JPH0457847A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To prepare the title compsn. having high heat resistance and rigidity as well as an excellent resistance to impact, solvent, and oil by compounding a specific glutarimide, a polyamide, a specific rubber-contg. copolymer, and a specific epoxidized copolymer. CONSTITUTION:The title compsn. comprises 5-75 wt.% glutarimide copolymer consisting of 5-100 mol% glutarimide units and 95-0 mol% ethylenically alpha,beta- unsatd. monomer units, 10-80 wt.% polyamide, 10-80 wt.% rubber-contg. copolymer obtd. by copolymerizing 90-20 wt.% at least one monomer selected from the group consisting of an arom. ethylenically alpha,beta-unsatd. monomer, an ethylenically alpha,beta-unsatd. nitrile monomer, and an ethylenically alpha,beta-unsatd. carboxylic ester monomer in the presence of 10-80 wt.% rubberlike polymer, and 0.1-20 wt.% epoxidized copolymer.

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to a resin composition comprising four types of thermoplastic resins and having various excellent properties.

<Prior Art> Thermoplastic resins have different 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.

Japanese Patent Publication No. 60-38404 proposes a method for producing a glutarimide polymer and blending the polymer with an ABS resin or an MBS resin as an impact modifier.

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

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

<Problems to be Solved by the Invention> In the blend of the glutarimide polymer and the impact modifier disclosed in Japanese Patent Publication No. 60-38404, the ratio of the impact modifier is required to meet the demand for higher impact resistance. As the heat resistance becomes higher, the heat resistance characteristic of the glutarimide polymer becomes insufficient.

Furthermore, this blend does not have sufficient oil resistance or solvent resistance.

The polymer blend disclosed in JP-A-59-117550 has both the heat resistance of polyglutarimide and the excellent mechanical strength of polyamide, but its impact resistance is still insufficient.

The resin composition of JP-A-2-22356 exhibits the characteristics of the component with a high proportion among the three resin components that constitute it, but the characteristics of the other components are suppressed and difficult to express.

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

(Means for Solving the Problems) The present invention provides (A) a glutarimide copolymer comprising 5 to 100 mol% of glutarimide units and 95 to 0 mol% of ethylenically α,β unsaturated monomer units. ;5-75% by weight
, (B) polyamide; 10 to 80% by weight, (C) [1]
In the presence of 10 to 80% by weight of a rubbery polymer, ■ aromatic ethylenically αβ unsaturated monomer, ethylenically α, β unsaturated monomer containing a cyan group, ethylenically α, β unsaturated carboxylic acid A rubber-containing copolymer obtained by polymerizing 90 to 20% by weight of at least one unsaturated monomer selected from ester monomers; 10 to 80% by weight, and (D) an epoxy group-containing copolymer; The present invention provides a thermoplastic resin composition comprising 0.1 to 20% by weight.

The glutarimide unit of the (^) glutarimide copolymer used in the present invention has the general formula (1)% formula% (In formula (1), R1 and R2 are hydrogen atoms or methyl groups, R3 is hydrogen atoms or carbon number 1 to 20 aliphatic,
) represents an aromatic or alicyclic hydrocarbon.

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 is 5 in the glutarimide copolymer.
~100 mol%.

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.

Ethylenically α,β unsaturated monomer units of the glutarimide copolymer include monomers such as (meth)acrylic acid ester, (meth)acrylic acid, styrene, α-methylstyrene, vinyltoluene, chlorostyrene, and acrylonitrile. Examples include mercury units.

Examples of (meth)acrylic esters include methyl (meth)acrylate, ethyl (meth)acrylate, (
Propyl (meth)acrylate, isobutyl (meth)acrylate, isobutyl (meth)acrylate, ter-butyl (meth)acrylate, dodecyl (meth)acrylate, (
cyclohexyl meth)acrylate, norbornyl (meth)acrylate, 2-ethylhexyl (meth)acrylate,
(meth)acrylic acid Hensyl unit, etc.

Note that these monomer units may be used alone or in combination of two or more types.

These monomer units are 95% in the glutarimide copolymer.
~0 mol%.

The weight average molecular weight of glutarimide copolymer is usually 40,000~
500,000, preferably 40,000 to 200,000.

If the molecular weight is less than 40,000, the mechanical strength will be poor, and if it exceeds 500,000, the moldability will be poor.

The method for producing glutarimide copolymer is described in Japanese Patent Publication No. 60-3.
Well-known methods such as those described in JP-A No. 8404 and JP-A-62-89705 may be used, and there are no particular limitations.

- For example, (meth)acrylic acid or
It can be obtained by heating and melting a homopolymer or copolymer containing (meth)acrylic acid ester as an essential component, mixing with an imidizing agent, and reacting the mixture.

Examples of the imidizing agent include ammonia, methylamine,
These include ethylamine, butylamine, hexylamine, octylamine, norylaminedecylamine, benzylamine, cyclohexylamine, aniline, halogenated aniline, urea, and dimethylurea.

The glutarimide copolymer produced by this method has
Although acid and/or acid anhydride units are present, it is preferred that such units be present in an amount of 10 mol% or less.

The composition of the present invention is characterized in that (A) the glutarimide copolymer contains 5
-75% by weight, preferably 10-65% by weight.

If it is less than 5% by weight, only a composition with extremely low heat resistance will be obtained, and if it exceeds 75% by weight, the impact resistance of the composition will decrease, which is not preferable.

The polyamide (CB) used in the present invention is well known.

For example, lactams with three or more membered rings, polymerizable ω amino acids,
It is obtained by polycondensation of 1 m of 2 salt and diamine, etc.

Specifically, ε-caprolactam, aminocaproic acid,
Polymers such as enantholactam, 7-aminohebbutanoic acid, 11-aminoundecanoic acid, hexamethylene diamine,
Obtained by polycondensing diamines such as nonamethylene diamine, undecamethylene diamine, dodecamethylene diamine, and metaxylidene diamine with dicarboxylic acids such as terephthalic acid, isophthalic acid, adipic acid, cepatic acid, dodecane dibasic acid, and glutaric acid. or copolymers thereof.

In other words, polyamide 6, polyamide 6.6,
Polyamide 6.10, Polyamide 11, Polyamide 12
, polyamide 6, ]2, aromatic polyamides such as polyhexamethylene diamine terephthalamide, polyhexamethylene diamine isophthalamide, xylene group-containing polyamide, etc. It may also be a polymer or a mixture of polymers.

In the composition of the present invention, the polyamide (B) has a content of 10 to 80
% by weight, preferably 15-70% by weight, 1
If it is less than 0% by weight, the oil resistance and solvent resistance of the composition will be insufficient, and if it exceeds 80% by weight, the heat resistance and impact resistance of the composition will decrease, which is not preferable.

The rubber-containing copolymer (C) used in the present invention is a rubbery polymer, such as polybutadiene rubber.

Acrylonitrile-butadiene copolymer rubber.

In the presence of styrene-butadiene copolymer rubber, ethylene-propylene-diene copolymer rubber, etc. Ethylenic α, β unsaturated monomers, such as acrylonitrile, methacrylotrile, etc., ethylenically α, β unsaturated carboxylic acid ester monomers, such as methyl (meth)acrylate, ethyl (meth)acrylate, etc. At least one monomer selected from
Polymers obtained by polymerization such as suspension polymerization, or
This polymer is mixed with polymers of these monomer units.

Typical examples include so-called ABS resin, MBS resin, A
Examples include BS resin.

The proportion of the rubbery polymer in this rubber-containing copolymer is preferably 10 to 80% by weight, particularly 30 to 70% by weight.

If the proportion of the rubbery polymer is less than 10% by weight, the resulting composition will have insufficient impact resistance, and if it exceeds 80% by weight, the resulting composition will have low rigidity and poor heat resistance. Undesirable.

In the composition of the present invention, the rubber-containing copolymer (C) contains 10
-80% by weight, preferably 15-70% by weight.

If it is less than 10% by weight, the impact resistance of the composition is insufficient;
If it exceeds 80% by weight, the heat resistance, rigidity, oil resistance,
This is not preferable because it reduces solvent resistance.

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

There is no particular restriction on the composition ratio of the epoxy group-containing copolymer, but
The ethylenically unsaturated monomer unit having an epoxy group is 0.
It is 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 and unsaturated glycidyl ethers represented by general formulas (2) and (3) below. .

It is a hydrocarbon group having a prime number of 2 to 18. ) (R 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.) Specifically, glycidyl (meth) ) Acrylate, itaconic acid glycidyl esters, allyl glycidyl ether, 2-methylallyl glycidyl ether, styrene-p
Examples include 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, maleic esters, fumaric esters, Examples include vinyl halides, styrenes, nitriles, vinyl ethers, and acrylamides.

Specifically, ethylene, propylene, butene 1, vinyl acetate, methyl (meth)acrylate, (meth)ethyl acrylate, dimethyl maleate, diethyl fumarate, vinyl chloride, vinylidene chloride, styrene, acrylonitrile,
Examples include isophthyl vinyl ether and 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.

Typical examples of epoxy group-containing copolymers include ethylene-
Contains glycidyl methacrylate.

Epoxy group-containing copolymers 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. How to obtain coalescence; other ethylenic α
There is a method in which a polymer of a β-unsaturated monomer is impregnated with an ethylenic α,β-unsaturated monomer having an epoxy group, and radical polymerization is performed to obtain a graft copolymer.

Specifically, by applying a high-pressure polyethylene manufacturing method, ethylene and an ethylenically α,β unsaturated monomer having an epoxy group are mixed in a 500 to 4,0
A method of copolymerizing at 00 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 and kneaded. There are methods such as graft copolymerization.

In the composition of the present invention, (D) the epoxy group-containing copolymer is present in an amount of 0.1 to 20% by weight, or 0.5 to 10% by weight.

If it is less than 0.1% by weight, sufficient impact resistance, oil resistance, and solvent resistance cannot be obtained, and if it exceeds 20% by weight, the heat resistance of the composition
This is not preferable because the rigidity and moldability decrease.

A well-known method can be used to blend the above polymers (A), (B), (c) and (D) to form a composition.

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 to precipitate; a method in which each polymer is kneaded in a molten state, and the melt mixture is -
In addition to the method using a kneading device such as a single or twin screw extruder or various kneaders used in 11R, there is also a method of directly kneading during a melt processing operation such as injection molding or extrusion molding.

The thermoplastic resin composition of the present invention contains antioxidants such as well-known hindered phenol antioxidants, phosphorus antioxidants, and sulfur antioxidants, as well as ultraviolet absorbers and hindered amine light stabilizers. Weathering agents, lubricants, antistatic agents,
It is also possible to add flame retardants, colorants, pigments, etc.
Further, depending on the purpose, reinforcing fibers such as glass fibers, inorganic fillers, etc. may also be blended.

<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, rigidity represented by flexural modulus, and oil resistance and solvent resistance. These properties can be utilized in various applications, such as electrical equipment parts, automobile parts such as automobile interiors and exterior panels, and miscellaneous goods.

<Example> The present invention will be further explained below with reference to Examples.

The measurement method used in the examples is as follows.

Heat distortion temperature: 18, according to ASTM D 648
6 kg/cm! Measure load L7.

Oil resistance :Drop brake oil onto the test piece and left at room temperature for 4 hours. Visually observe the subsequent changes, ○ Those that are not eroded Items with a little erosion△ Significant erosion and unevenness on the surface Some things were marked as x.

Examples 1-6, Comparative Examples 1-7 Luimito copolymer (KAMAX 8T-150
, l1ff-manufactured by M&Haas; glutarimide unit 75 mol%, acid value 5 mol%), nylon 6 (UBE nylon 1013B, manufactured by Ube Industries, Ltd., relative viscosity 2.6) as a polyamide, and a rubber-containing copolymer. ABS resin (Clarastic" MV resident - Manufactured by Gatak ■, 2
Melt 7 at 20tlOktr 9)
and JP-A-47-234 as a uboxy group-containing copolymer.
Ethylene 83 produced according to the method described in Publication No. 90
Copolymer of 5% by weight of vinyl acetate and 12% by weight of glycidyl methacrylate (Melt 7)
(2.16Kg, 1.90℃, 10 minutes)) in the amounts listed in Table 1, and then heated to a resin temperature of 25% using a twin-screw extruder.
A pellet of the resin composition was obtained by extrusion at 0°C.

Konohele left cylinder temperature 26 using injection molding machine
Test pieces were prepared by injection molding at 0°C and a mold temperature of 60°C, and their physical properties were evaluated.

The results obtained are shown in Table 1.

Claims (1)

[Claims] (1) (A) 5 to 100 mol% of glutarimide units,
and glutarimide copolymer consisting of 95 to 0 mol% of ethylenically α,β unsaturated monomer units; 5 to 75% by weight; (B) polyamide; 10 to 80% by weight; (C) [1] Rubber [2] Aromatic ethylenically α, β unsaturated monomer, ethylenically α, β unsaturated monomer having a cyan group, ethylenically α, β unsaturated monomer in the presence of 10 to 80% by weight of the A rubber-containing copolymer obtained by polymerizing 90 to 20% by weight of at least one monomer selected from saturated carboxylic acid ester monomers; 10 to 80% by weight, and (D) an epoxy group-containing copolymer. ;0.1-20% by weight,
A thermoplastic resin composition consisting of: