JPH0468066A - Polyphenylene sulfide resin composition - Google Patents

Abstract

PURPOSE:To obtain the title composition undergoing little change in melt viscosity even when kept in a molten and heated state for a long time and excellent in thermal stability by mixing polyphenylene sulfide irradiated with ultraviolet rays and an epoxy resin. CONSTITUTION:50-99pts.wt. polyphenylene sulfide irradiated with ultraviolet rays is mixed with 1-50pts.wt. resin having epoxy groups (e.g. styrene resin having epoxy groups) to give the title composition. This composition undergoes little change in melt viscosity even when kept in a molten and heated state for a long time and has excellent thermal stability.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a polyphenylene sulfide resin composition with excellent thermal stability.

The polyphenylene sulfide resin composition of the present invention, which has excellent thermal stability, can be injection-molded, extruded, and compression-molded, and can be used for injection-molded products, 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, so it is used to improve the rigidity and heat resistance of machinery, electrical/electronic parts, automobile parts, etc. Applications are being actively developed in fields where this is required.

However, when PPS is held at a temperature above its melting point, especially above 300°C, its melt viscosity increases, and in extreme cases it has almost no fluidity, making it difficult to perform injection molding or extrusion molding under stable conditions. It is known that PPS has excellent thermal stability, and PPS with excellent thermal stability is desired.

Conventionally, in order to improve the thermal stability of PP5O, resin compositions or branched PPS polymer compositions in which a curing/crosslinking retardant, a heat stabilizer, or a cured epoxy resin is blended with PPS, and the production of PPS polymers have been developed. Many methods have been proposed.

For example, JP-A-58-204045 discloses a resin composition consisting of PPS and an organic tin compound as a cure retarder, while JP-A-58-204046 discloses a resin composition consisting of PPS and a specific aminotriazole compound as a cure retardant. In JP-A No. 58-204047, the composition is PP.
A resin composition consisting of S and a stabilizer based on a specific phenolic amide or ester as a curing retarder,
In JP-A-59-108332, a resin composition consisting of PPS and a cured epoxy resin is disclosed in JP-A-59-11.
No. 5331 discloses a method for producing a PPS polymer in which low molecular weight PPS is removed and the molecular weight distribution is narrowed, as described in Japanese Patent Application Laid-Open No. 62-
No. 41227 discloses high molecular weight branched PPS.
The manufacturing method of P
A method for producing PPS has been proposed in which a nitrogen-containing cyclic organic residue is introduced into the PS main chain.

[Problem to be solved by the invention]

However, in the various proposals regarding the thermal stability of PP5O mentioned above,
Resin compositions consisting of PPS and various curing retarders disclosed in JP-A No. 8-204046 and JP-A-58-204047, or low molecular weight PPS disclosed in JP-A-59-115331. Method for producing PPS polymer with narrowed molecular weight distribution and JP-A-62-4
A method for producing a high molecular weight branched PPS disclosed in Japanese Patent Publication No. 1227, and a method for producing PPS in which a nitrogen-containing cyclic organic residue is introduced into the PPS main chain disclosed in Japanese Patent Application Laid-Open No. 177029/1982. Although the manufacturing method provides improved thermal stability during heating over conventional PPS, if held in the molten heated state for an insufficiently long time, the melt viscosity increases, limiting the range of applications.

PP disclosed in Japanese Patent Application Laid-Open No. 59-108332
A resin composition composed of S and a cured epoxy resin is said to have improved flow stability during molding, but the change in melt viscosity is large and the effect of improving thermal stability is small.

The present invention provides PPS with excellent thermal stability, which shows little change in melt viscosity even when kept in a melted and heated state for a long time.
The purpose is to provide a resin composition.

[Means to solve 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 (2) 1 to 50 parts by weight of a resin having an epoxy group.

The PPS resin composition of the present invention is comprised of a specific proportion of pps irradiated with ultraviolet rays as the (a) component and a resin having an epoxy group as the (2) component, and is molded to be kept in a melted and heated state for a long time. Even in processing methods, changes in melt viscosity are small and thermal stability is excellent.

The present invention will be explained in detail below.

The PPS irradiated with ultraviolet light, which is the component (a) of the present invention, is a known PPS, preferably a powdery PPS with a wavelength range of 1.
Using ultraviolet rays of 00 to 400 mμ, ultraviolet rays of 2 to 60 mμ
It can be produced by irradiating mW-hr/c+ll.

In order to make the UV irradiation uniform, PPS has a particle size of 150μ.
It is preferable to use powder having a diameter of less than m. Also, the irradiation amount is 2 m/hr/cIi! If it is less than 20%, it is not possible to obtain a PPS composition with excellent thermal stability, which is the object of the present invention. Also, if it exceeds 60+n1lhr/ctA, P
This is not preferable because it becomes harsh on the PS&11PPS composition and impairs the appearance of the product obtained by molding.

The PPS used in the present invention preferably has a phenylene sulfide unit structure represented by the following structural formula (1) in an amount of 70 mol % or more in view of heat resistance, solvent resistance, and mechanical properties. If the phenylene sulfide unit content is less than 70 mol%, heat resistance will decrease.

The remaining 30 mol% is a meta bond represented by the following structural formula (2), an ether bond represented by structural formula (3), a sulfone bond represented by structural formula (4), and an alkyl group in which R has 12 or less carbon atoms in structural formula (5). or a substituted phenylene sulfide bond of either an alkoxy group, a phenyl group, or a nitro group, structural formula (6)
It consists of a biphenyl bond, a naphthyl bond of structural formula (7), a trifunctional phenyl sulfide bond, etc.

In the present invention, the PPS having the above structure has a melt flow rate of 5 to 5 when measured at 315°C and a load of 5 dazzles using a melt indexer specified by ASTM D1238-74T.
10000 g/10 min, preferably 5-500
g/10 min is used.

Commercially available PPSs can be used as these PPSs. For example, the product name “Rydon P” manufactured by Philips
P5J, the product name "Toprene" manufactured by Topren Co., Ltd., the product name "Susteel" manufactured by Tosoh Sasteel Co., Ltd., and the product name "Fortron" manufactured by Kureha Chemical Industry ■.

The resin having an epoxy group, which is the component (2) of the present invention, is
It 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 α,β-unsaturated acid has the general formula (
8) and (9), and specific examples include glycidyl acrylate, glycidyl methacrylate, glycidyl ethacrylate, glycidyl itaconate, allyl glycidyl ether, and vinyl glycidyl ether. Among these, glycidyl methacrylate is preferred.

ROO vinyl monomers include ethylene, propylene, butylene, butadiene, isoprene, acrylonitrile,
Examples include methyl acrylate, methyl methacrylate, styrene, methylstyrene, vinylxylene, dichlorostyrene, bromstyrene, dibromstyrene, pt-butylstyrene, ethylstyrene, and vinylnaphthalene. These vinyl monomers may be used alone or in combination of two or more.

The reaction between the glycidyl group-containing compound of the α,β-unsaturated acid and the vinyl monomer can be carried out by bulk polymerization, solution polymerization, suspension polymerization, or emulsion polymerization using known radical polymerization methods. Further, in this reaction, both may be directly reacted, or the vinyl monomer may be polymerized in advance and then reacted.

The reaction ratio of the glycidyl group-containing compound of the α,β-unsaturated acid and the vinyl monomer is α in terms of weight ratio.

Glycidyl group-containing compound of β-unsaturated acid: Vinyl monomer -0.5-40: 99.5-60, preferably 2-40
It is preferable to set it as 20:9B-80. α.

If the amount of the glycidyl group-containing compound of the β-unsaturated acid is less than 0.5 parts by weight, the reactivity with the ultraviolet irradiated PPS of component (a) will be poor, making it difficult to obtain PPS with excellent thermal stability, making it impractical. Not. Moreover, if the amount exceeds 40 parts by weight, it is not preferable because it becomes difficult to synthesize a vinyl resin having these epoxy groups.

As mentioned above, the vinyl resin having an epoxy group of the present invention is a copolymer of a glycidyl group-containing compound of a d, β-unsaturated acid and a vinyl monomer, but this copolymer is a random copolymer, It may be a block copolymer, a graft copolymer or a mixture thereof. It is usually preferable to use a random copolymer.

The number average molecular weight of this vinyl resin having an epoxy group is 3,000 to 150,000, preferably 10,000 to 1
It is 00000. This number average molecular weight can be adjusted by adjusting the amount of radical initiator used in the copolymerization reaction, reaction temperature, etc.

Specific examples of resins having epoxy groups include styrene-
Glycidyl methacrylate copolymer, glycidyl compound modified product of hydrogenated styrene-butadiene-styrene block copolymer, ethylene-glycidyl methacrylate copolymer,
Examples include modified glycidyl compounds of ethylene-propylene copolymers.

The PPS resin composition of the present invention with excellent thermal stability includes component (a) 550 to 99 parts by weight of ultraviolet irradiated PP, preferably 55 to 95 parts by weight, and component (2) 50 to 1 part by weight of the resin having an epoxy group. parts, preferably 45 to 5 parts by weight. If the number of lids used for PPS irradiated with ultraviolet rays is less than the above lower limit, the melt viscosity of the PPS resin composition will decrease when held in the form of a molten heating stick, and not only will thermal stability not be improved, but parity during injection molding will decrease. This is not preferable as it tends to cause problems such as this. Furthermore, if the amount of PPS irradiated with ultraviolet rays is greater than the above upper limit, the melt viscosity of the PPS resin composition will increase and the thermal stability will not be improved, which is not preferable.

The production of the PPS resin composition with excellent thermal stability of the present invention is as follows:
PP irradiated with ultraviolet light as component (a) at room temperature prior to melting
After pre-kneading S and the resin having an epoxy group as the component (2) using a high-speed rotating stirrer such as a Henschel mixer or a juicer mixer that is used for normal pre-mixing,
It can be carried out at a temperature of 275° C. or higher, preferably 285 to 350° C., using ordinary melt-kneading processing equipment such as an extruder, Banbury mixer, or kneader. Furthermore, injection molding, compression molding, It can be processed into molded products for various uses by extrusion molding, etc.

In the PPS composition of the present invention having excellent thermal stability, reinforcing materials and fillers in various shapes such as fibers, powders, flakes, and mats can be used 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, organic fibers such as polyamide, fluororesin, polyester, and acrylic resin, copper, iron, nickel, zinc, soot, lead, stainless steel, aluminum, gold, and silver. Metal powders such as fumed silica, aluminum silicate, glass beads, carbon black, quartz powder, talc, titanium oxide, iron oxide, rhusium carbonate, etc.
There is diatomaceous earth. In the case of fibrous substances, 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.

These reinforcing materials and fillers may also be surface-treated with a known silane coupling agent or titanate camping 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 may be used alone or in combination of two or more.

The PPS resin composition with excellent thermal stability of the present invention may contain antioxidants such as hindered phenols, hydroquinone, thioethers, phosphites, substituted products thereof, copper compounds, etc., as long as the object of the present invention is not impaired. Heat stabilizers, ultraviolet absorbers such as resorcinol, salicylate, hensitriazole, 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, It is also possible to add one or more additives such as flame retardant aids such as antimony oxide, sodium dodecylbenzenesulfonate, antistatic agents such as polyalkylene glycol, crystallization promoters, dyes, and pigments.

Further, unirradiated PPS may be mixed with PPS irradiated with ultraviolet rays. In addition, small amounts of polyethylene, polypropylene, ethylene/propylene copolymer, ethylene/vinyl acetate copolymer, styrene/vinyl acetate copolymer, etc.
Butadiene copolymer, hydrogenated styrene-butadiene copolymer, polyamide, polyamide elastomer, polyester, polyester elastomer, polycarbonate,
Thermoplastic resins such as polysulfone, thermosetting resins such as phenol resins, melamine resins, silicone resins, and epoxy resins can also be added.

Examples of the present invention will be described in detail below. However, the present invention is not limited to this implementation.

Thermal stability evaluations described in Examples and Comparative Examples were conducted using a Toyo Seiki ruptured Labo Plastomill Model 100C-R60 as a batch-type melt-kneading evaluation device, and the PPS resin composition was heated at 300°C in air. Melt kneading was carried out, and kneading torque values were determined for each kneading time (10, 30°, 60.90 minutes) of the melt-kneaded product.

Also, the kneading time refers to the time after the temperature indicator for the resin temperature installed in the mixer of Labo Plastomill adds the kneading composition.
The time when the kneading set temperature was reached was defined as 0 hour.

Production example 1 [Production method of ultraviolet irradiated PPS (UVP)] PPS
Toprene T-4 (particle system 13) manufactured by Toprene Co., Ltd.
0 μm) in a stainless steel (20 x 5 cm) container for about 1 m.
253.7 mμ thick and irradiated with ultraviolet light having a main wavelength of 253.7 mμ. Ultraviolet irradiation is carried out by Sangabrinil (SAN G
ABURIEL), product name Mineralite (formerly RERA)
LIG)IT) was used. With this irradiation device, the PPS samples UVP-1, irradiated with ultraviolet light for 1 minute at an irradiation distance of approximately 1 cm and for 1 minute according to each irradiation amount at an output of 60 W,
Sample UVP-3 with irradiation time of 3 minutes and irradiation time of 5
Sample UVF-5 was obtained for minutes. Furthermore, UVP-3 and U
In VP-5, PPS was stirred once every minute in order to uniformly irradiate ultraviolet rays.

Production example 2 Fortron 205W manufactured by Kureha Chemical Industry ■ as PPS
Sample UVPP-3 was obtained by irradiating ultraviolet light for 3 minutes in the same manner as in Production Example 1.

Production Example 3 [Production of styrene resin (ES) having an epoxy group] 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 the mixture was uniformly mixed at 25° C. for 20 minutes while blowing nitrogen. Thereafter, the separable flask was placed in an oil bath at 85°C, and after stirring at 85°C for 60 minutes in a nitrogen atmosphere, the temperature was further raised to 105°C, and the mixture was reacted with stirring for 45 minutes.

After the reaction, the reaction polymerization solution was allowed to cool and was separated into methanol under strong stirring. Then dried glycidyl methacrylate 10
A polystyrene resin ES having an epoxy group and a number average molecular weight of 11,600 was obtained. The content of glycidyl methacrylate was determined by titration method of epoxy group concentration (
JIS K-7236).

Production Example 4 [Production method of styrene resin having epoxy group (ESEBS) Kotaftic H1041 (trade name, manufactured by Asahi Kasei Corporation, hydrogenated styrene-butadiene-styrene block copolymer) 97
Put the weight part into the solution kneader of Labo Plastomill and mix it at 260
After melting at °C, 2.5wt glycidyl methacrylate
% and 0.5 parts by weight of Perbutyl Z (trade name, manufactured by NOF Corporation) were added, and the mixture was uniformly mixed for 10 minutes under a nitrogen gas atmosphere to react. This reaction mixture was pulverized and washed with acetone to obtain a styrenic resin to which 2 wt % of glycidyl methacrylate was added. The content of glycidyl methacrylate was determined by titration method of epoxy group concentration (JIS K-7236).
It was measured with

Examples 1 to 5 Ultraviolet irradiated PPS obtained in Production Example 1 (UVP-1,
UVP-3, UVP-5) and the styrene resin (ES) having an epoxy group produced in Production Example 3 were blended in the proportions shown in Table 1, and heated to a temperature set at 300 using a laboplast mill manufactured by Toyo Seiki. ”c Melt kneading and kneading time (
10, 30, 60° 90 minutes) and the kneading torque value was measured. The results are shown in Table 1.

Example 6 Ultraviolet irradiated PPS obtained in Production Example 2 (UVPP-3
) and the styrene resin (ES) having an epoxy group produced in Production Example 3 were blended in the proportions shown in Table 1, and melted and kneaded at a set temperature of 300°C using Toyo Seiki's Laboplast Mill for a kneading time (10 , 30°60.90 minutes) and the kneading torque value was measured. The results are shown in Table 1.

Example 7 Ultraviolet irradiated PPS obtained in Production Example 1 (UVP-3)
and the styrene resin with epoxy groups (ESEBS) produced in Production Example 4 were blended in the proportions shown in Table 1, and the temperature was set at 300°C using a new Laboplast Mill manufactured by Toyo Seiki.
Melt and knead the kneading time (10, 30, 60, 90 minutes).
The relationship between this and the kneading torque value was measured. The results are shown in Table 1.

Example 8 Ultraviolet irradiated pps (uvp-3) obtained in Production Example 1
and Bond First E (product name: manufactured by Sumima Kagaku Co., Ltd., polyethylene with epoxy groups, epoxy concentration 6.86Xl)
moffi/g) in the proportions shown in Table 1, and set the temperature to 30 using a new Laboplast Mill manufactured by Toyo Seiki.
Melt kneading at 0°C, kneading time (10, 30, 60, 9
0 minutes) and the kneading torque value was measured. Results first
Shown in the table.

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

Comparative Example 3 UVP-3 produced above and polystyrene resin (trade name: Denka GP-1 manufactured by Denki Kagaku Co., Ltd.) were blended in the proportions shown in Table 1, and melted and kneaded in the same manner as in Example 1. The relationship between time (10, 30, 60, 90 minutes) and kneading torque value was measured. The results are shown in Table 1.

Comparative Example 4 The UVP-3 produced above, polystyrene resin (trade name: Denka GP-1 manufactured by Denki Kagaku Co., Ltd.) and trade name Epicron 3050 (bisphenol A type epoxy resin manufactured by Dainippon Ink and Chemicals) are shown in Table 1. The mixture was melt-kneaded in the same manner as in Example 1, and the kneading time (10, 30
, 60, 90 minutes) and the kneading torque value was measured.

The results are shown in Table 1.

〔Effect of the invention〕

A PPS resin composition containing a specific proportion of PPS irradiated with ultraviolet rays and a resin having an epoxy group exhibits small change in melt viscosity even when kept in a molten and heated state for a long time, and has excellent thermal stability.

Claims (2)

[Claims] (1) (a) 50 to 99 parts by weight of polyphenylene sulfide irradiated with ultraviolet rays; (2) A polyphenylene sulfide resin composition comprising 1 to 50 parts by weight of a resin having an epoxy group.