JPH04298558A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To provide a heat-resistant resin compsn. which comprises a plurality of thermoplastic resins and has an excellent balance between stiffness and impact resistance. CONSTITUTION:The title compsn. comprises 1-99 pts.wt. glutarimide copolymer consisting of 5-100mol% glutarimide units and 95-0mol% ethylenically alpha,beta-unsatd. monomer units, 1-99 pts.wt. polyamide, and an epoxy polymer in an amt. of 0.1-25 pts.wt. based on 100 pts.wt. the sum of above two resins.

Description

[Detailed description of the invention]

0001

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin composition comprising three types of thermoplastic resins and having various excellent properties.

0002

BACKGROUND OF THE INVENTION Thermoplastic resins have their own characteristics depending on their type, and are used in various fields. Recently, it has been discovered and proposed to mix two or more different types of resin to create a material with higher performance.

[0003] JP-A-59-117550 proposes a polymer blend consisting of polyglutarimide and polyamide that exhibits the characteristics of each.

[0004] JP-A-2-22356 discloses a low-gloss thermoplastic resin composition comprising polyglutarimide, ABS, and polyamide.

[0005]

[Problem to be solved by the invention] Japanese Patent Application Laid-Open No. 59-117
The polymer blend disclosed in Japanese Patent No. 550 has both the heat resistance of polyglutarimide and the excellent mechanical strength of polyamide, but its impact resistance is still insufficient.

[0006] The resin composition of JP-A-2-22356 exhibits the characteristics of the component with a high proportion of the three resin components that make up the composition, but the characteristics of the other components are suppressed and difficult to express. .

[0007] Therefore, it is an object of the present invention to provide a well-balanced resin composition that has high heat resistance, high rigidity, and excellent impact resistance.

[0008]

[Means for Solving the Problems] The present invention provides (A) 5 to 100 mol% of glutarimide units and ethylenic α,
Glutarimide copolymer consisting of 95 to 0 mol% of β-unsaturated monomer units; 1 to 99 parts by weight, preferably 3 to 90 parts by weight
parts by weight, (B) polyamide; 1 to 99 parts by weight, preferably 10 to 97 parts by weight, and (C) epoxy group-containing copolymer; 0.0 parts by weight per 100 parts by weight of the total amount of (A) and (B). 1 to 25 parts by weight, preferably 1 to 20 parts by weight, is provided.

The glutarimide unit of the glutarimide copolymer (A) used in the present invention is represented by the following formula (1).

[Chemical formula 1]

(In [Chemical formula 1], R1 and R2 are a hydrogen atom or a methyl group, and R3 is a hydrogen atom or a carbon number 1
~20 aliphatic, aromatic or alicyclic hydrocarbons. ). Among them, a methyl group in which R3 is hydrogen is particularly excellent in heat resistance, and a cyclohexyl group is excellent in that it has little hygroscopicity.

The glutarimide unit accounts for 5 to 100 mol % in the glutarimide copolymer. Preferably it is 20 mol% or more. If the amount of glutarimide units is small, the resulting resin composition will not have sufficient heat resistance.

Ethylenic α of the glutarimide copolymer,
Examples of the β-unsaturated monomer unit include monomer units such as (meth)acrylic ester, (meth)acrylic acid, styrene, α-methylstyrene, vinyltoluene, chlorostyrene, and acrylonitrile. Examples of (meth)acrylic esters include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, These include ter-butyl meth)acrylate, dodecyl (meth)acrylate, cyclohexyl (meth)acrylate, norbornyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, and benzyl (meth)acrylate units. Note that these monomer units may be used alone or in combination of two or more types.

These monomer units account for 95 to 0 mol % in the glutarimide copolymer.

The weight average molecular weight of the glutarimide copolymer is usually 40,000 to 500,000, preferably 40,000 to 200,000. If the molecular weight is less than 40,000, the mechanical strength is poor,
If it exceeds 10,000, the moldability is poor.

The method for producing the glutarimide copolymer is described in Japanese Patent Publication No. 60-38404 and Japanese Patent Application Laid-open No. 62-89705.
A well-known method such as that described in the above publication may be used, and the method is not particularly limited.

[0017] To give an example, a homopolymer containing (meth)acrylic acid or (meth)acrylic acid ester as an essential component among the monomers exemplified as the ethylenically α,β unsaturated monomer unit mentioned above. Alternatively, it can be obtained by heating and melting the copolymer, mixing with an imidizing agent, and reacting the copolymer. Examples of the imidizing agent include ammonia, methylamine, ethylamine, butylamine, hexylamine, octylamine,
These include norylamine, decylamine, benzylamine, cyclohexylamine, aniline, halogenated aniline, urea, dimethylurea, and the like.

The glutarimide copolymer produced by such a method contains acid and/or acid anhydride units, and preferably 10 mol% or less of such units is present.

In the composition of the present invention, the more the glutarimide copolymer (A) is added, the higher the heat resistance and rigidity become.

[0020] The polyamide (B) used in the present invention is:
It is well known. For example, it is obtained by polycondensation of a lactam having three or more membered rings, a polymerizable ω-amino acid, a dibasic acid, and a diamine.

Specifically, polymers such as ε-caprolactam, aminocaproic acid, enantholactam, 7-aminoheptanoic acid, 11-aminoundecanoic acid, hexamethylene diamine, nonamethylene diamine, undecamethylene diamine, dodecamethylene diamine , polymers obtained by polycondensing diamines such as metaxylidene diamine with dicarboxylic acids such as terephthalic acid, isophthalic acid, adipic acid, sebacic acid, dodecane dibasic acid, and glutaric acid, or copolymers thereof. It will be done.

In other words, aliphatic polyamides such as polyamide 6, polyamide 6,6, polyamide 6,10, polyamide 11, polyamide 12, polyamide 6,12: polyhexamethylene diamine terephthalamide, polyhexamethylene These include aromatic polyamides such as diamine isophthalamide and xylene group-containing polyamides, and copolymers of two or more of these and mixtures of polymers may also be used.

In the composition of the present invention, the higher the amount of polyamide (B), the higher the impact resistance.

The epoxy group-containing copolymer (C) used in the present invention is composed of an ethylenic α, β unsaturated monomer unit having an epoxy group and other ethylenically α, β unsaturated monomer units. It is a copolymer.

The composition ratio of the epoxy group-containing copolymer is not particularly limited, but the amount of ethylenically unsaturated monomer units having epoxy groups is 0.1 to 50% by weight, preferably 1 to 30% by weight.

Examples of the ethylenically α,β unsaturated monomer having an epoxy group include unsaturated glycidyl esters represented by the following formulas [Chemical formula 2] and [Chemical formula 3],
Examples include unsaturated glycidyl ethers.

[Chemical formula 2] (In [Chemical formula 2], R4 is a hydrocarbon group having 2 to 18 carbon atoms and having an ethylenic α, β unsaturated bond.)

[
[Chemical formula 3] (In [Chemical formula 3], R5 is a hydrocarbon group having 2 to 18 carbon atoms and having an ethylenically unsaturated bond, and A is an alkylene oxide group or phenylene oxide group having 1 to 6 carbon atoms. be.)

Specifically, glycidyl (meth)acrylate, itaconic acid glycidyl esters, allyl glycidyl ether, 2-methylallyl glycidyl ether,
Examples include styrene-p-glycidyl ether.

Other ethylenically α,β unsaturated monomers include olefins, vinyl esters of aliphatic carboxylic acids having 2 to 6 carbon atoms, (meth)acrylic esters and maleic esters, and fumaric acid. Examples include esters, vinyl halides, styrenes, nitriles, vinyl ethers, and acrylamides. Specifically, ethylene, propylene, butene-1, vinyl acetate, methyl (meth)acrylate, ethyl (meth)acrylate, dimethyl maleate, diethyl fumarate, vinyl chloride, vinylidene chloride, styrene, acrylonitrile, isobutyl vinyl ether, and Examples include acrylamide. Among these, when lowering the glass transition point and improving impact resistance at low temperatures, ethylene-vinyl acetate and ethylene-vinyl acetate are used.
It is suitable to combine two or more components such as methyl acrylate.

A typical example of the epoxy group-containing copolymer is ethylene-glycidyl methacrylate.

The epoxy group-containing copolymer can be obtained by various well-known methods. For example, an ethylenically α,β unsaturated monomer having an epoxy group and another ethylenically α,β unsaturated monomer are subjected to bulk polymerization or radical polymerization in an inert organic solvent, and then random copolymerization is performed. Method for obtaining a copolymer; impregnating a polymer of other ethylenically alpha, beta unsaturated monomers with an ethylenically alpha, beta unsaturated monomer having an epoxy group, performing radical polymerization, and forming a graft copolymer. There is a way to do it.

Specifically, by applying the high-pressure polyethylene manufacturing method, ethylene and an ethylenically α,β unsaturated monomer having an epoxy group are mixed in the presence of a radical generator,
A method of copolymerization at 00 to 4,000 atm and 100 to 300°C; polypropylene is melted in an extruder, and an ethylenically α, β unsaturated monomer having an epoxy group and a radical generator are added thereto. There are methods such as kneading and graft copolymerization.

In the composition of the present invention, if the epoxy group-containing copolymer (C) is less than 0.1 part by weight, sufficient impact resistance cannot be obtained, and if it exceeds 25 parts by weight, the heat resistance of the composition This is not preferable because the rigidity and moldability decrease.

[0035] The above polymers (A), (B), and (C
) can be blended into a composition using a well-known method. For example, there is a method in which solutions of each polymer are mixed and then the solvent is evaporated or injected into a non-solvent and precipitated; a method in which each polymer is kneaded in a molten state; In addition to methods using commonly used kneading devices such as single-screw or twin-screw extruders and various types of kneaders, there is also a method of kneading directly during melt processing operations such as injection molding and extrusion molding.

The thermoplastic resin composition of the present invention may contain antioxidants such as well-known hindered phenol antioxidants, phosphorus antioxidants, and sulfur antioxidants, ultraviolet absorbers, and hindered amine photostabilizers. Weathering agents such as agents, lubricants,
Antistatic agents, flame retardants, colorants, pigments, etc. can be added, and depending on the purpose, reinforcing fibers such as glass fibers, inorganic fillers, etc. can also be added.

[0037]

[Effects of the Invention] The thermoplastic resin composition of the present invention has an excellent balance of heat resistance represented by heat distortion temperature, impact resistance, and rigidity represented by flexural modulus. For example, it can be used for electrical equipment parts, automobile parts such as automobile interiors and exterior panels, miscellaneous goods, etc.

[0038]

[Examples] The present invention will be further explained by the following examples. The measurement method used in the examples is as follows.

- Heat distortion temperature: Measured under a load of 18.6 kg/cm2 in accordance with ASTM D 648. (℃)

- Impact strength: Notched Izod impact strength was measured in accordance with ASTM D 256. (k
gf・cm/cm)

・Bending elastic modulus: A
Compliant with STM D 790. (kgf/cm2)

Examples 1 to 7, Comparative Examples 1 to 3 Glutarimide copolymer (KAMAX T-150, manufactured by Rohm and Haas; glutarimide unit 75 mol%, acid value 5 mol%) and nylon 6 as the polyamide. (UBE nylon 1013B, manufactured by Ube Industries, Ltd., relative viscosity 2.6),
and JP-A-47-234 as an epoxy group-containing copolymer.
Ethylene 83 produced according to the method described in Publication No. 90
After blending a copolymer of 5% by weight of vinyl acetate and 12% by weight of glycidyl methacrylate (Melt Flow Index 7 (2.16Kg, 190°C, 10 minutes)) in the amounts (parts by weight) listed in Table 1. The resin composition was extruded using a twin-screw extruder at a resin temperature of 250° C. to obtain pellets of the resin composition.

[0043] This pellet was injection molded using an injection molding machine at a cylinder temperature of 260°C and a mold temperature of 60°C to prepare a test piece, and its physical properties were evaluated. The results obtained are shown in Table 1.

[0044]

Claims (1)

[Claims] [Claim 1] (A) 5 to 100 glutarimide units
mole%, and ethylenic α,β unsaturated monomer units: 95
Glutarimide copolymer consisting of ~0 mol%; 1-99
parts by weight, (B) polyamide; 1 to 99 parts by weight, and (
C) Epoxy group-containing copolymer: A thermoplastic resin composition comprising 0.1 to 25 parts by weight based on 100 parts by weight of the total amount of (A) and (B).