydrocarbon resin. , and organic peroxide 0.01
-5% by weight, preferably 0.03-1% by weight. If the amount of carboxyl compound having an unsaturated bond or its anhydride and organic peroxide added is less than the above range, sufficient modification effect will not be obtained, and if it is more than 4M
This is not preferable because it causes coloring of the fat and a decrease in molecular weight.

There are no particular restrictions on the method for producing the modified vinyl aromatic hydrocarbon resin of the present invention; It is produced by reacting a vinyl aromatic hydrocarbon resin, a carboxyl compound having an unsaturated bond or its anhydride, and an organic peroxide in a solvent at the decomposition temperature of the organic peroxide. or
After uniformly mixing the vinyl aromatic hydrocarbon resin, the carboxyl compound having an unsaturated bond or its anhydride, and the organic peroxide using a high-speed stirrer, etc., a single-screw or multi-screw extruder with sufficient kneading capacity is used. Manufactured by melt-kneading. The reaction temperature in the extruder is preferably 150 to 250°C, and the reaction time is preferably 10 seconds to 30 minutes. In the present invention, it is preferable to produce the modified vinyl aromatic hydrocarbon resin in an extruder from the viewpoint of economy.

The ratio of each component constituting the resin (^) of the present invention is 5 to 100% by weight of the modified polyolefin resin, 95 to 0% by weight of the polyolefin resin, preferably 30 to 100% by weight of the modified polyolefin resin, and 70-0% by weight of the polyolefin resin. % range. Further, the ratio of each component constituting the resin (B) is 5 to 100% by weight of the modified vinyl aromatic hydrocarbon resin, 95 to 0% by weight of the vinyl aromatic hydrocarbon resin, preferably 30% by weight of the modified vinyl aromatic hydrocarbon resin. ~100% by weight
, the vinyl aromatic hydrocarbon resin ranges from 70 to 0% by weight.

Further, the ratio υ1 of the resin (A) and the resin (B) constituting the resin composition of the present invention is in the range of 5 to 95% by weight for the resin (A) and 95 to 5% by weight for the resin (B).

There are no particular restrictions on the method for producing the thermoplastic resin composition of the present invention, and after uniformly mixing the above-mentioned resins using a high-speed stirrer or the like, a single-screw or multi-screw extruder with sufficient kneading capacity may be used. It is manufactured by melt-kneading.

In addition, depending on the purpose, various elastomers, pigments, dyes, reinforcing agents such as glass fiber, metal fiber, carbon fiber, talc,
Fillers such as calcium carbonate, antioxidants, ultraviolet absorbers, lubricants, flame retardants, antistatic agents, conductive carbon, and the like can be added.

EXAMPLES: Examples The present invention will be explained in more detail with reference to Examples below. Note that the physical property evaluations described in Examples and Comparative Examples were performed according to the following method.

(1) Eye impact strength Based on JIS-7110.

(2) Tensile strength and elongation Compliant with JIS-7113.

Reference Example 1 Polypropylene resin [manufactured by Mitsui Toatsu Chemical Co., Ltd., trade name: Mitsui Noblen JS-GE] 100 parts by weight, glycidyl methacrylate 2 parts by weight, dicumyl peroxide 0.
After mixing 1 part by weight in a Henschel mixer, the mixture was extruded into pellets using a twin-screw extruder with a screw diameter of 30 mm and L/D = 30 at a melting temperature of 200°C and a screw rotation speed of 1100 rp, resulting in a modified polypropylene resin. And so.

Reference Example 2 Propylene-ethylene propylene copolymer resin: manufactured by Seito Atsushi Kagaku Co., Ltd., trade name: Mitsui Noblen BEB-GI 10
0 parts by weight, h-:4-(2,3-epoxypropoquine)
-3-Methylhensyl:acrylamide] manufactured by Kanebuchi Kagaku Co., Ltd. 11 parts by weight, 1,3-bis-(t-butylperoxy-isopropyl) Hensen 1-layer lid was mixed in a Henschel mixer, and then mixed with a screw diameter of 30 mm. L/D=
A modified propylene-ethylene bronok copolymer was extruded into pellets using a No. 30 twin-screw extruder at a melting temperature of 210°C and a screw rotation speed of 1100 rpm.

Reference Example 3 Polyethylene resin manufactured by Nimitsui Petrochemical Co., Ltd., trade name HIZESOX 2200J, 3100 parts by weight, N-(4-(2,
3-epoxypropoquine)-3,5-dimethylhensyl]methacrylamide 1'1 Manufactured by Kanebuchi Chemical Co., Ltd.: 1 part by weight, 2,5-dimethyl-2,5-di(t-butylperoxy) ) After mixing 0.3 parts by weight of hexane in a Henschel mixer, the mixture was heated to a melting temperature of 200°C and a screw rotation speed of 11 using a twin-screw press ratio machine with a screw diameter of 30 mm and L/D = 30.
A modified polyethylene resin was extruded into pellets at 00 rpm.

Reference Example 4 Polystyrene resin: manufactured by Mitsui Toatsu Chemical Co., Ltd., trade name Topolenox 550-05] 1100 parts by weight Maleic anhydride 1 part by weight, 1,3-bis-(t-butylperoxy-isopropyl)hen 20. After mixing 3 parts by weight with a Henschel mixer, screw diameter 30 mm, L
A modified polystyrene resin was extruded into pellets at a melting temperature of 200° C. and a screw rotation speed of 200 rpm using a twin-screw extrusion ratio machine of /D=30.

Reference example 5 High impact polystyrene resin [Mitsui Toatsu Chemical Co., Ltd.]
100 parts by weight of Topolenox 830-05, 2 parts by weight of acrylic acid, 0.1 parts of dicumyl peroxide
The weight parts were mixed in a Henschel mixer and then extruded into pellets using a twin-screw extruder with a screw diameter of 30 mm and L/D 30 at a melting temperature of 200°C and a screw rotation speed of 1100 rpm to obtain a modified high-impact polystyrene resin. And so.

Reference example 6 ABS resin ε Manufactured by Mitsui Toatsu Kagaku Co., Ltd. Product name Suncook 5T-s3 ]oo heavy part, ], 9-decadienyl-
Sukunninoku - 2 parts by weight of anhydride, 1,3-
After mixing 0.1 part by weight of bis-(t-butylperoxy-isopropyl)benzene in a Henschel mixer, the mixture was heated to a melting temperature of 200°C and a screw rotation speed using a twin-screw presser with a screw diameter of 30 mm and a L/D of 30. A modified ABS resin was extruded into pellets at 1100 rpm.

Examples 1 to 18 Using the modified resins and unmodified resins obtained in Reference Examples 1 to 6, the melting temperature was in the range of 200 to 250 °C in the twin screw press ratio machine at the ratios shown in Tables 1 to 3, Screw rotation speed 1100
It was extruded into pellets using RP. Physical property tests were conducted using test pieces injection molded from this pellet, and the results are shown in Tables 1-
Shown in 3. It has sufficient mechanical properties to withstand practical use.

Comparative Examples 1 to 12 Table 1 shows the results when no modified resin was used in Examples 1 to 8, or when only one modified resin was used.
~3. Mechanical properties are extremely low and cannot be put to practical use.

[Effects of the present invention]

The thermoplastic resin composition of the present invention is I! It has excellent mechanical properties and can be used in the automobile field, home appliance field, industrial parts, etc., and has great utility value.

Claims (1)

[Scope of Claims] 1) (A) 5 to 95 parts by weight of a resin consisting of 5 to 100% by weight of a modified polyolefin resin modified with an epoxy group-containing vinyl monomer and 95 to 0% by weight of a polyolefin resin, and (B) unsaturated. Modified vinyl aromatic hydrocarbon resin modified with a carboxyl compound having a bond or its anhydride 5-
100% by weight and vinyl aromatic hydrocarbon resin 95-0
A thermoplastic resin composition containing 95 to 5 parts by weight of a resin. 2) The thermoplastic resin composition according to claim 1, wherein the modified polyolefin resin is obtained by melt-kneading a polyolefin resin, an epoxy group-containing vinyl monomer, and an organic peroxide in an extruder. 3) The modified vinyl aromatic hydrocarbon resin is obtained by melt-kneading a vinyl aromatic hydrocarbon resin, a carboxyl compound having an unsaturated bond or an anhydride thereof, and an organic peroxide in an extruder. The thermoplastic resin composition according to claim 1.