JP2748662B2 - Polyphenylene sulfide resin composition - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a polyphenylene sulfide resin composition having excellent thermal stability.

The polyphenylene sulfide resin composition having excellent thermal stability of the present invention can be injected, extruded, and compression-molded, and can be used for injection-molded articles, films, fibers, and the like.

[Conventional technology and problems]

Polyphenylene sulfide (hereinafter simply referred to as PPS) has excellent mechanical strength, heat resistance, solvent resistance, etc., and is flame-retardant. Application development in the field where is required is actively performed.

However, PPS has the drawback that if it is kept at a temperature higher than the melting point, especially at a temperature higher than 300 ° C, the melt viscosity will increase, and in extreme cases, it will have almost no fluidity, making it difficult to perform injection molding or extrusion under stable conditions. It is known that
PPS with excellent thermal stability is desired.

Conventionally, in order to improve the thermal stability of PPS, a resin composition or a branched PPS polymer composition in which a curing / crosslinking retarder or a heat stabilizer or an epoxy resin cured product is blended with PPS, and a polymer of PPS Many methods such as a manufacturing method have been proposed.

For example, JP-A-58-204045 discloses a resin composition comprising PPS and an organotin compound as a curing retarder.
Japanese Patent Application Laid-Open No. 58-204046 discloses a resin composition comprising PPS and a specific aminotriazole compound as a curing retarder.
In JP-A-58-204047, a resin composition comprising PPS and a stabilizer based on a specific phenolic amide or ester as a curing retarder is disclosed in JP-A-59-108332.
JP-A-59-115331 discloses a method for producing a PPS polymer in which a resin composition comprising S and a cured epoxy resin has a narrow molecular weight distribution by removing low-molecular-weight PPS.
No. 27 proposes a method for producing a branched PPS having a high molecular weight, and JP-A-62-177029 proposes a method for producing a PPS in which a nitrogen-containing cyclic organic residue is introduced into a PPS main chain. .

[Problems to be solved by the invention]

However, in the proposals regarding the thermal stability of the various PPSs described above, JP-A-58-204045, JP-A-58-204046
PPS disclosed in JP-A-58-204047
Or a resin composition comprising
A method for producing a PPS polymer having a narrow molecular weight distribution by removing low molecular weight PPS disclosed in JP-A-59-115331 and a high-molecular-weight branched chain disclosed in JP-A-62-41227. The method for producing PPS and the method for producing PPS in which a nitrogen-containing cyclic organic residue is introduced into the main chain of PPS disclosed in JP-A-62-177029 are more thermally stable than conventional PPS during heating. Although improved, the melt viscosity increases when held in an inadequately prolonged melt heating state, limiting the range of applications.

The resin composition comprising PPS and epoxy resin cured product disclosed in JP-A-59-108332 is said to have improved flow stability during molding, but the change in melt viscosity is large, The effect of improving the thermal stability is small.

The present invention has a small change in melt viscosity even when held in a melt-heated state for a long time, and has excellent thermal stability PPS.
The purpose is to provide a resin composition.

[Means for solving the problem]

 The object of the present invention can be achieved by a PPS resin composition comprising (a) 50 to 99 parts by weight of PPS irradiated with ultraviolet rays and (b) 1 to 50 parts by weight of a resin having an epoxy group.

The PPS resin composition of the present invention comprises a specific proportion of a PPS irradiated with ultraviolet rays as the component (a) and a resin having an epoxy group as the component (b), and the molding is held in a state of being melted and heated for a long time. Even in the processing method, the change in melt viscosity is small and the thermal stability is excellent.

 Hereinafter, the present invention will be described in detail.

The UV-irradiated PPS, which is the component (a) of the present invention, is a known PPS, preferably a powdery PPS, and has a wavelength range of 100 to 400.
It can be produced by irradiating ultraviolet rays of ² to 60 mW · hr / cm ² using ultraviolet rays of mμ. In order to make the irradiation of ultraviolet rays uniform, it is preferable to use PPS having a particle diameter of 150 μm or less. Further, when the irradiation amount is less than ² mW · hr / cm ^2, the PPS composition having excellent thermal stability for the purpose of the present invention cannot be obtained. On the other hand, if it exceeds 60 mW · hr / cm ² , the coloring of the PPS composition becomes inferior, and the appearance of the product obtained by molding is unfavorably deteriorated.

The PPS used in the present invention preferably has a phenylene sulfide unit structure represented by the following structural formula (1) of 70 mol% or more from the viewpoint of heat resistance, solvent resistance and mechanical properties. If the phenylene sulfide unit is less than 70 mol%, the heat resistance decreases. The remaining 30 mol% is a meta bond of the following structural formula (2), an ether bond of the structural formula (3), a sulfone bond of the structural formula (4), and R is a carbon atom in the structural formula (5).
Substituted phenylene sulfide bond of any of 12 or less alkyl or alkoxy groups, phenyl group and nitro group, biphenyl bond of structural formula (6), naphthyl bond of structural formula (7), trifunctional phenyl sulfide bond, etc. .

In the present invention, the PPS having the above structure, the melt flow rate of which is measured at 315 ° C. with a load of 5 kg using a melt indexer specified by ASTM D1238-74T, is 5 to 10,000 g / 10 minutes, preferably 5 to 500 g / 10. Minutes are used.

As these PPSs, commercially available ones can be used. For example, the product name “Lyton PP” manufactured by Philips
S ", a product name" Toprene "manufactured by Toprene, a product name" Sastile "manufactured by Tosoh Sastile, a product name" Fortron "manufactured by Kureha Chemical Industry Co., Ltd.

The resin having an epoxy group as the component (b) of the present invention is a copolymer of a glycidyl group-containing compound of an α, β-unsaturated acid and a vinyl monomer.

The glycidyl group-containing compound of an α, β-unsaturated acid is represented by the general formula (8), and specific examples include glycidyl acrylate, glycidyl methacrylate, and glycidyl ethacrylate. Of these, glycidyl methacrylate is preferred.

Vinyl monomers include ethylene, propylene,
Examples include butylene, butadiene, isoprene, acrylonitrile, methyl acrylate, methyl methacrylate, styrene, methyl styrene, vinyl xylene, dichlorostyrene, bromostyrene, dibromostyrene, Pt-butylstyrene, ethylstyrene, vinylnaphthalene, and the like. These vinyl monomers may be used alone or in combination of two or more.

The reaction between a glycidyl group-containing compound of an α, β-unsaturated acid and a vinyl monomer is carried out by using a known radical polymerization method.
It can be carried out by bulk, solution, suspension or emulsion polymerization. In this reaction, the two may be reacted directly, or the vinyl monomers may be polymerized in advance and then reacted.

The reaction ratio between the glycidyl group-containing compound of the α, β-unsaturated acid and the vinyl monomer is 0.5% by weight of the glycidyl group-containing compound of the α, β-unsaturated acid: vinyl monomer = 0.5
-40: 99.5-60, preferably 2-20: 98-80. The glycidyl group-containing compound of α, β-unsaturated acid is 0.5%
If the amount is less than part by weight, the reactivity of the component (a) with the PPS irradiated with ultraviolet rays becomes poor, and it is difficult to obtain PPS having excellent thermal stability, which is not practical. On the other hand, if it exceeds 40 parts by weight, it becomes difficult to synthesize these vinyl resins having an epoxy group, which is not preferable.

The epoxy resin having an epoxy group of the present invention is a copolymer of a glycidyl group-containing compound of an α, β-unsaturated acid and a vinyl monomer as described above, and this copolymer is a random copolymer, It may be a block copolymer, a graft copolymer or a mixture thereof. Usually, it is preferable to use a random copolymer.

The number average molecular weight of the vinyl resin having an epoxy group is 3,000 to 150,000, preferably 10,000 to 100,000.
This number average molecular weight can be adjusted by the amount of the radical initiator used in the copolymerization reaction, the reaction temperature and the like.

Specific examples of the resin having an epoxy group include a styrene-glycidyl methacrylate copolymer, a hydrogenated styrene-butadiene-styrene block copolymer modified glycidyl compound, an ethylene-glycidyl methacrylate copolymer, and an ethylene-propylene copolymer. Modified glycidyl compounds of polymers and the like.

The PPS resin composition of the present invention having excellent thermal stability is preferably 50 to 99 parts by weight, preferably 55 to 9 parts by weight, of the PPS irradiated with the component (a).
5 parts by weight, 50 to 1 resin having epoxy group of component (b)
It consists of parts by weight, preferably 45 to 5 parts by weight. When the amount of the PPS that has been irradiated with ultraviolet light is less than the above lower limit, the melt viscosity of the PPS resin composition decreases when held in a melt-heated state, not only does the thermal stability not improve, but also burrs during injection molding. Is likely to occur, which is not preferable. If the amount of UV-irradiated PPS is more than the upper limit, PPS
It is not preferable because the melt viscosity of the resin composition is increased and the thermal stability is not improved.

The production of the PPS resin composition having excellent heat stability of the present invention includes:
PPS irradiated with component (a) ultraviolet rays at room temperature prior to melting
And a resin having an epoxy group as the component (b) are preliminarily kneaded with a high-speed rotary stirrer such as a Henschel mixer or a juicer mixer used for normal premixing.
Extruder, Banbury mixer, can be performed using a conventional melt kneading equipment such as a kneader at a temperature of 5 ° C or more, preferably 285 to 350 ° C, and further, injection molding, compression molding, extrusion molding, etc. It can be processed into molded products for various uses.

The PPS composition of the present invention having excellent thermal stability can use reinforcing materials and fillers of various shapes such as fibrous, powdery, flake or matte shapes as long as the moldability and physical properties are not impaired.

Specific examples of reinforcing materials and fillers that can be used in the present invention include glass fiber, asbestos fiber, carbon fiber, silica fiber, silica-alumina fiber, alumina fiber, zirconia fiber, boron nitride fiber, silicon nitride fiber, boron fiber, Metal fibers such as stainless steel, aluminum, titanium, copper, brass, and magnesium; and organic fibers such as polyamide, fluororesin, polyester, and acrylic resin;
Metal powders such as copper, iron, nickel, zinc, tin, lead, stainless steel, aluminum, gold, silver, etc., fumed silica, aluminum silicate, glass beads, carbon black,
Examples include quartz powder, talc, titanium oxide, iron oxide, calcium carbonate, and diatomaceous earth. In the case of a fibrous substance, those having an average fiber diameter of 0.1 to 30 μm and a fiber length of 50 μm or more can be preferably used. As these reinforcing materials and fillers, those surface-treated with a known silane coupling agent or titanate-based coupling agent can also be used.

The amount of the reinforcing material and the filler used is the resin composition 100 of the present invention.
It is 1 to 300 parts by weight, preferably 10 to 250 parts by weight based on parts by weight.

These reinforcing materials and fillers may be used alone or in combination of two or more.

The PPS resin composition excellent in heat stability of the present invention is an antioxidant such as hindered phenol, hydroquinone, thioether, phosphites and their substituted or copper compounds, as long as the object of the present invention is not impaired. Heat stabilizers, ultraviolet absorbers such as resorcinol, salicylate, benzotriazole, and benzophenone; mold release agents such as stearic acid and its salts; stearyl alcohol; halogen-based, phosphate-based, melamine or cyanuric-based flame retardants; It is also possible to add one or more additives such as a flame retardant aid such as antimony oxide, an antistatic agent such as sodium dodecylbenzenesulfonate and polyalkylene glycol, a crystallization accelerator, a dye, and a pigment.

In addition, unirradiated PPS can be mixed with ultraviolet-irradiated PPS and used. In addition, a small amount of polyethylene, polypropylene, ethylene-propylene copolymer, ethylene-vinyl acetate copolymer, styrene-butadiene copolymer, hydrogenated styrene-butadiene copolymer,
Polyamide, polyamide elastomer, polyester,
Thermoplastic resins such as polyester elastomers, polycarbonates, and polysulfones, and thermosetting resins such as phenol resins, melamine resins, silicone resins, and epoxy resins can also be added.

Hereinafter, examples of the present invention will be described in detail. However, the present invention is not limited to the present embodiment.

Evaluation of the thermal stability described in Examples and Comparative Examples was performed using a Labo Plastomill manufactured by Toyo Seiki Seisakusho Co., Ltd .: Model 100C-R60 as a batch-type melt-kneading evaluation device. The kneading was performed according to the kneading torque value for each kneading time (10, 30, 60, 90 minutes) of the melt-kneaded product.

The kneading time was defined as 0 hour when the temperature indicated for the resin temperature provided in the mixer of the Labo Plastomill reached the kneading set temperature after the kneading composition was charged.

Production Example 1 [Production method of ultraviolet-irradiated PPS (UVP)] Toplen T-4 (130 μm particle size) manufactured by Topren Co., Ltd. as a PPS was placed in a stainless steel (20 × 5 cm) container with a thickness of about 1 mm, and the main wavelength was measured. Irradiation was performed with 253.7 mμ ultraviolet light. The ultraviolet irradiation used Mineralite (MIRERA LIGHT) manufactured by San Gabriel. With this irradiation device, at a power of 60 W, a PPS sample UVP-
1. A sample UVP-3 having an irradiation time of 3 minutes and a sample UVP-5 having an irradiation time of 5 minutes were obtained. UVP-3 and UVP-
5 is PP once a minute to irradiate ultraviolet rays evenly
S was stirred.

Production Example 2 Fortron 205W manufactured by Kureha Chemical Industry Co., Ltd. as PPS
As in Production Example 1, a sample UVPP-3 having an irradiation time of 3 minutes was irradiated in the same manner as in Production Example 1.

Production Example 3 [Production of styrene resin having epoxy group (ES)] 216 g of styrene was placed in a separable flask equipped with a stirrer.
24 g of glycidyl methacrylate, 160 g of toluene and 2 g of azobisisobutyronitrile were added, and mixed uniformly at 25 ° C. for 20 minutes while blowing nitrogen. After that, place the separable flask in an oil bath at 85 ° C, and in a nitrogen atmosphere,
After stirring at 85 ° C for 60 minutes, the temperature was further raised to 105 ° C,
The reaction was stirred for 5 minutes.

After the reaction, the reaction polymerization solution was allowed to cool and separated into methanol under strong stirring. Then dried glycidyl methacrylate 10
A polystyrene resin ES containing wt% and having an epoxy machine with a number average molecular weight of 11600 was obtained. The content of glycidyl methacrylate was determined by titration of the epoxy group concentration (JIS K-7
236).

Production Example 4 [Production Method of Styrene Resin Having Epoxy Group (ESEBS)] 97 parts by weight of Tuftec H1041 (trade name, manufactured by Asahi Kasei Corporation, hydrogenated styrene-butadiene-styrene block copolymer) was kneaded with a solution in a Labo Plastomill. After melting at 260 ° C, 2.5 wt% of glycidyl methacrylate and 0.5 parts by weight of Perbutyl Z (trade name, manufactured by NOF CORPORATION) are added, and the mixture is uniformly mixed in a nitrogen gas atmosphere for 10 minutes to react. Was. The reaction mixture was pulverized and washed with acetone to obtain a styrene resin to which 2% by weight of glycidyl methacrylate was added.
In addition, the content of glycidyl methacrylate was measured by a titration method (JIS K-7236) of an epoxy group concentration.

Examples 1 to 5 UV-irradiated PPS (UVP-1, UVP-3, UP) obtained in Production Example 1
VP-5) and the styrene resin having an epoxy group (ES) produced in Production Example 3 were blended in the proportions shown in Table 1, respectively.
Using a Labo Plastomill manufactured by Toyo Seiki Seisaku-sho, Ltd., the mixture was melted and kneaded at a set temperature of 300 ° C., and the relationship between the kneading time (10, 30, 60, 90 minutes) and the kneading torque value was measured. The results are shown in Table 1.

Example 6 The ultraviolet-irradiated PPS (UVPP-3) obtained in Production Example 2 and the styrene resin having an epoxy group produced in Production Example 3 (E
S) was blended at the ratio shown in Table 1 and melted and kneaded at a set temperature of 300 ° C using Labo Plastomill of Toyo Seiki Seisaku-sho, Ltd.
The relationship between the kneading time (10, 30, 60, 90 minutes) and the kneading torque value was measured. The results are shown in Table 1.

Example 7 The ultraviolet-irradiated PPS (UVP-3) obtained in Production Example 1 and the styrene-based resin having an epoxy group produced in Production Example 4 (ES
EBS) at the ratios shown in Table 1 and melt-kneading at a set temperature of 300 ° C using Labo Plast Mill manufactured by Toyo Seiki Seisaku-sho, Ltd., kneading time (10, 30, 60, 90 minutes) and kneading torque value Was measured. The results are shown in Table 1.

Comparative Example 1 Using PPS (Toprene, T-4), melt kneading was performed in the same manner as in Example 1, and the relationship between the kneading time (10, 30, 60, 90 minutes) and the kneading torque value was measured. The results are shown in Table 1.

Comparative Example 2 The above-mentioned trade name Topren T-4 and Denka GP-1 (trade name, manufactured by Denki Kagaku Co., Ltd., polystyrene resin) were blended in the ratio shown in Table 1, and were melt-kneaded in the same manner as in Example 1. The relationship between the kneading time (10, 30, 60, 90 minutes) and the kneading torque value was measured. The results are shown in Table 1.

Comparative Example 3 The above-prepared UVP-3 and Denka GP-1 (trade name, manufactured by Denki Kagaku Co., Ltd., polystyrene resin) were blended in the proportions shown in Table 1, and were melt-kneaded in the same manner as in Example 1, and kneaded. Time (1
0, 30, 60, 90 minutes) and the kneading torque value were measured. The results are shown in Table 1.

Comparative Example 4 UVP-3 and Denka GP-1 (trade name, manufactured by Denki Kagaku, polystyrene resin) and Epicron 3050 produced above
(Trade name, Bisphenol A type epoxy resin, manufactured by Dainippon Ink and Chemicals, Inc.) in the proportions shown in Table 1, melt-kneaded in the same manner as in Example 1, and kneading time (10, 30, 60) , 9
0 min.) And the kneading torque value were measured. First result
It is shown in the table.

[Effect of the Invention] The PPS resin composition in which the ultraviolet ray-irradiated PPS and the resin having an epoxy group are blended in a specific ratio has a small change in melt viscosity even when held for a long time in a melt-heated state, and has excellent heat stability. I have.

Claims (1)

(57) [Claims] 1. A polyphenylene sulfide resin composition comprising: (a) 50 to 99 parts by weight of polyphenylene sulfide irradiated with ultraviolet rays; and (b) 1 to 50 parts by weight of a resin having an epoxy group.