JPH0286652A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To obtain the title composition excellent in mechanical strengths, elongation, impact strength and thermal properties by mixing a mixture of a polyarylene sulfide resin with a polyphenylene ether resin with a specified styrene copolymer. CONSTITUTION:100 pts.wt. mixture comprising 20-98 pts.wt. polyarylene sulfide resin preferably comprising at least 70mol% phenylene sulfide units and the balance of units selected from among those of formulas I-VI (wherein R is a 12 C or lower alkyl, an alkoxy, a phenyl or a nitro) and 80-2 pts.wt. polyphenylene ether resin (e.g., 2,6-dimethylphenol polymer) is mixed with 1-50 pts.wt. epoxy styrene copolymer obtained, desirably, by reacting a styrene monomer (e.g., styrene) with an alpha,beta-unsaturated glycidyl ester (e.g., glycidyl methacrylate).

Description

Detailed Description of the Invention [Industrial Field of Application] The present invention is a thermoplastic resin IIII & II composition containing a polyarylene sulfide resin as one component, which material substantially reduces the mechanical strength of the polyarylene sulfide resin. The invention relates to thermoplastic resin compositions with improved elongation, impact strength, thermal properties, etc., without causing damage.

The thermoplastic resin composition of the present invention is used in a wide range of fields such as mechanical parts, automobile parts, and electrical/electronic parts.

[Prior art and problems to be solved by the invention] Polyarylene sulfide resins, represented by polyphenylene sulfide (pps) resins, have excellent mechanical strength and chemical resistance, and are flame retardant, so in recent years, they have become popular. Application development is being attempted in fields that require rigidity and heat resistance, such as electrical/electronic parts and automobile parts.

However, this resin has drawbacks such as low elongation and impact resistance, lack of flexibility, and a large decrease in strength at high temperatures because the glass transition temperature is not very high, so its field of use is limited.

In order to improve the above-mentioned drawbacks, many proposals have been made regarding thermoplastic resin compositions made by melt blending polyarylene sulfide resins and engineering plastics such as polyphenylene ether (PPE) resins, and methods for improving the same.

For example, in Japanese Patent Application Laid-open No. 50-156561, PPS
A resin composition comprising a resin and a PPE resin is disclosed. JP-A-55-135160 discloses a thermoplastic resin composition containing a PPS resin and a PPE resin, a nylon resin, or a saturated polyester resin in a specific ratio. In Japanese Patent Application Laid-open No. 58-157859, PP
A thermoplastic resin composition comprising an S resin and a PPE resin copolymer grafted with a styrene polymer is disclosed. JP-A-59-164360 discloses a thermoplastic resin composition comprising a PPS resin, a PPE resin, and an epoxy resin. Also, JP-A-5!11-213
No. 758 discloses a thermoplastic resin composition comprising a PPS resin, a PPE resin or a polyamide resin, and an epoxy resin. However, the thermoplastic resin compositions disclosed in these publications have drawbacks such as insufficient improvement in elongation and impact strength, and furthermore, poor mechanical strength and thermal properties.

Therefore, an object of the present invention is to provide a thermoplastic resin composition containing a polyarylene sulfide resin as one component, which improves elongation, impact strength, and thermal strength without substantially reducing the mechanical strength of the polyarylene sulfide resin. The object of the present invention is to provide a thermoplastic resin composition with improved thermal properties such as deformation temperature.

[Means for Solving the Problems] As a result of intensive studies, the present inventors found that when melt blending polyarylene sulfide resin and PPE resin,
It has been found that the above object can be achieved by adding a specific styrene copolymer.

The present invention was made based on the above findings, and includes (A) 20 to 98 parts by weight of polyarylene sulfide resin and (
B) 100 parts by weight of a mixture consisting of 80 to 2 parts by weight of polyphenylene ether resin (hereinafter referred to as PPE resin),
(C) Styrene copolymer having epoxy group 1 to 50
The object of the present invention is to provide a thermoplastic resin composition characterized in that it contains parts by weight.

Hereinafter, the thermoplastic resin composition of the present invention will be explained in detail.

The polyarylene sulfide resin (A) used in the present invention preferably contains 70 mol% or more of its repeating units in terms of heat resistance, chemical resistance, and mechanical properties. If the phenylene sulfide unit content is less than 70 mol%, heat resistance tends to decrease. The remaining 30 mol% or less of the components include mek bond (where R is selected from the group consisting of an alkyl group or alkoxy group having 12 or less carbon atoms, a phenyl group, and a nitro group), trifunctional phenyl sulfide. There are connections, etc.

In particular, the present invention uses a polyarylene sulfide resin having the above structure, which conforms to ASTM D 1238-74.
315°C 1 load 5k with melt indexer specified by T
The melt flow rate measured under g conditions is 5 to 1000
0 g/10 min is preferable.

As the above-mentioned polyarylene sulfide resin, commercially available products such as Rydon PPS manufactured by Phillips Oil Company, Toprene manufactured by Toprene Company, Susteel manufactured by Tosoh Sasteel Co., Ltd., and Fortron manufactured by Kureha Chemical Industry Co., Ltd. can be used.

Furthermore, examples of the (B) P PE resin used in the present invention include those represented by the following general formula (1).

The above PPE resin can be obtained by polymerizing the following phenol compound.

Such phenolic compounds include 2.6-diethylphenol, 2.6-diethylphenol, 2-methyl-
6-ethylphenol, 2-methyl6-allylphenol, 2-methyl-6-phenylphenol, 2.6-diphenylphenol, 2.6-sibutylphenol, 2
-Methyl-6propylphenol, 2.3.6-drimethylphenol, 2.3-dimethyl-6-ethylphenol, 2,3.6-toluethylphenol, 23.6-
) Liprovirphenol, 2.6-dimethyl-3-ethylphenol, 2. 6-'; Examples include methyl 3-propylphenol. These phenol compounds can be used alone or in combination of two or more. The most preferred PPE resins include polyphenylene ether obtained from 2,6-diethylphenol;
Examples include polyphenylene ether obtained by copolymerization of diethylphenol and 2.3.6-)diethylphenol or 2.6-diphenylphenol. The PPE resin preferably has an intrinsic viscosity "η" (chloroform 0.5% solution, 30°C) of 0°3 to 3.0. Furthermore, a PPP resin copolymerized with a styrene monomer or a mixture of a styrene polymer can also be used.

Furthermore, the styrene copolymer having an epoxy group (C) used in the present invention can be produced by reacting a styrene monomer with a glycidyl ester of an α,β-unsaturated acid,
Preferably, it does not contain monomers other than these.

Examples of the styrene monomer include styrene, methylstyrene, vinylxylene, dichlorostyrene, bromstyrene, dibromstyrene, PL-butylstyrene, ethylstyrene, vinylnaphthalene, and among these, styrene is preferred.

The glycidyl esters of the above α,β-unsaturated acids include:
Examples include those represented by the following general formula (2).

The glycidyl esters of the above α,β-unsaturated acids include:
Specific examples include glycidyl acrylate, glycidyl methacrylate, glycidyl ethacrylate, glycidyl itaconate, allyl glycidyl ether, and vinyl glycidyl ether.

The above-mentioned styrene copolymer having an epoxy group can be produced by bulk polymerization, solution polymerization, suspension polymerization, or emulsion polymerization using a known radical polymerization method. In addition, the above styrene copolymer having an epoxy group can be produced by reacting the above styrene monomer with the glycidyl ester of the above α, β unsaturated acid, or by reacting the above styrene monomer with the above α, β unsaturated acid. -Can also be produced by reaction with glycidyl esters of unsaturated acids.

Further, when the reaction is carried out in a molten state, the desired product can be easily obtained in a relatively short time by using a melt mixer such as an extruder, co-kneader, or Banbury mixer.

The reaction ratio of the styrene monomer and the glycidyl ester of the α,β-unsaturated acid is as follows:
Glycidyl esters of α,β-unsaturated acids-40-99.
5% by weight: 60-0.5% by weight, more preferably 60-0.5% by weight
99% by weight; 40-1% by weight.

In addition, the above styrene copolymer having an epoxy group is
Number average molecular weight is 3000 to 120000, especially 5000
A range of 70,000 is preferred.

If the reaction ratio of the styrene monomer and the glycidyl ester of an α,β-unsaturated acid and the number average molecular weight of the styrene copolymer are outside the above ranges, the effect of improving the compatibility between the polyarylene sulfide resin and the PPE resin will be small. Become.

The thermoplastic resin composition of the present invention comprises (8) 20 to 98 parts by weight of the polyarylene sulfide resin, preferably 3 parts by weight.
0 to 95 parts by weight and ([1) 80 to 2 parts by weight, preferably 70 to 5 parts by weight of the PPE resin 100
1 to 50 parts by weight, preferably 3 to 40 parts by weight of the styrene copolymer having an epoxy group (C) is blended in each part by weight.

If the blending ratio of the polyarylene sulfide resin, PPE resin, and styrene copolymer having an epoxy group is out of the above range, the mechanical properties and thermal properties of the resulting composition will deteriorate, which is not preferable.

Furthermore, if the amount of PPE resin used is more than 80 parts by weight, the moldability will deteriorate, and if it is less than 2 parts by weight, the thermal properties will not be improved.

Various reinforcing materials and fillers can be added to the thermoplastic resin composition of the present invention within a range that does not impair its moldability and physical properties.

Such reinforcing materials and fillers include glass fiber, asbestos fiber, carbon fiber, silica fiber, silica/alumina fiber, alumina fiber, zirconia fiber, boron nitride fiber, silicon nitride fiber, boron fiber, stainless steel, aluminum, titanium, and copper. , metal fibers such as brass and magnesium, organic fibers such as polyamide, fluororesin, polyester, and acrylic resin, copper, iron, nickel, zinc,
Examples include metal powders such as soot, lead, stainless steel, aluminum, gold, and silver, hiemed silica, aluminum silicate, glass beads, carbon blank, quartz powder, talc, titanium oxide, iron oxide, lucium carbonate, and diatomaceous earth. The fibrous substance has an average fiber diameter of 5 to 50 μm,
Those having a fiber length of 50 μm to 60 M can be used. These reinforcing materials and fillers may also be surface-treated with a known silane coupling agent or titanate coupling agent.

The amount of the reinforcing material and filler used is preferably 1 to 300 parts by weight per 100 parts by weight of the thermoplastic resin composition of the present invention.
Parts by weight, more preferably 10 to 250 parts by weight.

The above reinforcing materials and fillers can be used alone or in combination of two or more.

In addition, the thermoplastic resin composition of the present invention may contain hinderers such as phenol, hydroquinone, thioether, phosphites, substituted products thereof, and copper such as copper iodide, as long as the object of the present invention is not impaired. Antioxidants and heat stabilizers such as compounds, ultraviolet absorbers such as redulucinol, salicylate, benzotriazole, hensifenone, stearic acid and its salts, mold release agents such as stearyl alcohol, halogens, phosphate esters, melamine or cyanuric. It is also possible to add one or more additives such as acid flame retardants, flame retardant aids, sodium dodecylhenzenesulfonate, antistatic agents such as polyalkylene glycol, crystallization accelerators, dyes, and pigments. , the thermoplastic resin composition of the present invention includes a small amount of polyethylene, polypropylene, ethylene/vinyl acetate copolymer, ethylene/propylene copolymer, styrene/butadiene copolymer, hydrogenated styrene/butadiene copolymer,
Thermoplastic resins such as polyamide, polyester, polyester elastomer, polyacetal, thermoplastic polyurethane, polycarbonate, and polysulfone, and thermosetting resins such as phenol resin, melamine resin, silicone resin, and epoxy resin can also be added.

The thermoplastic resin composition of the present invention can be pelletized using ordinary melt-kneading processing equipment such as an extruder, Banbury mixer, or kneader, and can be further processed into pellets for various purposes by injection molding, compression molding, extrusion molding, etc. Can be processed into molded products.

〔Example〕

EXAMPLES Hereinafter, the present invention will be explained in more detail by giving examples of the present invention together with production examples of PPE resins, production examples of styrene copolymers having epoxy groups, and comparative examples.

The methods for measuring tensile strength, elongation, impact strength, heat distortion temperature, and average dispersed particle diameter described in Examples and Comparative Examples are as follows.

(1) Tensile strength, elongation Measured according to ASTM D638.

(Unit: kgf/c+a2) u(2) Impact strength (notched isot impact strength) AS
Measured according to TM D256. The thickness of the test piece is
It is 1/8 inch.

(Unit: kgf-cta/cm) (3) Heat distortion temperature Measured according to ASTM 0648.

(Load 18.6 kg/cTA, unit 'C) (4
) Average Dispersed Particle Size The particle size of the dispersed component was measured from an SEM photograph of the fracture surface of a test piece (thickness 2.5 m) cooled with liquid nitrogen.

(Unit: μm) In a reactor equipped with an oxygen blower, a cooling coil, and a stirrer, 32.2 g of cupric bromide and 32.2 g of di-n
-666 g of butylamine, and 24 g of toluene! 2,
After 5.25 kg of 6-xylenol was dissolved and dissolved uniformly, the mixture was polymerized for 90 minutes while keeping the inside of the reaction vessel at 30°C while rapidly blowing oxygen.
After the polymerization was completed, 18ffi of toluene was added, and then a 20% aqueous solution of ethylenediaminetetraacetic acid was added to stop the reaction. The resulting product mixture was centrifuged, the polymer dissolved phase was removed, and methanol was gradually added while stirring. After the separation, it was dried to obtain a PPE resin with an intrinsic viscosity of 0.50.

Production Example 2 216g of styrene in a separable flask equipped with a stirrer
, glycidyl methacrylate 24g, toluene 160g
Add 2g of azobisisobutyronitrile and heat at 25°C.
The mixture was uniformly mixed for 20 minutes while blowing nitrogen. Thereafter, the separable flask was transferred to an oil bath at 85°C, stirred at the same temperature in a nitrogen atmosphere for 60 minutes, and then the temperature of the oil bath was raised to 105°C and the temperature was increased to 45°C at the same temperature.
Stir for a minute to allow reaction. Thereafter, the separable flask was taken out from the oil bath and cooled, and the polymerization liquid was added dropwise to methanol under strong stirring and separated. After fractionation, it was dried to obtain a styrene copolymer having epoxy groups ((, -1).

The obtained styrene copolymer having epoxy groups (C-=
The number average molecular weight of 1) was approximately 21,300 as determined by GPC, and the epoxy group concentration was 6.8×10−′ of/g as determined by titration.

Production Example 3 A styrene polymer (C-2) having an epoxy group was obtained in the same manner as Production Example 2, except that the amount of styrene was 192 g and 48 g of glycidyl acrylate was used instead of glycidyl methacrylate. This copolymer (C-2
) has a number average molecular weight of about 12,000, and an epoxy group concentration of 13. l Xl 0-'mol/g.

Production Example 4 A styrene copolymer having an epoxy group (C-3) was produced in the same manner as Production Example 2, except that the amount of styrene used in C-3 was changed to 234 g, and the amount of glycidyl methacrylate was changed to 6 g. 3) was obtained.The number average molecular weight of this copolymer (C-3) was about 42,000, and the epoxy group concentration was 1.7 x 10-'mol/
It was g.

Examples 1 to 3 and Comparative Examples 1 to 5 Polyarylene sulfide resin (Toprene T-4,
(manufactured by Toprene), the PPE resin obtained in Production Example 1, and the styrene copolymer (C-1) having an epoxy group obtained in Production Example 2 were blended in the proportions shown in Table 1 below, respectively,
Screw diameter 3 with each formulation set at 320 °C
The mixture was melt-kneaded using a No. 011 twin-screw kneader to produce pellets. These pellets are molded at a temperature of 320°.
Injection molding was performed at a C1 mold temperature of 130°C to obtain test pieces for measuring physical properties. Their physical properties and average dispersed particle diameter are shown in Table 1 below.

Examples 4-8 Polyarylene sulfide resin (Toprene T-4,
Toprene T-1 (manufactured by Toprene), PPE resin obtained in Production Example 1, styrene copolymer having epoxy groups (C-2) obtained in Production Examples 3 and 4 and (C-3L glass fiber ( CS-03-MA-411, manufactured by Asahi Fiberglass Co., Ltd.), and calcium carbonate (Whiten SO
1 (manufactured by Shiraishi Riki Rusium Co., Ltd.) in the proportions shown in Table 2 below, and the physical properties of the test pieces prepared were measured in the same manner as in Examples 1 to 3. The results are shown in Table 2 below.

Table [Effects of the Invention] The thermoplastic resin composition of the present invention has improved thermal properties such as elongation, impact strength, and heat distortion temperature without substantially reducing the mechanical strength of polyarylene sulfide resin. It is something that

Claims (1)

[Claims] (C) 1 to 50 parts by weight of a styrene copolymer having an epoxy group is blended into 100 parts by weight of a mixture consisting of 20 to 98 parts by weight of (A) polyarylene sulfide resin and 80 to 2 parts by weight of (B) polyphenylene ether resin. A thermoplastic resin composition characterized by: