JPH02227446A - Resin composition - Google Patents

Abstract

PURPOSE:To provide a resin composition having excellent elongation, impact strength, etc., without deteriorating the mechanical strength and suitable for mechanical parts, etc., by compounding a styrenic polymer-addition reacted polyphenylene sulfide with styrene polymer, etc. CONSTITUTION:(A) 40-98 pts.wt., preferably 50-95 pts.wt., of a styrenic polymer- addition reacted polyphenylene sulfide resin is compounded with (B) 2-60 pts.wt., preferably 5-50 pts.wt., of styrene polymer and/or a styrenic copolymer (e.g. polystyrene resin or ABS resin) to provide the objective resin composition.

Description

Detailed Description of the Invention [Industrial Application Field] The present invention relates to a resin or composition comprising a polyphenylene sulfide resin to which a styrene polymer is added, and a styrene polymer and/or a styrene copolymer, The present invention relates to a resin composition that has good elongation, impact strength, etc. without substantially impairing mechanical strength.

This resin composition is used in a wide range of fields such as mechanical parts, automobile parts, and electrical and electronic parts.

[Prior art and problems] Polyphenylene sulfide wood If& (hereinafter abbreviated as PPS) has excellent mechanical strength, chemical resistance, etc., and is flame retardant, so it has been used in electrical/electronic parts and automobile parts in recent years. Attempts are being made to develop applications in fields where rigidity and heat resistance are required.

However, PPS has extremely low elongation and impact strength.

It is well known that PPS cannot be used alone as a molded part because it is a very brittle resin.

To compensate for this drawback, PPS is usually used as a reinforced resin composition mixed with a reinforcing material such as glass fiber.

However, when PPS is reinforced with glass fiber, etc., the impact strength is improved, but the elongation is hardly improved, and the melt viscosity increases significantly compared to the case of PPS alone, resulting in poor moldability. The use of reinforcing materials such as glass fiber deteriorates the surface smoothness of molded products, resulting in poor appearance, which limits the field of application.

Also, for the purpose of improving the brittle properties of PPS.

A resin composition has been proposed in which PPS is melt-blended with a styrene-based polymer having excellent flexibility.

For example, in JP-A-51-62849.

A resin composition comprising PPS and a styrenic polymer or styrenic copolymer is disclosed.

JP-A-56-118456 discloses a resin composition comprising PPS and a copolymer of a vinyl aromatic compound and a conjugated diene compound.

In general, it is difficult to uniformly mix different types of resins by melt blending, and the strength and flexibility of the resin composition obtained by melt blending are lower than the values expected from the constituent polymers, and the appearance of the molded product. However, most of them are of no industrial use value because they deteriorate due to phase separation.

PPS has particularly poor miscibility with other polymers.

In the case of the above-mentioned known resin compositions as well, the flexibility cannot be uniformly mixed using the normal melt blending method.
Although it is slightly improved compared to using PS alone, it is not sufficient and has the disadvantage that the appearance of the molded product is poor.

[Means for Solving the Problems] An object of the present invention is to improve the elongation and impact strength of PPS without substantially impairing its mechanical strength.

An object of the present invention is to provide a resin composition that can be used without being particularly reinforced with a reinforcing material such as glass fiber.

As a result of intensive studies, the present inventors discovered that PPS to which a styrene polymer is added and a styrene polymer are a special combination that can be easily and uniformly mixed using a normal melt blending method, and have arrived at the present invention. .

That is, one purpose of the present invention is.

This can be achieved by a resin composition consisting of (A) 40 to 95 parts by weight of a polyphenylene sulfide resin to which a styrene polymer has been added, and (B) 60 to 5 parts by weight of a styrene polymer.

According to the present invention, PPS to which a styrenic polymer is added
The dispersibility of the styrene polymer and styrene copolymer is good, the dispersed particle size is small, and the adhesion between the resins is also good, resulting in a resin composition with excellent practical mechanical strength and flexibility. be able to.

PP added with styrenic polymer used in the present invention
S can be produced by subjecting PPS to an addition reaction with a styrenic polymer using an appropriate method.

Generally, it is very difficult to react PPS with other polymers, but it is a feature of the present invention that we have discovered that it is possible to react with styrenic polymers that have specific epoxy groups, and that styrenic polymers can be added to PPS. There is one.

In terms of heat resistance, chemical resistance, and mechanical properties, PPS used in the present invention has at least 80 mol% of its repeating units.
It is represented by the structural formula -e-S. If the phenylene sulfide unit content is less than 80%, the heat resistance decreases, which is not preferable.

The remaining 20% or less components include meta-bond 4#3h,
Ether bond -Eo-O-o-, sulfone bond -Q-s
o2-Q, biphenyl bond 41CF(]-s +-
, naphthyl bond-Eao-S.

Examples include substituted phenylene sulfide bond -fQ-S (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), a trifunctional phenyl sulfide bond, and the like.

In the present invention, a PPS having the above structure and an ASTM
D 1238-74, melt indexer specified by T
The melt flow rate measured at 315°C and a load of 5 kg is 1 to 10,000 g for 710 minutes, more preferably 5
~500/10 min is used.

Specific examples of PPS include Rydon PPS manufactured by Phillips Oil Company, Toprene manufactured by Toprene, Susteel manufactured by Tosoh Susteel, and Fortron manufactured by Kureha Chemical Industry Co., Ltd.

Styrenic polymers with epoxy groups.

It can be produced by a copolymerization reaction of a glycidiester of an α,β-unsaturated acid and a styrene monomer.

Glycidyl esters of α,β-unsaturated acids are.

There are compounds represented by deceased (I) and (■).

Specific examples of glycidyl esters of α,β-unsaturated acids include glycidyl acrylate, glycidyl methacrylate, glycidyl ethacrylate, glycidyl itaconate, allyl glycidyl ether, and vinyl glycidyl ether. Among these, glycidyl methacrylate is most preferred.

Examples of styrene monomers include styrene, methylstyrene, vinylxylene, dichlorostyrene dibromstyrene, dibromstyrene, pt-butylstyrene, ethylstyrene, vinylnaphthalene, and among these, styrene is the most preferred. .

Further, the styrene polymer containing epoxy groups of the present invention is ethylene, propylene, butylene, if it is 20 parts by weight or less, more preferably 10 parts by weight or less, based on 100 parts by weight of this polymer.

One of the seven triads such as butadiene, isoprene, acrylonitrile, methyl acrylate, methyl methacrylate, etc.
A species or a copolymer of two or more species can also be used.

The reaction between the glycidyl ester of an α,β-unsaturated acid and a styrene monomer is carried out using a known radical polymerization method.
It can be produced by bulk polymerization, solution polymerization, suspension polymerization or emulsion polymerization. This reaction is.

Even if a glycidyl ester of an α,β-unsaturated acid is directly reacted with a styrene monomer, a styrenic polymer prepared by prepolymerizing a styrenic monomer and an α,β
-Can also be produced by reaction with glycidyl esters of unsaturated acids.

Copolymers produced by these methods may be random copolymers, block copolymers, graft copolymers, or mixtures thereof, but among these, random copolymers are more preferred. preferable.

The reaction ratio of the glycidyl ester of an α,β-unsaturated acid and the styrene monomer is: glycidyl ester of an α,β-unsaturated acid:styrene monomer=0.5 to 30 parts by weight:
The range is 99.5 to 70 parts by weight, more preferably 2 to 20 parts by weight: 98 to 80 parts by weight.

Further, the number average molecular weight of the styrene polymer having an epoxy group is 3,000 to 120,000, more preferably 50
A value in the range of 00 to 50,000 can be used. The number average molecular weight of the styrene polymer having epoxy groups can be adjusted by adjusting the amount of radical initiator used in one reaction and the reaction temperature.

If the proportion of the glycidyl ester of α,β-unsaturated acid is outside the above range, it will be very difficult to produce PPS to which the styrenic polymer used in the present invention is added due to the relationship with the epoxy group concentration, and this is not preferred. do not have.

PPS to which the styrenic polymer of the present invention is added is PP
530 to 98 parts by weight, more preferably 50 to 95 parts by weight, and 70 to 2 parts by weight, more preferably 5 to 50 parts by weight of the styrenic polymer having an epoxy group. After reacting in a solution such as methylpyrrolidone at a temperature of 200° C. or higher, preferably 250 to 380° C., with uniform stirring, the resulting reaction mixture is washed with a solvent such as chloroform. 0 can be produced by removing styrenic polymers with unreacted epoxy groups.
When the reaction temperature is 250 to 380°C for 10 minutes or more, almost complete reaction occurs. Styrenic polymers with unreacted epoxy groups may remain, but due to the miscibility of PPS to which styrene polymers have been added with styrene polymers or styrene copolymers, the styrene polymers with epoxy groups may remain on the surface of the molded product. From the viewpoint of bleeding, etc., it is preferable to remove it.

If the proportion of PPS used exceeds the above upper limit, the miscibility with the styrene polymer or styrenic copolymer will deteriorate, and if it falls below the lower limit, the mechanical strength will decrease. Unobtainable and undesirable.

The styrene polymers and styrene copolymers used in the present invention include polystyrene resin, ABS resin (acrylonitrile/butadiene φ styrene resin), As resin (acrylonitrile/styrene resin), SBS (styrene butadiene styrene), 5EBS (water Added styrene/butadiene styrene) 2 acid anhydride modified 5EBS
, 5IS (styrene, isoprene, styrene), etc.

Among these, PS resin, ABS resin, etc. are preferable.

The resin composition of the present invention has PP540-98f! to which the styrenic polymer (A) is added! L parts, more preferably 50 to 95 parts by weight and (B) styrene polymer and/or
Alternatively, it is a mixture comprising 2 to 60 parts by weight of a styrenic copolymer, more preferably 5 to 50 parts by weight.

If the amount of the styrene polymer or styrene copolymer exceeds the above upper limit, it is not practical because the resin composition has disadvantages such as poor mechanical strength and thermal properties, and if it is less than the lower limit.

This is because the elongation and impact strength of the resin composition are not improved.

Undesirable.

Further, in the case of further improving the impact strength according to the present invention, a known thermoplastic elastomer can be added. The amount of these thermoplastic elastomers used is based on 100 parts by weight of the resin composition of the present invention.

It is 1 to 60 parts by weight, more preferably 3 to 40 parts by weight.

Specific examples of thermoplastic elastomers that can be used include known resin-based resins, urethane-based materials, polyester-based materials, polyamide-based materials, vinyl chloride-based materials, and chlorinated polyethylenes.
Examples include 2-polybutadiene, fluorine-based, ioimer, and elastomers of these having acid anhydride groups or epoxy groups.

Specific examples of olefins include Milastomer (manufactured by Mitsui Petrochemical Industries, Ltd.), Sumitomo TPE (manufactured by Sumitomo Chemical Co., Ltd.), and Thermolan (manufactured by Japan Synthetic Rubber Co., Ltd.).

5ANTOPRENE (manufactured by Monsanto),
Examples include LEVAFLEX-EP (manufactured by Bayer).

Specific examples of urethane-based materials include Elastolan (manufactured by Nippon Elastolan Co., Ltd.), ESTENE (B, F, Goo
(manufactured by drich).

A specific example of polyester is Hytrel (Toshi・
(manufactured by DuPont) and Pelprene (manufactured by Toyobo Co., Ltd.).

Specific examples of polyamides include Glylux (manufactured by Dainippon Ink), Tsubamitsu (manufactured by Mitsubishi Kasei), and Diamid-PAE (manufactured by Daicel-Hüls).

Specific examples of vinyl chloride-based materials include Sumiflex (manufactured by Sumitomo Bakelite Co., Ltd.), Sunbren (manufactured by Mitsubishi Monsanto Kasei Co., Ltd.), and Aronelasto (manufactured by Toagosei Kagaku Co., Ltd.).

1. Specific examples of 2-polybutadiene are as follows.

Examples include JSRRB (manufactured by Japan Synthetic Rubber Co., Ltd.).

Specific examples of fluorine-based materials include Daiel TPE (manufactured by Daikin Industries, Ltd.).

Examples of iOimers include Himilan (manufactured by DuPont Mitsui Polychemicals).

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

Specific examples of reinforcing materials and fillers used in the present invention include:
Glass fiber, asbestos TA fiber, carbon M fiber, silica fiber, silica number alumina fiber, alumina fiber, zirconia JLL male, boron nitride fiber, silicon nitride fiber, boron LA fiber, stainless steel, aluminum, titanium, copper, brass, magnesium metals such as I/IAra, and organic fibers such as polyamide, fluororesin, polyester, acrylic resin, copper, iron, nickel, zinc, soot,
Metal powders such as lead, stainless steel, aluminum, gold, and silver, fumed silica, aluminum silicate, glass beads, carbon black, quartz powder, and talc.

0 mm-shaped materials such as titanium oxide, iron oxide, lucium carbonate, and diatomaceous material having an average fiber diameter of 5 to 30 mm and a fiber length of 50 mm to 30 mm 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 reinforcing material and filler used is 100% of the resin composition of the present invention.
1 to 300 parts by weight, preferably 10 to 2 parts by weight
It is 50 parts by weight. These reinforcing materials and fillers can be used alone or in combination of two or more.

The resin composition of the present invention contains antioxidants and heat stabilizers such as hindered phenols, hydroquinone, thioethers, phosphites, substituted products thereof, and copper compounds, resorcinol, UV absorbers such as salicylate, benzotriazole, benzophenone, stearic acid and its salts, mold release agents such as stearyl alcohol, halogen-based, phosphate ester-based, melamine or cyanuric acid-based flame retardants, flame retardant aids, dodecylbenzene It is also possible to add one or more additives such as antistatic agents such as sodium sulfonate and polyalkylene glycol, crystallization promoters, dyes, and pigments.

Also small amounts of polyethylene, polypropylene, ethylene, vinyl acetate copolymers, polyamides, polyesters, polyacetals, and polycarbonates.

Thermoplastic resins such as polysulfone, phenolic resins,
Thermosetting resins such as melamine resins, silicone resins, and epoxy resins can also be added.

The resin composition of the present invention can be produced using ordinary melt-mixing processing equipment such as an extruder, Banbury mixer, or kneader, and can also be made into molded products for various uses by injection molding, compression molding, extrusion molding, etc. Can be processed.

The present invention will be explained below by way of examples.

[Example] 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 0838.

(Unit: kg f/c) (2) Impact strength (Notched Izo impact strength) AST
Measured according to MD256. The thickness of the test piece is 1
It is 78 inches.

(Unit: kgfIIcm/cm) (3) Heat distortion temperature Measured according to ASTM D648.

(Load: 18゜6 kg/c, unit: °C) (4
) Average Dispersed Particle Size The particle size of the dispersed components was measured from a TEM photograph.

(Unit: #Lm) Production Example 1 216g of styrene was placed in a separable flask equipped with a stirrer.
, 24 g of glycidyl methacrylate, 160 g of xylene, and 2 g of azobisisobutyronitrile were added and mixed uniformly at 25° C. for 20 minutes while blowing nitrogen. after that,
The separable flask was transferred to an 85°C oil bath and stirred at the same temperature in a nitrogen atmosphere for 60 minutes, and then the temperature of the oil bath was further raised to 130°C and stirred at the same temperature for 90 minutes to react. . Thereafter, the separable flask was taken out from the oil bath, cooled, and the polymerization liquid was added dropwise to methanol under strong stirring to be fractionated. After 0 fractionation, the flask was dried to obtain styrene bolts having epoxy groups. The yield was 91%.

The number average molecular weight of the produced polystyrene resin having epoxy groups was approximately 52,900 as measured by GPC (in terms of styrene polymer), and the epoxy group concentration was determined by titration method - t
's, 8 x 10-' mat/g. In addition, using the same method, we varied the blending ratio of styrene and glycidyl methacrylate, the amount of 7zobisisobutyronitrile, and the reaction temperature, and produced styrene polymers (C-2, C-2, C-3) was produced.

Table 1 Production Example 2 The epoxy group was prepared in the same manner as in Production Example 1, except that 187.5 g of styrene, 50 g of glycidyl methacrylate, and 12-5 g of methyl methacrylate were used instead of 216 g of styrene and 24 g of glycidyl methacrylate. A copolymer of styrene and methyl methacrylate was obtained. The number average molecular weight of this copolymer was 12,600, and the epoxy group concentration was 6.6×10-4 sol/g.

Manufacturing example 3 After thorough washing with acetone and drying, a reaction product was obtained.

Unreacted C-1 was about 3% by weight. The melting point (DSC peak temperature) of the obtained reaction product was 281°C.

Using the same method and changing the composition ratio and the epoxy group-containing styrene polymers (C-2, C-3), PPS to which styrenic polymers were added as shown in Table 2 was produced.

Table 2 After melting 90 parts by weight of PP5 (Toprene T-4) at 300°C, 10 parts by weight of polystyrene resin having an epoxy group (C-1 of Production Example 1) was added, and a Prabender type mixer was used. The mixture was reacted for 20 minutes while being mixed uniformly in a nitrogen gas atmosphere. After cooling, the reaction mixture was pulverized to form a pps (D
-1) and ABS resin (TOYOLAC 500, manufactured by Toshi ■) in the proportions shown in Table 3 and melt-kneaded using a two-wheel mixer with a screw diameter of 30 mm set at 300°C to produce pellets. This pellet was injection molded at a molding temperature of 300°C and a mold temperature of 145°C to obtain a test piece for measuring physical properties. Their physical properties and average dispersed particle diameter were measured and shown in Table 3.

Comparative Example 1 Pellets were produced using PP5 ()-Prene T-4) using a twin-screw mixer with a screw diameter of 30 mm and set at 300°C. A test piece was prepared from this pellet in the same manner as in Examples 1 and 2, and its physical properties were measured. The results are shown in Table 3.

Comparative Example 2 PPS (Toprene T-4) and ABS resin (Toyolac 500) were blended in the proportions shown in Table 3.

Test pieces were prepared in the same manner as in Examples 1 and 2, and the physical properties and average dispersed particle diameter were measured. The results are shown in Table 3.

Comparative Example 3 'pps (Toprene T-4), ABS resin (Toyolac 500), glycidyl methacrylate, and polystyrene resin (Dencastyrol MT-2, manufactured by Denki Kagaku Kogyo ■) were blended in the proportions shown in Table 3.

Test pieces were prepared in the same manner as in Examples 1 and 2, and the physical properties and average dispersed particle diameter were measured. The results are shown in Table 3.

Comparative Examples 4 to 5 PPS ()-prene T-4), ABS resin (Toyolac 500) and Modiper A4100 (manufactured by NOF Corporation, copolymer of glycidyl methacrylate, styrene, and ethylene, ethylene content 20% by weight or more) or Epicron 3050 (manufactured by Dainippon Ink and Chemicals, bisphenol A type epoxy resin) was mixed in the proportions shown in Table 3, and test pieces were prepared in the same manner as in Examples 1 and 2, and the physical properties and average dispersed particle diameter were determined. was measured. The results are shown in Table 3.

(Hereinafter, blank spaces) Examples 3 to 5 PPS to which various styrene polymers were added, ABS resin (Toyolac 500), polystyrene resin (Denka Styrol MT-2), thermoplastic elastomer (Toughtic Ml 913, manufactured by Asahi Kasei ■), Glass fiber (C3
-03-MA-411゜Made by Asahi Fiberglass ■) etc. in the proportions shown in Table 4. was measured. The results are shown in Table 4.

(Hereinafter, the margins) [Effects of the invention] A resin composition consisting of PPS to which a styrenic polymer has been added and a styrene polymer and/or a styrene copolymer has improved strength compared to PPS without substantially impairing the strength of the PPS resin. It has significantly superior flexibility in terms of elongation and impact strength, so it does not need to be reinforced with reinforcing agents such as glass fiber.

Can be used as a molding material.

Patent applicant: Ube Industries Co., Ltd.

Claims (1)

[Scope of Claims] A resin composition comprising (A) 40 to 98 parts by weight of a polyphenylene sulfide resin to which a styrene polymer has been added and (B) 60 to 2 parts by weight of a styrene polymer and/or a styrene copolymer. thing.