JPH02255858A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To obtain a thermoplastic resin composition as an engineering plastic improved in compatibility and excellent in moldability, heat resistance, flame retardancy and mechanical properties by adding an acid imide compound to a composition prepared by blending a polyphenylene sulfide resin with a polyphenylene ether resin. CONSTITUTION:0.5-20 pts.wt., desirably 1-10 pts.wt. acid imide compound such as N-cyclohexylmaleimide is added to 100 pts.wt. resin comprising 10-90wt.%, desirably 30-80wt.% polyphenylene sulfide resin containing a linear polyphenylene sulfide and 90-10wt.%, desirably 20-70wt.% polyphenylene ether resin to obtain a thermoplastic resin composition useful for automobile parts, industrial components, electrical materials, etc.

Description

Detailed Description of the Invention (Industrial Application Field) The present invention relates to a resin composition, and in particular to a thermoplastic resin composition that has excellent moldability, heat resistance, flame retardancy, and improved mechanical strength. It is about things.

(Prior art) Polyphenylene ether resin (hereinafter referred to as PPE) is a resin that is inexpensive and has excellent heat resistance, but because it has a high melt viscosity and requires high temperatures during molding, it is prone to discoloration and oxidative deterioration. It is not used alone for boat fishing. Usually PPE
and polystyrene or rubber-modified polystyrene. However, although this resin composition improves the moldability of the bo9life;-lene ether resin, it has the problem that the heat distortion temperature is significantly lowered.

On the other hand, polyphenylene sulfide resin (hereinafter referred to as pps) has extremely good molding processability, heat resistance, chemical resistance, flame retardance, mechanical strength, etc., but because it is a crystalline resin, molding shrinkage is large. It has the disadvantage of poor dimensional stability.

Therefore, attempts have been made to obtain resin compositions with excellent moldability, chemical resistance, heat resistance, mechanical strength, and dimensional stability by using PPE and PPS together. In this issue, a resin composition consisting of PPE and PPS is proposed.

However, since PPE and PPS have poor compatibility, none of them exhibits satisfactory mechanical strength. Also,
JP-A-59-2T3758 states that compatibility is improved by mixing a polyamide resin and an epoxy resin with a mixture of PPE and PPS. However, although this method improves mechanical strength,
The improvement in moldability was not satisfactory.

[Problem to be solved by the invention]

The problem to be solved by the present invention is to provide a thermoplastic resin composition for engineering plastics that improves the compatibility between PPE and pps and has excellent moldability, heat resistance, flame retardance, mechanical properties, etc. .

[Means to solve the problem]

As a result of intensive studies to solve the above problems, the present inventors found that a resin composition obtained by blending and melt-kneading an acid imide compound in a specific ratio to PPS and PPE solved the above problems. We have discovered that this is possible, and have arrived at the present invention.

That is, the present invention is a thermoplastic resin composition using 065 to 20 parts by weight of an acid imide compound to 100 parts by weight of a resin consisting of 510 to 90% by weight of P P and 90 to 10% by weight of PPE.

According to the findings of the present inventors, simply mixing PPS and PPE improves flame retardancy, but
is poorly compatible with wood, and even if it is kneaded using an extruder with excellent kneading properties, only a molded product with a burl-like pattern can be obtained, and a product with mechanical strength of do not have. However, in the present invention, by mixing the acid imide compound in a stiff manner, it has excellent moldability and compatibility, and
It is distinctive in that it provides a resin composition with improved mechanical strength.

It is necessary to contain 90 mol% or more of pps constituting the thermoplastic resin composition of the present invention, and if it is less than 90 mol%, it is difficult to obtain excellent properties. As long as the constituting copolymer component is less than 10 mol %, there is no problem as long as the meta bond does not significantly affect the crystallinity and stretching orientation of the 5-polymer, and preferably the copolymer component is 5 mol % or less.

As a method for polymerizing PPS, a method using a reaction between a halogen-substituted aromatic compound and an alkali sulfide (U.S. Pat. No. 251
3188, Japanese Patent Publication No. 45-3368), a method of condensation reaction of thiophenols in the coexistence of an alkali catalyst, etc. (U.S. Pat. No. 3,274,165), condensation of aromatic compounds with sulfur chloride in the coexistence of a Lewis acid catalyst, etc. A method of reacting (Japanese Patent Publication No. 46-27255), etc. can be mentioned. PPS produced by these methods is difficult to obtain a polymer with a high degree of polymerization, and it is common to increase the molecular weight by crosslinking after polymerization, so generally crosslinked PP
It's called s. Commercially available cross-linked pps include Rydon P-6 (manufactured by Philips Vetrolume).

In addition, a method for obtaining a high molecular weight linear polymer by coexisting an alkaline earth metal oxide or hydroxide during the polymerization of PPS (Japanese Patent Application Laid-Open No. 60-55029,
60-55030), and PPS produced by these methods is generally called linear PPS. A commercially available linear pps is FORTRON 205 (manufactured by Kenbetsu Kagaku Kogyo Co., Ltd.).

The pps constituting the thermoplastic resin of the present invention may be either cross-linked PPS or linear PPS, and is not particularly limited, but when cross-linked PPS is used, the heat distortion temperature Preferably used in applications requiring heat resistance. Linear PPS has improved Izod impact strength and is therefore preferable for applications requiring good mechanical properties.

The PPE used in the present invention is preferably a homopolymer or copolymer containing one or more units represented by formula (I).

(wherein R+, R2, R3, and R4 are each independently selected from the group consisting of hydrogen, halogen, hydrocarbon, halohydrocarbon, hydrocarbonoxy, and halohydrocarbonoxy, and n is the total number of monomer units. , and is an integer of 20 or more.) The method for manufacturing the PPE described above is not particularly limited, but is described in U.S. Patent No. 3,306,874.
No. 3,306,875, No. 3,257,357 and No. 3,257,358 by reacting phenols. These phenols include 2゜6-dimethylphenol, 2,6-ethylphenol, 2.6-sibutylphenol, 2.6-dilaurylphenol, 2.6-dipropylphenol,
．． 6-diphenylphenol, 2-methyl-6-nitylphenol% 2-methyl-6-cyclohexylphenol, 2-methyl-6-medoxyphenol, 2-methyl-6-butylphenol, 2.6-simethoxyphenol, 2゜3.6-drimethylphenol, 2,3.5.
These include, but are not limited to, 6-titramethylphenol and 2,6-dinitoxyphenol. Preferred PPE in the present invention is poly(2,6-
dimethyl-1,4-phenylene) ether.

The acid imide compound constituting the thermoplastic resin composition of the present invention generally includes NH3 or a primary amine compound and 2
Examples of the cyclic imide derived from the acyl group of a basic acid include aniline, cyclohexylamine, 4-hydroxyaniline, 4-hydroxyaniline, and 4-hydroxyaniline.
-Carboxyaniline, 4-chloroaniline, etc. are used, and dibasic acids include succinic acid, glutaric acid, phthalic acid, maleic acid, etc. Representative examples of acid imide compounds include succinimide, glutarimide, phthalimide, N-phenyl phthalimide, N-phenylmaleimide, N-cyclohexylmaleimide, N-(4-hydroxyphenyl)maleimide, N-(4-carboxyphenyl) Examples include maleimide, N-(4-chlorophenyl)maleimide, and the like.

In the thermoplastic resin composition of the present invention, straight arI-like PP
The blending ratio of PPS and PPE containing S is P P S
10-90% by weight, preferably 30-80% by weight, PP
The amount of the acid imide compound used is 0.5 to 20 parts by weight, based on 100 parts by weight of the PPS or PPE resin composition.
Preferably it is 1 to 10 parts by weight. 90% by weight PPE
If the PPE content exceeds 10% by weight, the effect of improving moldability decreases [7. If the PPE content is less than 10% by weight, the dimensional stability deteriorates. Furthermore, if the acid imide compound is less than 0.5 parts by weight, the effect of improving molding processability will be reduced, and if it exceeds 20 parts by weight, impact resistance will be reduced.

There are no particular limitations on the method for producing the thermoplastic resin composition of the present invention, and generally known methods can be employed. That is, a method can be employed in which PPS, PPE, and acid imide compounds are uniformly mixed using a high-speed stirrer or the like, and then melt-kneaded using a single-screw or multi-screw extruder with sufficient cross-mixing capacity.

Depending on the purpose, the thermoplastic resin composition of the present invention may contain pigments, dyes, reinforcing agents such as glass fibers, metal fibers, carbon ya strings, etc.
Fillers such as talc and calcium carbonate, antioxidants, and ultraviolet absorbers can be added.

(Example) The present invention will be described in more detail with reference to Examples below. The characteristics of the polymers and molded articles described in Examples and Comparative Examples were evaluated according to the following method.

(1) Izot' & Gakudo Compliant with JIS-7110.

(2) Heat distortion temperature Compliant with JXS-7207.

Bending stress 18.56 kg/cm2 (3) Melt flow index (formability) JIS
- Compliant with 7210.

Load: 2.16 kg, temperature: 300°C (4) Average afterflame time (combustion test) Compliant with IJL-94 (vertical conditions).

(5) Molding shrinkage rate Based on ASTM D-955.

(6) Tensile strength Compliant with JIS-7113.

Example 1 As cross-linked PPS, 20 parts by weight of [Rydon P-6: manufactured by Philips Vetroleum Co., Ltd.], as Pr-E (O
Manufactured by EM Polymer ■, PPE, trade name 380 weight (4 parts,
and N-cyclohexylmaleimide (CHMI) as an acid imide compound in the proportion shown in the table to reduce stiffness by 2.
The mixture was kneaded into pellets at a temperature of 80 to 310°C. Injection molded test pieces were prepared from this pellet, and the physical properties were measured. Table 1 shows the results. Impact resistance, heat resistance, moldability,
It had flame retardancy, molding shrinkage rate and 'bib', and had sufficient practical physical properties.

Example 2 Example 1 except that the proportions of PPS, PPE, and acid imide compounds used in Example 1 were changed as shown in the 'in 1 table.
It was carried out in the same way. The results are shown in Table 1. Impact resistance, heat resistance, moldability, flame retardancy, and molding shrinkage rate are all 1.
The material had sufficient practical physical properties. .

Examples 3 to 5 N-phenylmaleimide (N
The same procedure as in Example 1 was carried out except that PMI) was used and pps and PPE were adjusted to the proportions shown in Table 1. The results are shown in Table 1. It had excellent impact resistance, heat resistance, molding processability, flame retardancy, and molding shrinkage rate, and had sufficient practical physical properties.

Examples 6 to 7 In Example 1, using phthalimide instead of CHMl as the acid imide compound, and using PPS and PPE in the proportions shown in Table 1, the results of actual HL!iSino::.6 are shown in Table 1. It was excellent in impact resistance w$, strength, heat resistance +11, molding processability, flame retardance, and molding shrinkage rate, and had +-minor practical physical properties.

Comparative Examples 1 to 3 PPS and PPE alone and PPS
The same procedure as in Example 1 was carried out for the case where 17 and PPE were mixed. The results are shown in Table 1. Isuwa also lacked a balance in impact resistance, heat resistance, moldability, and flame retardancy.

Comparative Example 4 The same procedure as Example 3 was carried out except that the PPS, PPE, and acid imide compound used in Example 3 were blended in the proportions shown in Table 1, but the impact resistance was poor.

Example 8 I・0RTRON 1f-205 (as a linear pps)
Chemistry by prefecture? 4'! ! u) 20 parts, as PPE (O
EM Polymer η Kikusha, PPE, trade name 180 parts by weight,
and N-cyclohexylmaleimide (CHMI) as an acid imide compound in the proportions shown in Table 2,
The dough was kneaded into pellets at a temperature of 280 to 310°C.

Injection molded test pieces were prepared from this pellet, and the physical properties described in 4-4 were measured. The results are shown in Table 2. impact resistance, heat resistance,
It had excellent moldability and flame retardancy, and had excellent practical physical properties.

Example 9 The same procedure as Example 1 was carried out except that the proportions of linear PPS, PPE and acid imide compounds used in Example 8 were changed as shown in Table 2. The results are shown in Table 2. It was excellent in impact resistance, heat resistance, moldability, and flame retardancy, and had sufficient practical physical properties.

Examples 10 to 12 Using N-phenylmaleimide (NPM) as the acid imide compound, PPS and PPE were added in the proportions shown in Table 2,
The rest was carried out in the same manner as in Example 8. The results (-) were shown to a second person.The material had excellent impact resistance, heat resistance, ε-addition properties, and flame retardancy, and had sufficient practical physical properties.

Examples 13 to 14 In Example 8, phthalimide was used instead of CHMl as the acid imide compound, and u'c3 ['l-like P PS
and PPE were used at the formulation rates shown in Table 2. The results are summarized in Table 2. It had excellent impact resistance, heat resistance, moldability, flame retardancy, etc., and had excellent practical physical properties.

Comparative Example 5 - 7 In the case of linear pps and )) P E, Q' and linear P 1) The same procedure as in Example 8 was carried out for the case of mixing S and PPE. The results are shown in Table 2. All of them lacked a balance in impact resistance, heat resistance, moldability, and flammability.

Comparative Example 8 Example I except that the linear PPS, PPE, and acid imide compound used in Example IO were blended in the proportions shown in Table 2.
Although it was the same as O, it was inferior in 8J impact resistance.

〔Effect of the invention〕

The polyphenylene sulfide resin composition of the present invention has excellent impact resistance, heat resistance, bimodality before molding, and flame retardancy, and is suitably used for automobile parts, industrial parts, electrical materials, and the like.

Patent applicant: Mitsui Toatsu Chemical Co., Ltd.

Claims (2)

[Claims] (1) Add 0.5 to 0.5 to 100 parts by weight of an acid imide compound to 100 parts by weight of a resin consisting of 10 to 90% by weight of polyphenylene sulfide resin and 90 to 10% by weight of polyphenylene ether resin.
A thermoplastic resin composition using 20 parts by weight. (2) The thermoplastic resin composition according to claim 1, wherein the polyphenylene sulfide resin is a linear polyphenylene sulfide resin.