JPH059386A - Resin composition - Google Patents

Abstract

PURPOSE:To provide a resin composition having high glass transition temperature and excellent in flame-retardance, chemical resistance, moldability, flexibility, impact resistance, heat-resistance, etc., and suitable for pneumatic part, electronic part, etc. CONSTITUTION:The objective composition is produced by compounding (A) an aromatic sulfide/sulfone polymer having the recurring unit of formula (-phi- is p-phenylene) and a melt viscosity of 10-10<5> poise and obtained by the polycondensation of p-dimercaptobenzene and 4,4'-dihalodiphenylsulfone, (B) one or more kinds of miscible resins (e.g. polyamide, thermoplastic polyester and polysulfone) and, as necessary, (C) a filler.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION The present invention has a high glass transition temperature (T
g), and an aromatic sulfide / sulfone polymer which is an amorphous polymer having excellent heat resistance, flame retardancy and mechanical properties. The resin composition can give molded articles of various shapes by molding methods such as injection molding, compression molding and extrusion molding. Electric / electronic parts, automobile parts, or construction, civil engineering, aviation, space, and marine fields. It is used as a molding material in various fields such as.

[0002]

2. Description of the Related Art In recent years, a wide variety of polymeric materials have been developed, among which high heat resistance and glass transition temperature (Tg) are high.
A variety of engineering plastics having the following are attracting attention. Amorphous engineering plastics such as polycarbonate (hereinafter abbreviated as PC), polyarylate (hereinafter abbreviated as PAr) and polysulfone (hereinafter abbreviated as PSF) have various uses due to their high impact resistance and heat resistance. Is used for. However, these resins have problems that they are inferior in moldability and chemical resistance, or inferior in flame retardancy.

On the other hand, a repeating unit (-φ-SO ₂ -φ-S-) (however, -φ-) is one of the polyarylene sulfide-based resins (hereinafter, abbreviated as PAS-based resins) having excellent flame retardancy.
Is a p-phenylene group, which will be referred to hereinafter. Also disclosed in JP-B-53-25880 and the like are polyphenylene sulfide sulfones (hereinafter, abbreviated as PPSS). This resin is amorphous, has a high Tg, and is relatively excellent in mechanical properties such as impact resistance, which has been a problem with other PAS-based resins, making it attractive as a high-performance engineering plastic. Came.
However, this resin has a problem that it has poor high-temperature fluidity, has a problem in moldability, and is inferior to an aromatic or ketone organic solvent such as toluene or acetone.

Further, polyphenylene sulfide having the above-mentioned PPSS and (-φ-S-) repeating units (hereinafter referred to as "
A random copolymer with PPS) and a block copolymer (Japanese Patent Laid-Open No. 63-13066) are already known, but in the case of a random copolymer, the properties of the resulting polymer are very high. There were large variations, and it was very difficult to reduce this variation. Regarding the block copolymer, mechanical properties such as impact resistance are insufficient, and the glass transition temperature Tg of PPS (80 to 80
Above 90 ° C., there was a problem that the elastic modulus remarkably decreased and the resin softened.

[0005]

DISCLOSURE OF THE INVENTION The present inventors
General formula [-φ-SO ₂ -φ-S-φ-S-] (however,
-Φ- represents a p-phenylene group. The aromatic sulfide / sulfone polymer (hereinafter abbreviated as PPSSS), which is an amorphous resin having a repeating unit represented by the formula (1), was found to have high Tg, heat resistance, and flame retardancy. It has excellent mechanical properties and moldability. Especially regarding impact resistance and flexibility, PPS and PPS / PPS
It is superior to PAS resins such as S block copolymers.

An object of the present invention is to provide a highly functional resin composition having more excellent properties by blending another miscible resin with PPSSS, which is an amorphous resin having such excellent performance. To get.

[0007]

That is, the present invention provides (A) the general formula [-φ-SO ₂ -φ-S-φ-S-] (provided that
φ-represents a p-phenylene group. The present invention relates to a resin composition comprising an aromatic sulfide / sulfone polymer having a repeating unit represented by the formula (4) and (B) at least one miscible resin, and optionally a filler.

The aromatic sulfide / sulfone polymer (PPSSS) of the present invention is a polymer having 90 mol% or more of the repeating unit represented by the above general formula. A main structural unit other than the above formula may be formed in the synthetic process (-φ-
SO ₂ -φ-S-) and (-φ-S-). Further, the aromatic ring has F, Cl, Br, CH ₃ , COOH, NH ₂ ,
Substituents such as OH, CN and NO ₂ may be introduced.

The PPSSS has a melt viscosity of 10 to 10.
10 ⁵ poise, particularly preferably 50 to 5 × 10 ⁴ poise. Good results can be expected in high temperature fluidity and mechanical strength during molding within the range where the melt viscosity is high. The P
The glass transition temperature (Tg) of PSSS is 150 ° C or higher,
It is particularly preferably 160 ° C. or higher. The viscosity is 27
It is a value at a dynamic viscosity [η '] at 0 ° C and 10 rad / sec, and Tg is a value at a temperature rising rate of 10 ° C / min in a scanning differential calorimeter (DSC).

Such a PPSSS is disclosed in Japanese Patent Laid-Open No. 59-813.
It can be produced according to the synthesis method disclosed in JP-A-35-35 or JP-A-61-210027. That is, 4,4'-dihalodiphenyl sulfone and p-dimercaptobenzene are used as raw materials, an organic amide solvent or an aliphatic or aromatic sulfone which is an aprotic polar solvent is used as a solvent, and an alkali metal salt such as In the presence of at least one selected from carbonates, hydroxides and bicarbonates, substantially equimolar amounts of p-dimercaptobenzene and 4,4'-at a temperature in the range of 200 to 400 ° C. It can be synthesized by polycondensation with dihalodiphenyl sulfone.

The starting monomers used are p-dimercaptobenzene (HS-φ-SH) and the general formula (X ¹ -φ-
SO ₂ -φ-X ² ) (X ¹ and X ² in the formula represent a halogen atom, and they may be the same or different.)
Is 4,4'-dihalodiphenyl sulfone. Specific examples of the 4,4'-dihalodiphenyl sulfone include 4,4'-dichlorodiphenyl sulfone, 4,
4'-dibromodiphenyl sulfone, 4,4'-difluorodiphenyl sulfone and the like can be mentioned. Among them, 4,
4'-Dichlorodiphenyl sulfone is easily available and its use is preferable from the industrial viewpoint. Further, these monomers may be used alone or in combination of two or more kinds.

Among the solvents used, the organic amide solvent is hexamethylphosphoric triamide (HMPA),
N-methylpyrrolidone (NMP), N-cyclohexylpyrrolidone (NCP), tetramethylurea (TMU),
Examples thereof include dimethylformamide (DMF) and dimethylacetamide (DMA). The aliphatic or aromatic sulfone solvent has the general formula (R ¹ —SO ₂ —R ² ), wherein R ¹ and R ² are aliphatic residues or aromatic residues, which may be the same or different. Well, R ¹ and R ² are carbon-
A compound represented by a carbon bond which may be directly bonded or may be bonded through a hetero atom such as an oxygen atom, and specifically, dimethyl sulfone (DM
S), diethyl sulfone (DES), sulfolane, diphenyl sulfone (DPS), methylphenyl sulfone (MPS), dibenzothiophene oxide, 4-phenylsulfenylbiphenyl and the like.

The alkali metal salts such as carbonates, hydroxide compounds and bicarbonates used include sodium carbonate, potassium carbonate, rubidium carbonate, cesium carbonate, sodium hydroxide, potassium hydroxide, sodium hydrogencarbonate and hydrogencarbonate. Examples thereof include potassium, rubidium hydrogen carbonate, and cesium hydrogen carbonate. These salts may be used alone or in combination of two or more. Of these, sodium carbonate, potassium carbonate, sodium hydrogen carbonate and potassium hydrogen carbonate are particularly preferable.

A preferred embodiment of the synthetic method will be described.
First, in at least one solvent selected from aliphatic sulfones, aromatic sulfones, and organic amide solvents, at least one selected from the required amount of alkali metal carbonate, hydroxide compound, or bicarbonate. The seed alkali metal salt and p-dimercaptobenzene and 4,4'-dihalodiphenyl sulfone are added.

The solvent is usually 100 in total of p-dimercaptobenzene and 4,4'-dihalodiphenyl sulfone.
It is used in the range of 10 to 1000 parts by weight per part by weight.

The alkali metal salt is used in a proportion such that the amount of the alkali metal atom is 1.6 to 2.4 gram atom per mol of p-dimercaptobenzene. It is preferable to use anhydrous ones of these alkali metal salts, but those having crystal water or bound water should be distilled off from the polymerization system by simple distillation or distillation using an azeotropic solvent. Can be used.
Further, these alkali metal salts can be divided and added to the polymerization system. For example, when the reaction is charged, the amount of the alkali metal atom is added in such a ratio that it becomes 2 gram atom per mol of p-dimercaptobenzene, and when the polymerization reaction proceeds to some extent, p-dimercaptobenzene 1 is further added as the alkali metal atom. The method is to add 0.4 gram atom of alkali metal salt per mole.

4,4'-dihalodiphenyl sulfone and p
The use ratio of dimercaptobenzene needs to be substantially equimolar, but usually the former is selected in the range of 0.95 to 1.20 mol per mol of the former. When the latter is slightly in excess, such as 1.01 to 1.10 mol, a polymer having a high molecular weight is obtained.

Next, the mixture of the above-mentioned solvent, alkali metal salt and monomer is heated in an atmosphere of an inert gas such as nitrogen or argon to 100 to 400 ° C., preferably 150 to 300.
The polymerization reaction is carried out in the temperature range of ° C. Also, in order to avoid local heating that causes side reactions such as decomposition reactions, the temperature is not raised rapidly, but is raised stepwise or gradually to keep the polymerization reaction system at a uniform temperature as much as possible. It is good to devise so that The reaction time is 1 to 20 hours, preferably 3 to 15 hours. In a reaction at a high temperature where the decomposition reaction and the polymerization reaction compete with each other, the reaction time may be set short.

The polymerization reaction is carried out by using a suitable terminal stopper such as a monofunctional or polyfunctional halide, specifically methyl chloride, methyl iodide, tert-butyl chloride, 4,
It can be stopped by adding 4'-dichlorobenzophenone, p-nitrochlorobenzene, monomer 4,4'-dihalodiphenyl sulfone, etc. to the reaction system at the above-mentioned polymerization temperature. This makes it possible to obtain a polymer having a thermally stable alkyl group, aromatic halogen group, or aromatic group at the terminal.

To recover the polymer, at the end of the reaction, the reaction mixture is first heated under reduced pressure or normal pressure to distill off only the solvent, and then the bottom solid is treated with a solvent such as water, acetone, methyl ethyl ketone or alcohols. It can be performed by washing once or twice or more, and then neutralizing, washing with water, filtering and drying. Further, as another method, after the reaction is completed, water, acetone, methyl ethyl ketone, alcohols, ethers, halogenated hydrocarbons are added to the reaction mixture,
A solvent such as an aromatic hydrocarbon or an aliphatic hydrocarbon (which is soluble in the used polymerization solvent and is a non-solvent for at least the produced polymer) is added as a precipitating agent to precipitate the polymer. It can also be carried out by filtering it, washing and drying it. The "washing" in these cases can be carried out in the form of extraction. Further, after the reaction is completed, the reaction solvent or a low-molecular weight polymer equivalent thereto is dissolved in the reaction mixture, for example, a sulfone-based or amide-based solvent other than the reaction solvent is added and stirred, and then filtered to remove the low-molecular weight polymer. After that, it can be also carried out by washing once or twice or more with a solvent such as water, acetone, methyl ethyl ketone, alcohols, and then neutralizing, washing with water, filtering and drying.

The PPSSS used in the composition of the present invention is thermally crosslinked by heating in the presence of oxygen. Utilizing this property, a low-molecular weight polymer can be synthesized and thermally crosslinked to increase the molecular weight, and then used. Further, if this thermal crosslinking is hindered when a high molecular weight polymer is used, zinc oxide, carbonate, hydroxide compound, periodic table II
It is also possible to add and use a heat stability improver such as a hydroxide compound, an oxide, a carbonate or an aromatic carboxylate of Group A.

On the other hand, as the other miscible resin used in the composition of the present invention, known resins can be used.
The following resins are preferred.

PAS resins represented by PPS, polyphenylene sulfide ketone (hereinafter abbreviated as PPSK), PPSS and various block copolymers containing these as block components; nylon 6, nylon 66, nylon 4
Polyamide represented by 6, Nylon 12, Nylon MXD6 (copolymer obtained from metaxylenediamine and adipic acid), etc .; Thermoplastic polyester represented by polyethylene terephthalate, polybutylene terephthalate, poly (cyclohexane dimethylene terephthalate); (-Φ-SO _2- ), (-φ-O-φ-SO _2- ),
_{(-Φ-C (CH 3)} 2 -φ-O-φ-SO 2 -) polyethersulfone having repeating units such as, polyaryl sulfone, polysulfone; (- φ-CO-φ -O
-), Polyether ketone having a repeating unit such as (-φ-O-φ-CO-φ-O-), a polyether ether ketone; a polymer of 2,6-disubstituted phenol or 2,6-substituted phenol Polyphenylene oxide which is a polymer with polyhydric phenol; polycarbonate; polyarylate; homopolymers and copolymers of monomers of ethylene, propylene, butylene and pentene, and these monomers and butadiene, isoprene, (meth) Acrylic ester, (meth) acrylonitrile, etc. and copolymer α
-Olefin copolymer; hydrogenated styrene / butadiene rubber or other conjugated diene-based copolymer hydrogenated product; styrene copolymer; ABS resin, MBS resin, ABS such as AES resin
Resins such as polyether imide, phenoxy resin, fluorine resins such as polytetrafluoroethylene and polyvinylidene fluoride, epoxy resin, phenol resin and the like. These may be modified with an acid or the like.

The addition rate to PPSSS varies depending on the resin used and the purpose of use, and therefore cannot be specified unconditionally, but when epoxy resin is used, it is usually 0.1 to 30 parts by weight, preferably 100 parts by weight to PPSSS. , 0.5-
When 20 parts by weight uses an α-olefin copolymer, a conjugated diene-based copolymer, a styrene copolymer, or a phenoxy resin, 1 to 100 parts by weight, preferably 2 to 80 parts by weight is used as another resin, for example. PPSSS for PAS resin
5 to 95 parts by weight, preferably P to 95 to 5 parts by weight
10 to 90 parts by weight (total 100 parts by weight) is used for 90 to 10 parts by weight of PSSS.

In particular, since PPSSS has an excellent affinity with PAS resins such as PPS, the toughness of PPS and the elastic modulus above Tg are improved, the formability of PPSS and PPSK is improved, or the PPS / PPSS block copolymer is improved. And PPS / PP
Its addition is suitable for improving the elastic modulus of a block copolymer such as an SK block copolymer in a high temperature range. On the other hand, the addition of these PAS-based resins improves the chemical resistance and heat resistance of PPSSS. Further improvements can be made.

A filler may be added to the composition of the present invention for the purpose of further improving impact resistance, heat resistance and dimensional stability.

As the filler used in the present invention, fibrous fillers such as carbon fiber, glass fiber, silane-treated glass fiber, ceramic fiber, aramid fiber, boron fiber,
Metal fibers, potassium titanate, silicon carbide, whiskers and the like, as the granular filler, barium sulfate, calcium sulfate, clay, bilophyllite, bentonite, sericite, zeolite, mica, mica, talc,
Atarupulgite, ferrite, calcium silicate, calcium carbonate, magnesium carbonate, glass beads and the like can be mentioned. Generally, the fibrous filler is used alone, or the fibrous filler is used in combination with one or more other inorganic fillers.

The amount of the filler added varies depending on the fibrous filler, the granular filler, etc., but cannot be specified unconditionally.
It is used in an amount of 300 parts by weight or less based on 100 parts by weight of the resin component. Especially when used for injection molding, the amount of filler is 3
A range of up to 230 parts by weight is preferred. The granular filler is usually used in an amount of 80 parts by weight or less.

In the composition of the present invention, a small amount of a releasing agent such as polyethylene wax, a coloring agent such as various pigments, an antioxidant of phosphorus compounds and hindered phenol compounds, etc. may be used within a range not departing from the object of the present invention. It is possible to use agents, heat resistance stabilizers, UV stabilizers, foaming agents, flame retardants, flame retardant aids, rust inhibitors, silane coupling agents such as aminosilane and epoxysilane, and titanate coupling agents. still,
Examples of the antioxidant include hindered phenol compounds, hindered amine compounds, phosphorus compounds and the like, preferably trivalent phosphorus compounds. As the heat resistance stabilizer, hydroxides, oxides and aromatic carboxylates of Group IIa metals of the periodic table excluding magnesium, and aromatic carboxylates, carbonates and hydroxides of Group Ia metals of the periodic table, Phosphates, borates and the like can be mentioned, but among them, hydroxides of calcium and barium are preferable. Examples of the rust preventive include carbonates of alkali metals such as lithium and potassium, oxides and carbonates of metals belonging to Group IIa and b of the periodic table such as magnesium, calcium and zinc. Among them, zinc oxide and carbonate Zinc or the like is preferably used.

The method for preparing the composition of the present invention may be a known method. For example, a method in which the raw materials are mixed with a mixer such as a tumbler or a Henschel mixer, and then melt-kneaded at 200 to 380 ° C. to form pellets using a single-screw or twin-screw extruder, or the raw materials are preliminarily dissolved in a solvent There is a method in which PPSSS and / or another resin to be blended is melt-blended with the resinous substance obtained by the mixing treatment in (1).

[0031]

The present invention will be further described below with reference to examples, but the present invention is not limited to these examples.

Synthesis Example 1 (Synthesis of PPSSS) 4,4'-dichlorodiphenylsulfone 287.17 g (1.00 mol) and p-dimercaptobenzene 149 were placed in a stainless steel (titanium lining) 2 liter autoclave equipped with a stirring blade. .34 g (1.05 mol), anhydrous potassium carbonate 145.12 g (1.05 mol) and diphenyl sulfone 700 g were charged, the system was sufficiently replaced with nitrogen while stirring, and then the temperature was raised to 200 ° C. over 3 hours. Then
Hold for 5 hours. After this, anhydrous potassium carbonate 7.3g
(0.05 mol) was added, the temperature was raised to 250 ° C., and the temperature was maintained for 2 hours. Then blow methyl chloride at this temperature for 20 minutes, cool, grind, and then twice with acetone and 2 times with warm water.
And then washed once with acetone, and the repeating unit is [-φ-SO ₂ -φ-S-φ-S-] (however, -φ-
Represents a p-phenylene group. ) To obtain 340.0 g of an amorphous polymer (PPSSS-1).

The melt viscosity of this PPSSS-1 is 950 poise, Tg is 171 ° C., and the result of elemental analysis is CHOS measurement value (%) 60.5 3.2 9.1 26.7 theoretical value ( %) 60.67 3.40 8.99 26.94.

The melt viscosity of the obtained polymer was measured by a melt viscoelasticity measuring device (RDS-II) manufactured by Rheometrics.
Was used as the dynamic viscosity [η ′] at 270 ° C. and 10 rad / sec. The glass transition point (Tg) is DSC200 manufactured by Seiko Denshi, the sample amount is about 5 mg, and the heating rate is 1
It was measured under the condition of 0 ° C./min.

[Synthesis Example 2] (Synthesis of PPSSS) The PPSSS-1 obtained in the above Synthesis Example 1 was heated to 150 ° C. in air.
PPS with a melt viscosity of 3200 poise after being thermally crosslinked for about 7 hours
SS-2 was obtained.

[Synthesis Example 3] (Synthesis of block copolymer composed of PPS and PPSS) N-methylpyrrolidone (NM) was placed in a 10 L autoclave.
P) 1980 g, sodium hydrosulfide 1.2 hydrate (N
aSH) 388 g, sodium hydroxide (NaOH) 200 g, bis (p-chlorophenyl) sulfone 143
6 g was charged and reacted at 200 ° C. for about 6 hours under a nitrogen atmosphere. Furthermore, bis (p-chlorophenyl) sulfone 7
2g and NMP200g were added, and it was made to react at 200 degreeC for 1 hour, and the terminal chloro group type PPSS reactant slurry was obtained.

Next, NMP 3 was placed in a 10 L autoclave.
10 g, NaSH 597.5 g, and NaOH 308
g was charged, the temperature was raised while allowing water to flow out, and dehydration treatment was performed. Then, the autoclave was sealed, and at 220 ° C., p-dichlorobenzene 10 was added to the dehydrated system.
29g and 700g of NMP are press-fitted, and further 26
Reaction was carried out at a temperature of 0 ° C. for 2 hours to obtain a terminal sodium sulfide group type PPS reactant slurry.

The above PPSS reactant slurry and PPS reactant slurry were charged into an autoclave and reacted at 220 ° C. for 3 hours, and the reaction product was purified with hot water, methanol and acetone, and the PPSS portion contained 50 parts by weight of block copolymer. A combination (PPS / PPSS) was obtained. Scanning differential calorimeter (D
The melting point of PPS / PPSS determined by SC) was 270 ° C., and the dynamic viscosity at 290 ° C. and 10 rad / sec was 800 poise.

The evaluation methods of physical properties are as follows. (1) Izod impact test (without notch, 'IZ in the table
Abbreviated as OD ') No glass fiber: Measured using a rod-shaped test piece having a cross-sectional area of 3.2 × 3.2 cm ² .

With glass fiber: According to ASTM D-256.

(2) Bending test No glass fiber: width 10 mm, thickness 2 mm, span length 3
Measured at 0 mm and deformation speed of 2 mm / min.

With glass fiber: According to JIS (K7055).

(3) Penetration test A load of 50 g was applied to a 0.5 mmφ needle probe, and measurement was performed at a temperature rising rate of 5 ° C./min. The test used was TMA-SS120C manufactured by Seiko Instruments Inc.

(4) Elastic Modulus (Storage Elastic Modulus) Using a test piece having a width of 1 cm, a thickness of 2 mm and a length of 3 cm, it was measured by DMS-100 manufactured by Seiko Denshi Kogyo.

(5) Chemical resistance test (toluene) The weight increase rate was measured by immersing in toluene for 24 hours.

(6) Friction test A load of 700 g was applied to a sample piece having a cross-sectional area of 5 × 5 cm ² and calculated from the force required to slide on steel at a speed of 500 mm / min.

(7) Weather resistance test Irradiation was carried out for about 200 hours with a Sunshine weather meter manufactured by Suga Test Instruments Co., Ltd., and the brightness before and after irradiation was measured with a micro flat curved surface photometer manufactured by Nippon Denshoku.

(8) Water absorption test A sample piece was immersed in warm water at 70 ° C. for 24 hours, and the water absorption rate (weight change) was measured.

[Examples 1 to 4] PPSSS-2 and PP
S and glass fiber were blended as shown in Table-1, melt-kneaded at 310 ° C. in an extruder, pellets were prepared, and a molding sample was prepared by injection molding. Moldability was good in all cases. An Izod impact test (no notch), a bending test, an elastic modulus at 120 ° C., and a chemical resistance test (toluene) were performed. In addition, DPC-PPS B-600 manufactured by Dainippon Ink and Chemicals, Inc. was used as PPS, and chopped strand CS06MA404 manufactured by Asahi Fiber Glass Co., Ltd. was used as glass fiber.

[Comparative Example 1] The block copolymer of PPS and PPSS (PPS / PPSS) obtained in Synthesis Example 3 and P
It measured similarly using PS. The results are shown in Table-1.

[0051]

[Table 1]

[Examples 5 to 7] PPSSS-1 and modified polyphenylene oxide (modified PPO) were blended as shown in Table 2 and melt-kneaded at 320 ° C in an extruder to prepare pellets. Molded samples were made using injection molding. Moldability was good in all cases. The Izod impact strength (without notch) and the elastic modulus at 200 ° C. (storage elastic modulus) were measured. By adding PPO, impact resistance and elastic modulus at high temperature are improved. Also, the moldability of PPO is improved. As the modified PPO, Noryl 534J-801 manufactured by General Electric Co. was used.

Example 8 Sample pieces were prepared in the same manner for PPSSS-1 42 parts by weight, modified PPO 28 parts by weight, and glass fiber 30 parts by weight. The moldability was good. The results of the Izod impact test (without notch) are shown in Table 2.

[0054]

[Table 2]

[Examples 9 and 10] PPSSS-1 and polyether sulfone (PES), polyether imide (P
EI) was blended in a one-to-one manner, sample pieces were prepared, and the same examination was performed. The moldability was good. The Izod impact strengths were 47 and 38 (Kgf · cm / cm ² ), respectively, and the elastic moduli at 200 ° C. were 1.2 and 1.0 (GPa). Impact resistance, high temperature elastic modulus, and moldability are improved.

[Examples 11 and 12, Comparative Examples 2 and 3] PP
SSS-2 and polyethylene terephthalate (PET),
Polybutylene terephthalate (PBT) was blended in a ratio of 1: 1 and a sample piece was prepared by the same method. The melt-kneading temperature was 270 ° C. The moldability was good. A combustion test using a gas burner and a friction test on steel were performed.
In each of the examples, the flame disappeared instantly, and the self-extinguishing property was observed. On the other hand, PPSSS-2 (Comparative Example 2) showed self-extinguishing property, but PBT (Comparative Example 3) burned violently. The measurement results of the friction test on steel are also shown in Table-3.

PET is Mitsui PET manufactured by Mitsui Pet Co., Ltd.
J-125 and PBT used were PLANAC BT-128 manufactured by Dainippon Ink and Chemicals, Inc.

[Examples 13 and 14] PPSS-2 and PB
T was mixed in the composition as shown in Table 3, a sample was prepared in the same manner as in Example 11, and a friction test on steel was examined. The results are shown in Table-3.

Example 15 PPSS-2, PBT and glass fiber were mixed in a composition as shown in Table 3, a sample was prepared in the same manner as in Example 11, and a friction test on steel was examined. It was The results are shown in Table-3.

[0060]

[Table 3]

[Example 16] PPSSS-2 and polytetrafluoroethylene (PTFE) were mixed in a ratio of 7/3, and a sample piece was prepared in the same manner. Melt kneading temperature is 32
It was set to 0 ° C. A friction test on steel was performed. The coefficient of friction was 0.14. Polyflon TFE M-31 manufactured by Daikin Industries, Ltd. was used as PTFE.

[Examples 17 to 19] In the case of using polycarbonate (PC), the compounds were blended as shown in Table 4 and samples were prepared by the same method, and Izod impact test (without notch), bending test, A needle penetration test was conducted. The melt-kneading temperature was 270 ° C. The results are shown in Table-4.
The PC is Iupilon S-200 manufactured by Mitsubishi Gas Chemical Co., Inc.
0 was used.

[0063]

[Table 4]

[Examples 20 to 22] With respect to the case where polyarylate (PAr) was used, it was blended as shown in Table 5 to prepare sample pieces in the same manner, and Izod impact test (without notch) and bending test and A weather resistance test was conducted. The results are shown in Table-5. The brightness before the test was almost 60 in all cases. PAr is U-polymer manufactured by Unitika Ltd.
U-100 was used.

[Examples 23 to 25] Polyethylene (P
E), an ionomer, and a phenoxy resin were blended as shown in Table-5, sample pieces were prepared in the same manner, and an Izod impact test (no notch) and a bending test were performed. The melt-kneading temperature was 260 ° C. The results are shown in Table-5. In addition, PE is Shorex MO manufactured by Showa Denko KK
-32, Ionomer is Mimi-DuPont Polychemical Co., Ltd., Himilan 1707, and phenoxy resin is Union Carbide Co., Ltd. UCAR Phenoxy PKHH.
Was used.

[0066]

[Table 5]

Examples 26 to 30 PPSSS-2, Nylon-66, Nylon-6, and glass fiber are shown in Table-6.
Samples were prepared in the same manner as described above. An Izod impact test (no notch), a bending test and, for some of the examples, a water absorption test were also performed. The results are shown in Table-6. The melt-kneading temperature was 290 ° C. Incidentally, the water absorption of nylon-66 alone is about 8% by weight.
S-2 alone was about 0.2% by weight. Nylon-
66 is UBE nylon 2026D manufactured by Ube Industries
For Nylon-6, MC-112L manufactured by Kanebo Ltd. was used.

[Example 31] A sample was prepared in the same manner as in the case of using PPSSS-2 and hydrogenated styrene / butadiene rubber (SBR) in a ratio of 5: 1, and a bending test was conducted. The results are shown in Table-6. As the SBR, Toughtics M193G manufactured by Asahi Kasei Corporation was used.

[0069]

[Table 6]

[0070]

The composition of the present invention has a high glass transition temperature (Tg) and has various properties such as flame retardancy, chemical resistance, flexibility, impact resistance, moldability, heat resistance and slidability. The resin composition is well balanced. This resin composition is injection molded,
Molded products of various shapes can be given by molding methods such as compression molding, extrusion molding, electrical / electronic parts, automobile parts, various parts such as construction, civil engineering field, aviation, space, marine field, sports equipment and It is preferably used as miscellaneous goods.

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Takahiro Kawabata             Green tau, 1551-1, Rosaki, Sakura City, Chiba Prefecture             9-202 (72) Inventor Yoshifumi Noto             2982 Sanmuro, Urawa City, Saitama Prefecture

Claims (3)

[Claims] 1. (A) General formula [-φ-SO ₂ -φ-S-
[phi] -S-] (where-[phi]-represents a p-phenylene group.) A resin composed of an aromatic sulfide / sulfone polymer having a repeating unit represented by (B) and at least one miscible resin. Composition. 2. (A) General formula [-φ-SO ₂ -φ-S-
φ-S-] (where -φ- represents a p-phenylene group), an aromatic sulfide / sulfone polymer having a repeating unit represented by (B) and at least one miscible resin (C). ) A resin composition comprising a filler. 3. As miscible resins, polyamide, thermoplastic polyester, polysulfone, polyphenylene oxide, polyarylene sulfide resin, polyether ketone, polyetherimide, polyarylate, polycarbonate, phenoxy resin, α-olefin copolymer. , Styrene copolymer, hydrogenated product of conjugated diene copolymer,
The resin composition according to claim 1, wherein at least one resin selected from an ABS resin, a fluorine resin, and an epoxy resin is used.