JPS6227456A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To provide the titled compsn. having excellent resistance to oils, heat and impact, consisting of a polyphenylene ether resin, a specified copoly mer, a polyamide and an impact modifier. CONSTITUTION:5-95wt% polyphenylene ether resin (A) obtd. by the oxidative coupling polymn. of a phenol compd. of formula I [wherein X is H, Cl, Br or I; R is a (halogenated) hydrocarbon(oxy) group; R, is R or a halogen; R2 and R2 are each H or R, and do not contain any tertiary hydrocarbon atom] in the presence of a catalyst, 0.5-90wt% copolymer (B) obtd. by copolymerizing a styrene monomer and at least one monomer selected from among unsaturated compds. contg. an epoxy group and having formulas II, III [wherein R is H or a (glycidyl ester group-substed.) lower alkyl group], alpha,beta-unsaturated acids and (meth)acrylate esters 1-90wt% polyamide (C) and 0-80wt% impact modifier (D) (e.g. styrene/butadiene block copolymer) are blended together.

Description

DETAILED DESCRIPTION OF THE INVENTION a. Field of Industrial Application The present invention relates to a highly heat-resistant thermoplastic resin composition with excellent oil resistance.

b. Conventional technology Polyphenylene ether resin has excellent mechanical properties, electrical properties, heat resistance, and good dimensional stability, so it is attracting attention as a resin suitable for a wide range of applications. However, its major drawbacks are poor moldability, impact strength, and oil resistance to chemicals such as gasoline.

In order to improve the molding processability of polyphenylene ether resin, it was proposed to incorporate polyamide into the polyphenylene ether resin.
Although it is proposed in Publication No. 7, polyphenylene ether resin and polyamide have very poor compatibility, and the resulting resin composition has poor mechanical properties (especially when the polyamide content exceeds 20%). (inferior), molded products obtained by injection molding of the resin composition exhibit delamination phenomenon,
A desirable molded product cannot be obtained.

In addition, in order to improve moldability and impact resistance,
No. 3-17812, JP-A No. 49-98858, etc. propose blending polystyrene or rubber-reinforced polystyrene with polyphenylene ether resin, but these resin compositions also have poor oil resistance. .

Acid resins made of rubber-reinforced polystyrene/polyphenylene resins have excellent impact resistance and moldability, and are produced in large quantities industrially, but their range of use is limited due to their poor oil resistance. Limited.

Furthermore, in JP-A No. 57-36150, oil-resistant properties are obtained by blending a copolymer consisting of a styrene compound and an α,β-unsaturated dicarboxylic anhydride into a composition of polyphenylene ether and polyamide. It is described that a resin composition with high heat resistance and high heat resistance can be obtained. However, this composition may cause foaming during molding, which is believed to be due to decomposition of the dicarboxylic acid anhydride, which may impair the appearance of the molded product.

C6 Problems to be Solved by the Invention The inventors of the present invention have conducted intensive studies to obtain a resin composition that has not only oil resistance but also high heat resistance and high impact strength, and can be used in a wide range of applications. , polyphenylene ether resin and polyamide, as well as styrenic monomer and epoxy base, unsaturated compounds, α, β-unsaturated acids and (meth)
By blending a copolymer containing a small amount of acrylic acid ester as a component and, if necessary, an impact strength reinforcing agent, a resin composition with unprecedented performance can be created. The present invention has been achieved based on this finding.

d. Means for solving the problem, that is, the present invention, +a+ Polyphenylene ether resin 5-95ff
lff1%, (b) Single styrenic substance, epoxy group-containing unsaturated compound, α, β-unsaturated acid and (meth)
0.5 to 90% by weight of a copolymer obtained by copolymerizing at least one selected from acrylic esters, (c1
The present invention provides a thermoplastic resin composition comprising 1 to 90% by weight of polyamide and 0 to 80% by weight of (dl impact reinforcement).

The polyphenylene ether resin as component (a) used in the present invention is obtained by oxidative coupling polymerization of one or more phenolic compounds represented by the general formula (1) in the presence of a known catalyst. It is something that can be done.

-C Among the compounds of formula (1), particularly preferred are the phenol compounds represented by the general formula ([1), and specific examples of the most preferred phenol compounds include 2.6-dimethylphenol, 2.6-dimethylphenol, and 2.6-dimethylphenol. -diethylphenol, 2-methyl-
6-ethylphenol, 2-methyl-6-allylphenol, 2-methyl-6-phenylphenol, 2,6-
diphenylphenol, 2,6-sibutylphenol,
2-Methyl-6-propylphenol, 2.3.6-1
-limethylphenol, 2,3-dimethyl-6-ethylphenol, 2,3.6-driethylphenol, 2.
Examples thereof include 3.6-)lipropylphenol, 2,6-dimethyl-3-ethylphenol, and 2,6-dimethyl-3-propylphenol.

Specific examples of the most preferred polyphenylene ethers include polyphenylene ether obtained from 2,6-dimethylphenol and polyphenylene ether obtained by copolymerization of 2,6-dimethylphenol and 2,3,6-dolimethylphenol. be. Also used is polyphenylene ether graft copolymerized with a styrene monomer. The copolymerized polyphenylene ether obtained from 2.3.6-1-limethylphenol and 2.6-dimethylphenol has good heat resistance, impact resistance, processability, and resistance to agents.

The intrinsic viscosity [η] (measured in chloroform at 30°C) of the polyphenylene ether resin (8) used in the present invention is not particularly limited, but is preferably 0.2 to ld.
j! /g, more preferably 0.25-0.7dA
/g. The blending amount of polyphenylene ether resin in the thermoplastic resin composition of the present invention is 5 to 95% by weight.
The content is preferably 10 to 60% by weight, more preferably 10 to 50% by weight. If the amount of polyphenylene ether resin is less than 5% by weight, no remarkable effect on improving heat resistance will be observed, and if it exceeds 95% by weight, solvent resistance and processability will be poor.

The styrenic monomers used in the component of the present invention include styrene, α-methylstyrene, P-methylstyrene, vinylxylene, monochlorostyrene, dichlorostyrene, monobromostyrene, dibromostyrene, P-j
Examples include ert-butylstyrene, ethylstyrene, and vinylnaphthalene, and these may be used alone or in combination of two or more. A particularly preferred styrenic monomer is styrene.

As the epoxy group-containing unsaturated compound, all compounds having an unsaturated group and an epoxy group in the molecule can be used.

Preferred epoxy group-containing unsaturated compounds include the following general formula (II) C11□-C-C-0-CIl□-CIl-C1l□1
! 1 \7/ and the following general formula (rV)CHz ”
C-CHz-0-Cll□-C11-CI! There is a compound represented by □O [R in the formula is the same as above].

Preferred specific examples include glycidyl acrylate, glycidyl methacrylate, glycidyl ethacrylate, glycidyl itaconate, and allyl glycidyl ether. Particularly preferred epoxy group-containing unsaturated compounds include glycidyl acrylate, glycidyl methacrylate, and allyl glycidyl ether. It is. These epoxy group-containing unsaturated compounds may be used alone or in combination of two or more.

Examples of α,β-unsaturated acids include acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, itaconic acid, and maleic acid. Preferred are acrylic acid and methacrylic acid.

These α,β unsaturated acids may be used alone or in combination of two or more.

The (meth)acrylic acid ester is preferably an alkyl ester having 1 to 20 carbon atoms, more preferably 1 to 20 carbon atoms.
~6 alkyl ester. Specific examples of these include methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, amyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate, dodecyl acrylate, octadecyl acrylate, phenyl acrylate, benzyl acrylate, etc. Acrylic acid alkyl ester, methyl methacrylate, ethyl methacrylate, butyl methacrylate, amyl methacrylate,
Hexyl methacrylate, octyl methacrylate, 2
- Methacrylic acid alkyl esters such as ethylhexyl methacrylate, cyclohexyl methacrylate, dodecyl methacrylate, octadecyl methacrylate, phenyl methacrylate, and benzyl methacrylate.

The fbl component of the present invention is a copolymer of the styrenic monomer and the epoxy group-containing unsaturated compound, a copolymer of the styrenic monomer and the α, β unsaturated acid or its ester, and copolymers of styrene monomers and two or more monomers selected from epoxy group-containing unsaturated compounds, α, β-unsaturated acids, and esters thereof.

Among the monomers to be copolymerized with the styrene monomer, those selected from epoxy group-containing unsaturated compounds and α,β-unsaturated acids are more preferable.

The fbl component of the present invention contains 99 to 60% by weight of a styrenic monomer, and 1 to 40% of at least one monomer selected from the group consisting of an epoxy group-containing unsaturated compound and an α,β-unsaturated acid. From the viewpoint of compatibility, it is preferable that the composition be the same.

It is also possible to copolymerize and contain 10% by weight or less of another vinyl monomer copolymerizable with the above-mentioned monomers in the fbl component. Examples of the other copolymerizable vinyl monomers include vinyl cyanide compounds such as methacrylate trile and acrylonitrile.

The component (b) of the present invention is composed of the polyamide of the fc) component and the component (a).
It functions to increase compatibility with the polyphenylene ether resin of component 1. This is an epoxy group-containing unsaturated compound in component Cb, methacrylic acid, acrylic acid,
This seems to be due to the chemical reaction between (meth)acrylic acid ester and polyamide. It is better to use an epoxy group-containing unsaturated compound from the viewpoint of the appearance of the molded article of the thermoplastic resin composition obtained.

(Among the bl components, among the compounds that copolymerize with the styrene monomer, epoxy group-containing unsaturated compounds and α,
At least one selected from β-unsaturated acids is more preferred.

Component (1) may also be a rubber-reinforced copolymer. The rubber reinforced copolymer comprises polybutadiene rubber,
In the presence of a rubbery polymer such as styrene-butadiene rubber, polybutene rubber, hydrogenated styrene-butadiene rubber, acrylonitrile-butadiene rubber, ethylene-propylene rubber, polyacrylate rubber, polyisoprene rubber, natural rubber, etc. Obtained by polymerizing the body.

The bl component used in the present invention can be produced by conventional bulk polymerization, solution polymerization, suspension polymerization, or emulsion polymerization using radical polymerization.

The amount of the bl component used in the thermoplastic resin composition of the present invention is 0.5 to 90% by weight, preferably 1 to 70% by weight.
, more preferably 2 to 50 double stars. If the amount is less than 0.5% by weight, the resulting molded article will peel off.

In addition, heat resistance is poor when the 1990s economy is exceeded.

The (c+ main component polyamide of the present invention) is a copolymer of nylon-6, nylon 6.6, nylon 6.10, nylon-11, nylon-12, nylon-4,6, terephthalic acid and trimethylhexamethylene diamine. , poly (
These are copolymers of xylylene diamine such as (meth-xylylene adipamide) and aliphatic carboxylic acids, and copolymers and modified products thereof.

The amount of these polyamides used is 1 to 90% by weight,
Preferably 5 to 70% by weight, more preferably 10 to 6%
It is 0% by weight. If it is less than 1% by weight, the oil resistance will be insufficient, and if it exceeds 90% by weight, the compatibility will decrease and the resulting molded product will peel off, and the heat resistance will also decrease.

The impact strength reinforcing agent of the +dl component, which has a large effect of improving impact strength, used in the present invention is a graft copolymer obtained by graft polymerizing a monomer mainly composed of a styrene monomer to a rubber-like polymer; Various thermoplastic elastomers are preferred.

The above-mentioned graft copolymer is a polymer obtained by emulsion graft polymerization of a styrene monomer to a latex-like rubbery polymer, or a polymer obtained by emulsion graft polymerization of a styrene monomer to a latex-like rubbery polymer, or a polymer obtained by subjecting a rubbery polymer to a solvent containing a styrene monomer as the main component. It refers to a polymer obtained by dissolving the polymer and polymerizing the solution by methods such as bulk polymerization, solution polymerization, and suspension polymerization. Examples of the rubbery polymer used here include polybutadiene, styrene-butadiene copolymer, ethylene-propylene copolymer, ethylene-propylene-polyene copolymer, polyacrylic acid ester, and polyisoprene. The styrene monomers used here include all monomers of the bl component mentioned above.
Monomers used with #mer include acrylic ester, methacrylic ester, acrylonitrile,
Examples include methacrylonitrile.

The content of the monomer copolymerized with the styrene monomer is preferably 10% by weight or less based on the total monomers from the viewpoint of compatibility. Although commercially available impact-resistant polystyrene can also be used as an impact strength reinforcing agent, more preferred graft copolymers are those with a high content of rubbery polymers, preferably Content is 1
It is 2% by weight or more, more preferably 30 to 70% by weight. The rubber particle size in the graft copolymer ranges from small particles (0.05 to 0.8 μm) obtained by emulsion polymerization to large particles (0.5 to 3 μm) obtained by bulk polymerization, solution polymerization, and suspension polymerization.
Up to m) can be used.

The above various thermoplastic elastomers include styrene-butadiene block copolymer, hydrogenated styrene-butadiene block copolymer, ethylene-propylene elastomer, styrene-grafted ethylene-propylene elastomer, thermoplastic polyester elastomer, and ethylene-based ionomer resin. and so on.

Styrene-butadiene Bronok copolymer has AB type,
Includes ABA type, ABA taper type, radial teleblock type, etc. In addition, one type or two or more types of impact reinforcing agents may be used.

Furthermore, other polymers may be blended with the thermoplastic resin composition of the present invention. Among these, polymers containing 80% by weight or more of styrenic monomers are particularly preferred from the viewpoint of improving moldability.

When component (b) specified in the present invention is mixed with the tc+ component, both polymers cause a chemical reaction with each other, forming a special polymer, and improving compatibility with the (al) component. In order to speed up this chemical reaction, a known catalyst may be added to the extent that it does not adversely affect the physical properties.

When using the thermoplastic resin composition of the present invention, glass fibers, carbon fibers, metal fibers, glass beads, asbestos,
Fillers such as walrus night, calcium carbonate, talc, and barium sulfate can be used alone or in combination. Among these fillers, glass fibers and carbon fibers preferably have a fiber diameter of 6 to 60 μm and a fiber length of 30 μm or more. It is preferable that these fillers are contained in an amount of 5 to 150 parts by weight based on 100 parts by weight of the thermoplastic resin composition.

Additionally, known additives such as flame retardants, antioxidants, desensitizers, colorants, and lubricants may be added. Preferred flame retardants are phosphorus-based flame retardants.

Furthermore, other polymers, such as polyethylene, polypropylene, polyester, etc., can be incorporated in amounts that do not impair the mechanical properties.

The thermoplastic resin composition of the present invention can be obtained by melt-mixing the above-mentioned components using an extruder roll mixer, a Banbury mixer, a kneader mixer, or the like.

Regarding the order of melt-mixing, all the components may be melt-mixed at the same time, two or three components may be melt-mixed in advance, or other components may be melt-mixed at the same time when graft polymerizing the styrene compound to the polyphenylene ether resin. A method such as melt-mixing some of the components can be used. fbl
In order to strengthen the reaction or interaction between the component and the polyamide, (bl component and polyamide are melt-mixed, and then other components are added and melt-mixed to form the thermoplastic resin composition of the present invention. In some cases, a method of obtaining the following is preferable in terms of mechanical properties and the like.

d. Examples Next, the present invention will be explained in more detail with reference to Production Examples and Examples, but these are merely illustrative and do not limit the content of the present invention.

Note that in each side below, parts and % indicate parts by weight and % by weight, respectively.

Production Example Polyphenylene ether used in Example and Comparative Example was obtained by the following method.

1) After thoroughly purging the inside of the stainless steel reactor, which is equipped with an oxygen blower, a cooling coil, and a stirrer at the bottom of the reactor for making polymer Ai (polyphenylene ether), with nitrogen,
53.6 g of cupric bromide, 111 g of di-n-butylamine
Further, 8.75 kg of 2.6-xylenol was dissolved in toluene 4 (H!) and added. After stirring to make a homogeneous solution, polymerization was carried out for 90 minutes while rapidly blowing oxygen into the reaction vessel. During the polymerization, water was circulated through a cooling coil to maintain the internal temperature at 30° C. After the polymerization was completed, 307! of toluene was added, and a 20% aqueous solution of 430 g of disodium ethylenediaminetetraacetate dissolved in water was added. The reaction was stopped.

The polymer solution phase was removed from the resulting product mixture by centrifugation. While stirring the polymer solution phase vigorously, methanol was gradually added to form a slurry. After separation, the polymer was thoroughly washed with methanol, further separated, and then dried to obtain Polymer A-1.

2) Production of Polymer A-2 (Polyphenylene Ether) In the production of Polymer A-1, a phenol compound was added to 2.
Polymerization was performed using 6-xylenol/2,3.6-drimethylphenol (molar ratio) of 90/10 to obtain polymer A-2.

Weir 1 After thoroughly replacing the inside of a stainless steel reaction vessel with a two-person stirrer with nitrogen, add 4.500 g of styrene, 500 g of glycidyl methacrylate, and 1 portion of sodium dodecylbenzenesulfonate.
00g, 25g of t-dodecylmercaptan, and 12.000g of ion-exchanged water were charged. 70 for salmon
℃ hot water is circulated, and when the temperature inside the container reaches 60℃, 27.5 g of potassium persulfate and 1.4 g of ion exchange water are added.
After adding 00 g of an aqueous solution and conducting a polymerization reaction for 2 hours, 4.50 g of styrene, 500 g of glycidyl methacrylate, and 50 g of sodium dodecylbenzenesulfonate were added.
An aqueous solution consisting of 25 g of t-dodecylmercaptan, 5,000 g of ion-exchanged water, 27.5 g of potassium persulfate, and 600 g of ion-exchanged water was added, and the polymerization reaction was further carried out for 2 hours. The obtained polymer latex was coagulated with calcium chloride, thoroughly washed with water, and then dried to produce a polymer B-1 having a glycidyl methacrylate content of 10%.

2) The following polymers B-2 to B-5 were obtained under the same production conditions as those for Polymer B-].

Production Example - After thoroughly filling the inside of a stainless steel reaction vessel with a stirrer with nitrogen for 1 m, polybutadiene latinx (JSR10700
) 2,000g (solid content), butadiene-styrene copolymer latex (JSR11056 manufactured by Japan Synthetic Rubber ■)
1) 2.000 g (solid content), 50 g of sodium dodecylbenzenesulfonate, 3 g of potassium hydroxide, 4,000 g of styrene, and 14,000 g of ion exchange water were charged. While circulating hot water at 70℃ through the jacket, when the internal temperature of the container reaches 60℃, add 20g of sodium pyrophosphate, 25g of glucose, 0.4g of sulfuric acid, and 95g of ion-exchanged water.
After adding 0 g of water/8 liquid and 25 g of cumene hydroperoxide, a polymerization reaction was carried out for 2 hours. Thereafter, an emulsion containing 2,000 g of styrene, 26 g of sodium dodecylbenzenesulfonate, 3 g of potassium hydroxide, and 8 g of cumene hydroperoxide was continuously added over 2 hours to carry out a polymerization reaction. After adding an aqueous solution consisting of 6.7 g of sodium pyrophosphate, 8.3 g of glucose, ferrous sulfate, and 317 g of ion-exchanged water and 5 g of cumene hydroperoxide, the polymerization reaction was further carried out for 1 hour. After adding an antioxidant emulsion to the obtained polymer Latte Nox, it was coagulated with calcium chloride, thoroughly washed with water, and then dried to obtain Polymer C.

↓ ■ Polymer B-150 parts and nylon-6 (amilan 1017
; Toshi Co., Ltd.) 50 parts of the blend was made into a pellet-shaped resin (Polymer D) using a co-rotating twin-screw extruder. Polymer D
, Polymer A-1, and Polymer A-2 in the proportions shown in Table 1, and melt-kneaded in a co-rotating twin-screw extruder at a temperature of 240°C to 280"C to produce a thermoplastic resin. A composition was obtained.

A test piece was made using an injection molding machine and passed JIS test method 687.
Tensile strength, elongation, Izot impact strength, and heat distortion temperature were measured by the method described in 1 above. The state of peeling of the molded product was determined by applying an adhesive tape to the fractured surface of the test piece and then removing it with glue, and then observing the state with the naked eye. The results are shown in Table-1.

In Example 2, nylon-6 and polymer 13-1 were kneaded at the same time without using polymer D. The results are shown in Table-1.

υ1 raw-1 In Example-5, (bl component (polymer B-
This is an example in which polystyrene was used without using 1). As shown in Table 1, peeling was significant and the mechanical strength was significantly reduced.

Table-1 ■ Umbrella Toborekusu 500-51 Mitsui Toatsu Umbrella Umbrella 71
^11 condition No publication: ○ Peeling ^11 present: Polymer E (Polymer B-
Polymer F (using Polymer B-3), Polymer G (using Polymer B-4), and Polymer H (using Polymer B-5) were obtained. Table 2 shows the formulation and evaluation results using these polymers.

Table 2 This is an example in which Polymer C and hydrogenated styrene-butadiene Bronok copolymer (Kraton G1650, manufactured by Shell) were blended and an impact reinforcing agent was added.

As a gasoline resistance test, an injection molded test piece was immersed in gasoline for 2 hours, and the state of crack generation was observed.

The formulation and evaluation results are shown in Table 3.

The state of occurrence of cracks was visually evaluated and indicated by ◯ if no cracks occurred and × if cracks occurred.

This test was carried out on a system containing an impact reinforcing agent (without adding the c1 component).The formulation and evaluation results are shown in Table 3.
It was shown to. A system to which no tc+ component is added has poor gasoline resistance.

Claims (1)

[Scope of Claims] (a) 5 to 95% by weight of polyphenylene ether resin;
(b) Copolymer 0 obtained by copolymerizing a styrene monomer and at least one selected from epoxy group-containing unsaturated compounds, α,β-unsaturated acids, and (meth)acrylic esters .5-90% by weight, (c) polyamide 1-9
0% by weight and (d) an impact reinforcing agent from 0 to 80% by weight.