JPH04285663A - Resin composition - Google Patents

Abstract

PURPOSE:To obtain a resin composition consisting of a polythioether aromatic ketone, a thermoplastic polyester and/or a fluororesin excellent in blend compatibility and characteristics, having excellent properties in both of the resins. CONSTITUTION:A resin composition containing (A) 95-5wt.%, preferably 90-10wt.% of a polythioether aromatic ketone having >=90mol% recurring units expressed by the formula (phi is p-phenylene group), (B) 5-95wt.% preferably 10-90wt.% of B1: a thermoplastic polyester (preferably polybutylene terephthalate or polyhexamethylene terephthalate and/or B2: flouroresin (e.g. vinylidene fluoride/hexafluoropropylene-based copolymer) and, as necessary, (C) a fibrous filler of 100-300 pts.wt., preferably 30-200 pts.wt. or a particulate filler of 2-100 pts.wt., preferably 5-80 pts.wt. based on 100 pts.wt. resin content.

Description

[Detailed description of the invention]

0001

[Field of Industrial Application] The present invention relates to a resin composition with improved heat resistance, chemical resistance, flexibility, flame retardance, sliding properties, etc. It is used as a molding material in various fields such as car parts, aircraft/automobile parts, interior materials, and sports equipment.

0002

[Prior Art] Polyarylene sulfide (hereinafter referred to as PA
We can improve the sliding properties, impact resistance, and flexibility, which are the disadvantages of PAS resins, or improve the heat resistance, chemical resistance, dimensional stability, and flame retardancy, which are the excellent properties of PAS resins. Many attempts have been made to blend thermoplastic polyesters or fluororesins with PAS resins for the purpose of imparting moldability and the like. However, all the attempts known so far have had problems such as poor mechanical properties such as impact resistance and flexibility due to poor affinity and blend compatibility between the resins. For example, polyphenylene sulfide (hereinafter abbreviated as PPS), which is a typical PAS resin, is disclosed in Japanese Patent No. 1005081,
No. 052, U.S. Patent No. 3,487,454, etc., but although problems such as sliding properties are improved,
There was a problem in that mechanical properties such as impact resistance and flexibility were significantly reduced. In addition, the cases of polyphenylene sulfide sulfone (hereinafter abbreviated as PPSS) and polyphenylene sulfide ketone (hereinafter abbreviated as PPSK) are also known, but in the case of PPSS, although the affinity between resins is improved, heat resistance In the case of PPSK, although it has excellent heat resistance, it tends to gel during molding and has poor molding stability.

0003

[Problems to be Solved by the Invention] In view of the above problems, the present invention has been developed to provide heat resistance, chemical resistance, flame retardance, dimensional stability, water resistance, flexibility, impact resistance, weather resistance, and sliding properties. The object of the present invention is to provide a highly functional resin composition with excellent affinity and compatibility, which mutually imparts the excellent properties of PAS resins, thermoplastic polyesters, and fluorine resins. .

0004

[Means for Solving the Problems] The present inventors have developed a PAS resin with the general formula [-φ-CO-φ-S-φ-S
-] (However, -φ- represents a p-phenylene group) In a resin composition using a polythioether aromatic ketone having a repeating unit, PAS resin, thermoplastic polyester, and fluororesin, respectively. The present inventors have discovered that it is possible to obtain a highly functional resin composition with excellent affinity and compatibility that imparts the excellent properties of resins to each other, and has completed the present invention.

That is, the present invention provides (1) general formula [-φ
-CO-φ-S-φ-S-] [1] (However, -φ- represents a p-phenylene group) A polythioether aromatic ketone having a repeating unit and (2) a thermoplastic polyester and The present invention relates to a resin composition made of (or) a fluororesin and, if necessary, further containing (3) a filler.

[0006] PTEK used in the composition of the present invention is
It is a PAS resin having 90 mol% or more of repeating units represented by the above formula [1]. The PTEK may contain other polymer components, oligomer components, etc. derived during production as long as they do not impair the effects of the present invention. The PTEK is disclosed in Japanese Patent Application Laid-open No. 59-81335 and 60-10.
4126, No. 61-200127, etc., and various other manufacturing methods. For example, it can be obtained by reacting an aromatic dithiol with a dihalogenobenzophenone in an aromatic sulfone solvent in the presence of a base such as an alkali metal carbonate.

[0007] The melt viscosity of the PTEK is 10 at 320°C.
Dynamic viscosity [η'] in rad/sec is 50 to 10
5 poise, preferably 100 to 50,000 poise.

On the other hand, examples of thermoplastic polyesters include terephthalic acid, isophthalic acid, orthophthalic acid, naphthalene dicarboxylic acid, 4,4'-diphenyldicarboxylic acid,
diphenyl ether dicarboxylic acid, α,β-bis(4-
Dicarboxylic acids such as (carboxyphenoxy)ethane, adipic acid, sebacic acid, azelaic acid, decanedicarboxylic acid, dodecanedicarboxylic acid, cyclohexanedicarboxylic acid, and dimer acid, or their ester-forming derivatives, and ethylene glycol, propylene glycol, butanediol, pentanediol , neopentyl glycol, hexanediol, octanediol, decanediol,
Glycols such as cyclohexanedimethanol, hydroquinone, bisphenol A, 2,2-bis(4-hydroxyethoxyphenyl)propane, xylene glycol, polyethylene ether glycol, polytetramethylene ether glycol, aliphatic polyester oligomers with hydroxyl groups at both ends It usually has an intrinsic viscosity {η} of 0.3 to 1.5 dl/g measured at 30°C in a mixed solvent of phenol and tetrachloroethane in a weight ratio of 6:4. A range of materials is used.

In addition, as a comonomer component, hydroxycarboxylic acids such as glycolic acid, hydroxybutyric acid, hydroxybenzoic acid, hydroxyphenylacetic acid, and naphthylglycolic acid, lactone compounds such as propiolactone, butyrolactone, valerolactone, and caprolactone, or thermal Within the range that can maintain plasticity, trimethylolpropane, trimethylolethane, glycerin, pentaerythritol, trimellitic acid, trimesic acid,
It may also contain a polyfunctional ester-forming component such as pyromellitic acid.

[0010] In addition, dibromoterephthalic acid, tetrabromoterephthalic acid, tetrabromophthalic acid, tetrachloroterephthalic acid, 1,4-dimethyloltetrabromobenzene, tetrapromobisphenol A, ethylene oxide adduct of tetrabromobisphenol A, etc. Also included are thermoplastic polyester resins in which an aromatic group has a halogen compound such as chlorine or bromine as a substituent, and a halogen compound having an ester-forming group is copolymerized.

Particularly preferable thermoplastic polyesters include polyethylene terephthalate (hereinafter abbreviated as PET), polybutylene terephthalate (hereinafter abbreviated as PBT), polyhexamethylene terephthalate, poly(ethylene butylene terephthalate), and poly(cyclohexane diphthalate). methylene terephthalate), poly(butylene/tetramethylene terephthalate), 2,2-bis(β-hydroxyethoxytetrabromophenyl)propane copolymerized polybutylene terephthalate, and the like.

Fluororesin is a general term for synthetic polymers containing fluorine atoms in their repeating units and their copolymers, including polytetrafluoroethylene, polychlorotrifluoroethylene, and tetrafluoroethylene/hexafluoroethylene. So-called fluororesins such as propylene copolymer, tetrafluoroethylene/perfluoroalkyl vinyl ether copolymer, polyvinylidene fluoride, polyvinyl fluoride, tetrafluoroethylene/ethylene copolymer, and vinylidene fluoride/hexafluoropropylene copolymer The main one is fluororubber, which is mainly made by combining.

[0013] The proportion of each resin in the composition of the present invention varies depending on the type of resin and purpose of use, and cannot be unconditionally defined, but usually (1) 95 to 5% by weight of PTEK and (2) thermoplastic polyester. and/or fluororesin 5 to 95% by weight, preferably (1) 90 to 10% by weight and (2) 10 to 90% by weight. When focusing on PTEK, adding thermoplastic polyester and/or fluororesin improves sliding properties and flexibility, and when focusing on thermoplastic polyester and/or fluororesin, adding PTEK improves sliding properties and flexibility. This improves the heat resistance and hot water resistance of thermoplastic polyester, and the rigidity and moldability of fluororesin.

[0014] The resin composition of the present invention may contain, if necessary,
By incorporating fibrous or granular fillers, it is possible to improve heat resistance, mechanical properties, and dimensional stability. Examples of fibrous fillers include glass fiber, carbon fiber,
Examples include silane glass fibers, boron fibers, whiskers, potassium titanate, asbestos, silicon carbide, aramid fibers, ceramic fibers, and metal fibers. Further, examples of the granular filler include silicates such as mica and talc, carbonates, sulfates, metal oxides, glass beads, and silica. Two or more of these may be used in combination, and these fillers can also be treated with a silane-based or titanium-based coupling agent that is usually used as a processing agent for fillers. The proportion of filler added varies depending on the type of filler and purpose of use, but usually the fibrous filler is added in an amount of 10 to 300 parts by weight, preferably 30 to 20 parts by weight, per 100 parts by weight of the resin.
In the case of granular fillers, the amount is 2 to 100 parts by weight, preferably 5 to 80 parts by weight.

The composition of the present invention may also contain small amounts of a mold release agent such as polyethylene wax, coloring agents such as various pigments, antioxidants, heat stabilizers,
UV stabilizers, foaming agents, flame retardants, flame retardant aids, rust inhibitors, silane coupling agents such as aminosilane and epoxysilane, titanate coupling agents, or olefin copolymers such as polyethylene, polypropylene, and styrene; nylon-66 , polyamides such as nylon-6; polycarbonates; polyarylates; polyacetals; polysulfones; polyphenylene oxides; polyetherketones; polyetherimides; ABS resins; hydrogenated SBR;
It can contain resins such as phenoxy resin; silicone resin; epoxy resin; phenol resin; and polyimide. Examples of antioxidants include hindered phenol compounds, hindered amine compounds, phosphorus compounds, etc. Among them, trivalent phosphorus compounds are preferable, and examples of heat-resistant antioxidants include water of group IIa metals of the periodic table except magnesium. Examples include oxides, oxides, aromatic carboxylates, and aromatic carboxylates, carbonates, hydroxides, phosphates, borates, etc. of Group Ia metals of the periodic table, among which calcium and barium Hydroxides and oxides are preferred, and rust preventives include carbonates of alkali metals such as lithium and potassium, oxides and carbonates of metals belonging to groups IIa and b of the periodic table such as magnesium, calcium, and zinc. Among them, zinc oxide, zinc carbonate, etc. are preferably used.

The composition of the present invention can be prepared by various known methods. For example, raw materials are mixed in a mixer such as a dumbler or Henschel mixer, then melt-kneaded at 290 to 380°C using a single-screw or twin-screw extruder, and then pelletized, or the raw materials are mixed in a solvent in advance. A method of melt-kneading the resinous material obtained by mixing in an extruder and preparing it as pellets, or a method of melt-blending the resinous material, PTEK, thermoplastic polyester, and/or fluororesin. and so on.

[0017]

[Examples] Examples will be shown below, but the present invention is not limited thereto.

[Reference Example 1] (Synthesis example of PTEK) 5
1000 g of xanthone in L autoclave, 4,4'-
Difluorobenzophenone 305.2g, p-dimercaptobenzene 214.0g, anhydrous potassium carbonate 193g
．． 2 g was charged, the temperature was raised to 250°C over 3 hours under a nitrogen atmosphere, and the temperature was further raised to 320°C over 1 hour, and the reaction was carried out for 2 hours. Furthermore, after blowing methyl chloride for 20 minutes, it was cooled and washed with acetone and warm water to obtain PTEK.

PT determined by scanning differential calorimeter (DSC)
EK had a melting point of 304°C, a glass transition temperature of 135°C, and a dynamic viscosity of 700 poise at 320°C and 10 rad/sec.

[Example 1, Comparative Example 1] PTEK and PBT
were blended in a 1:1 ratio, melted and kneaded at 320°C to form pellets, and then sample pieces were created using an injection molding machine. Both moldability and appearance of the molded product were good. An Izod impact test (no notch), a bending test, a friction test against steel, and a penetration test were performed. Also, as a comparative example, PP
Regarding the blended composition of S and PBT, as a reference example, P
Similar studies were conducted for TEK and PPS alone. In the comparative example, moldability was good, but the appearance of the molded product had a pearl color and was poor in appearance. The results are shown in Table-1.

When the fractured surface of the sample piece subjected to the Izod test was observed with a scanning electron microscope (SEM), particles of 1 to 8 microns were uniformly dispersed in the example.
In the comparative example, spherical particles of 3 to 20 microns were observed to be non-uniformly dispersed. If PTEK is used, P
It can be seen that the dispersibility between the resins is significantly improved compared to the case of PS, and the impact resistance, flexibility, and heat resistance are significantly improved. In addition, a friction test and a penetration test were conducted on PBT alone. The coefficient of dynamic friction was 0.12, and the penetration temperature was 207°C.

[0022] As PBT, Planac BT-128 manufactured by Dainippon Ink Chemical Co., Ltd. was used, and as PPS, B-600 manufactured by Dainippon Ink Chemical Co., Ltd. was used. In addition, all blending ratios are expressed as weight ratios, and the same applies hereinafter.

[0023] The physical properties were evaluated as follows. (1) Izod impact test has a cross-sectional area of 3.2 x 3.2
The test was carried out using a rod-shaped specimen measuring cm2 and 30 mm in length.

(2) In the bending test, the width was 10 mm and the length was 50 mm.
mm, using a sample piece with a thickness of 2 mm, and a span length of 30 m.
m, and the deformation speed was 2 mm/min. (3) Penetration test is performed by applying a load of 50 g to a probe with a cross-sectional area of 0.5 mmφ, increasing the temperature at a rate of 5° C./min, and determining the temperature at which the needle penetrates the sample. TMA-SS120C manufactured by Seiko Electronics Industries, Ltd. was used.

(4) Friction test on steel (dynamic friction coefficient)
is determined from the force required to apply a load of 700 g to a sample piece with a cross-sectional area of 5 x 5 cm2 and run it on steel at a speed of 500 mm/min.

[Example 2, Comparative Example 2] PTEK and PET
In this case, the same study as in Example 1 was conducted. Both moldability and appearance of the molded product were good. Further, as a comparative example, similar studies were conducted using PPS. The results are shown in Table-1. Regarding the examples, S of the fracture surface
We conducted EM observations. In the example, it was observed that particles of about 1 to 5 microns were uniformly dispersed, and in the comparative example, particles of about 5 to 5 microns were observed to be uniformly dispersed.
It was observed that coarse particles of about 30 microns were dispersed non-uniformly. It can be seen that when PTEK is used, the dispersibility of the resin is significantly improved and the impact resistance, flexibility, and heat resistance are significantly improved compared to when PPS is used. Furthermore, the coefficient of dynamic friction of PET alone was 0.14, and the penetration temperature was 225°C.

[0027] PET is Mitsui PET manufactured by Mitsui Pet Co., Ltd.
J-125 was used.

[Examples 3 and 4] Sample pieces were prepared in the same manner as in Example 1 when the ratio of PTEK and PBT was 7:3 (Example 3) and 3:7 (Example 4). A bending test, an Izod impact test (no notch), and a friction test were conducted. Both moldability and appearance of the molded product were good. The results are shown in Table-1. Further, as in Example 1, the fracture surface was observed by SEM, and it was observed that particles of about 1 to 10 microns were uniformly dispersed.

[Example 5, Comparative Example 3] PTEK and PBT
, and glass fiber were mixed as shown in Table 1, samples were prepared in the same manner as in Example 1, and the same studies were conducted. However, the total amount of resin and the amount of glass fiber were 6:4. A heat deformation test (HDT) was performed instead of a penetration test. Further, as a comparative example, a similar study was conducted using PPS. The results are shown in Table-1.

As the glass fiber, chopped strand CS06MA404 manufactured by Asahi Fiberglass Co., Ltd. was used. The physical properties of the sample pieces containing glass fibers were evaluated as follows.

(1) Izod impact test is performed according to ASTM (
D-256). (2) The bending test conforms to JIS (K7055). (3) Thermal deformation test (HDT) is ASTM (D-645
). (4) Friction test (dynamic friction coefficient) on steel was as described above.

[0032]

[Table 1]

[Example 6, Comparative Example 4 and Example 7] PT
Example 5 EK, polytetrafluoroethylene (PTFE), and glass or carbon fiber were blended as shown in Table 2.
A similar study was conducted. In both cases, moldability was good. The results are shown in Table-2.

The PTFE used was Polyflon TFE M-31 manufactured by Daikin Industries, Ltd., and the carbon fiber used was Dona Carbo S-233 manufactured by Donac.

[Example 8, Comparative Example 5 and Examples 9-10
] PTEK and tetrafluoroethylene/ethylene copolymer (ETFE) were blended as shown in Table 2, a sample piece was prepared in the same manner as in Example 1, and the Izod impact test (
(no notch), bending test, and friction test. In both cases, moldability was good. Further, as a comparative example, a similar study was conducted for a case where PPS and ETFE were in a 1:1 ratio. The results are shown in Table-2.

[0036] As the ETFE, Neoflon ETFE EP-520 manufactured by Daikin Industries, Ltd. was used.

[0037]

[Table 2]

[0038]

Effects of the Invention The composition of the present invention has significantly improved blend compatibility, and as a result of the improved compatibility, mechanical properties such as impact resistance and flexibility, which had been significantly reduced in the past, have been improved. Significantly improved. Therefore, the resin composition of the present invention has excellent sliding properties, flexibility, impact resistance, heat resistance, solder resistance, chemical resistance, hot water resistance, flame retardance, dimensional stability, moldability, rigidity, etc. Examples of molding materials include electrical and electronic parts such as connectors, printed circuit boards, and encapsulation molded products, automotive parts such as lamp reflectors and various electrical components, interior materials for various buildings, aircraft, and automobiles, and tennis. Injection molding and compression of leisure and sports equipment such as rackets, skis, golf clubs, and fishing rods, acoustic materials such as enclosures for speakers, back decks for stringed instruments, etc., and precision parts such as OA equipment parts, camera parts, and watch parts. It is used in various forming processing fields such as molding, extrusion molding, pultrusion molding of composite sheets, pipes, etc.

Claims (2)

[Claims] [Claim 1] (1) General formula [-φ-CO-φ-S-
φ-S-] [1] (However, -φ- represents a p-phenylene group) from a polythioether aromatic ketone having a repeating unit and (2) a thermoplastic polyester and/or a fluororesin A resin composition. 2. The resin composition according to claim 1, further comprising (3) a filler.