JPH04298567A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To obtain the title compsn. which has a high crystallization rate and excellent mechanical properties and gives a molded article with a good surface by compounding a polyphenylene sulfide resin with a specific polyamide resin in a specified ratio. CONSTITUTION:The title compsn. is produced 95-5wt.% polyphenylene sulfide resin with 5-95wt.% at least one polyamide resin which is selected from the group consisting of a polyamide resin obtd. by the ring-opening polymn. of caprolactam or laurolactam, a polyamide resin obtd. by the polycondensation of aminoundecanoic acid, and a polyamide resin obtd. by the polycondensation of a dicarboxylic acid selected from the group consisting of adipic acid, sebacic acid, and dodecanoic acid with a diamine selected from the group consisting of tetramethylenediamine, hexamethylenediamine, dodecanediamine, and m- xylylenediamine and has a relative viscosity (96% H2SO4, 25 deg.C, 1g/dl concn.) of 2.8 or higher.

Description

[Detailed description of the invention]

0001

[Industrial Application Field] The present invention relates to a resin composition comprising polyphenylene sulfide (hereinafter referred to as PPS) and a specific polyamide, which has a high crystallization rate. The present invention relates to a resin composition that achieves properties and a good surface condition of a molded product.

0002

BACKGROUND OF THE INVENTION A composition of PPS and polyamide is disclosed in Japanese Patent No. 1005081, and many compositions have been studied since then. For example, JP-A-55-135160 discloses that a small amount of polyamide resin is blended for the purpose of improving fluidity during molding of PPS. Furthermore, JP-A-59-155462 and JP-A-6
No. 1-126172 also discloses blending a polyamide resin with PPS for the purpose of improving its impact resistance and mechanical strength.

However, it is difficult to say that sufficient mechanical properties are obtained in any of these compositions, and in particular, the crystallization of the composition is slow, resulting in a decrease in mechanical strength and surface defects in molded products. Problems such as poor condition, such as clouding on the surface of the molded product, may occur.

0004

SUMMARY OF THE INVENTION The present invention provides a resin composition comprising PPS and polyamide resin, which has a high crystallization rate.

[0005]

[Means for Solving the Problems] As a result of extensive studies, the present inventors have found that by blending a specific polyamide into PPS, a high crystallization rate can be achieved in the composition, which is superior to conventional PPS-polyamide compositions. The inventors have discovered that the mechanical properties and surface condition of molded products are significantly improved compared to the previous method, and have arrived at the present invention.

That is, the present invention comprises a polyphenylene sulfide resin (A) and at least one polyamide resin (B) selected from the following, (A)/(B)=95/5 to 5/
95, and the relative viscosity of the polyamide resin is ηrel. However, ηrel. ≧2.8 (96%H2
The present invention provides a resin composition characterized in that the concentration is within the range of SO4, 25° C., and a concentration of 1 g/dl.

The PPS used in the present invention is preferably one containing 70 mol % or more of the structural unit represented by the general formula (1) since it provides a composition with excellent properties.

[0008]

[Chemical formula 1]

PPS polymerization methods include a method of polymerizing p-dichlorobenzene in the presence of sulfur and sodium carbonate, a method of polymerizing p-dichlorobenzene in the presence of sulfur and sodium carbonate, a method of polymerizing p-dichlorobenzene in the presence of sulfur and sodium carbonate, a method of polymerizing p-dichlorobenzene in the presence of sodium sulfide, sodium hydrosulfide and sodium hydroxide, or hydrogen sulfide and sodium hydroxide in a polar solvent. Examples include polymerization in the presence of p-chlorothiophenol and self-condensation of p-chlorothiophenol. A method in which benzene is reacted is suitable. At this time, in order to adjust the degree of polymerization, it is a preferable method to add an alkali metal salt of carboxylic acid or sulfonic acid, or to add alkali hydroxide. If the copolymerization component is less than 30 mol%, the crystallinity of the polymer will not be significantly affected even if it contains meta bonds, ortho bonds, ether bonds, sulfone bonds, sulfide ketone bonds, biphenyl bonds, phenyl sulfide bonds, etc. The amount of the copolymerized component is preferably 10 mol % or less, although it does not matter. In particular, when phenyl, biphenyl, naphthyl sulfide bonds, etc. having trifunctional or higher functional groups are selected for copolymerization, the amount is preferably 3 mol% or less, more preferably 1 mol% or less.

[0010] Such PPS can be produced by a common manufacturing method, for example (
1) Reaction between a halogen-substituted aromatic compound and an alkali sulfide (US Pat. No. 2,513,188, etc., Japanese Patent Publication No. 1986-276)
71 and Japanese Patent Publication No. 45-3368) (2) Condensation reaction of thiophenols in the presence of an alkali catalyst or copper salt, etc. (see US Pat. No. 3,274,615, British Patent No. 1,160,660) (3) Aromatic Condensation reaction of group compounds with sulfur chloride in the coexistence of a Lewis acid catalyst (Special Publication No. 46)
-27255, Belgian Patent No. 29437), and can be arbitrarily selected depending on the purpose.

On the other hand, the polyamide resin in the present invention is
At least one type of polyamide selected from the following.

Polyamide 1: A polyamide obtained by ring-opening polymerization of caprolactam or laurolactam, and further contains aminododecanoic acid, aminoundecanoic acid, adipic acid, sebacic acid, dodecanoic acid, tetramethylenediamine within the scope of the purpose of the present invention. , hexamethylene diamine, dodecane diamine, or m-xylylene diamine as a copolymerization component.

Polyamide 2: A polyamide obtained by polycondensation of aminoundecanoic acid, and further contains caprolactam, laurolactam, adipic acid, sebacic acid, dodecanoic acid, tetramethylene diamine, hexamethylene diamine, Dodecanediamine or m-xylylenediamine may be included as a copolymerization component.

Polyamide 3: dicarboxylic acid selected from adipic acid or sebacic acid and tetramethylene diamine, hexamethylene diamine, dodecane diamine, or m
- A polyamide obtained by polycondensation with a diamine selected from xylylene diamine, and may further contain caprolactam, laurolactam, or aminoundecanoic acid as a copolymer component without departing from the object of the present invention.

These polyamides have a relative viscosity ηrel
．． However, ηrel. ≧2.8 (96% H2SO4, 25℃
, concentration 1 g/dl). Furthermore, in the present invention, two or more of the above polyamides can be used in combination.

The composition of the present invention contains fibrous reinforcing agents such as glass fiber, carbon fiber, potassium titanate, asbestos, silicon carbide, ceramic fiber, metal fiber, silicon nitride, and aramid fiber; barium sulfate, calcium sulfate, kaolin, and clay. , pyrophyllite, pentonite, sericite, zeolite, mica, mica, nephelinsinite, talc, atalbulgite, wollastonite, PMF, ferrite, aluminum silicate, calcium silicate, calcium carbonate, magnesium carbonate, dolomite, 80% of the composition contains inorganic fillers such as ammonium oxide, zinc oxide, titanium oxide, magnesium oxide, iron oxide, molybdenum disulfide, graphite, gypsum, glass beads, glass balloons, and quartz powder.
It can be contained up to % by weight.

The composition of the present invention may also contain small amounts of a silane coupling agent, a mold release agent, a coloring agent, a heat stabilizer, a blowing agent, a flame retardant, a flame retardant aid, and the like, without departing from the purpose of the present invention. It can contain a rust preventive agent.

Furthermore, the following polymers can be mixed and used in the same manner. These polymers include ethylene, butylene, pentene, butadiene, isoprene, chloroprene,
Homopolymers or copolymers of monomers such as styrene, α-methylstyrene, vinyl acetate, vinyl chloride, acrylic esters, methacrylic esters, (meth)acrylonitrile, polyurethanes, polyesters, liquid crystal polymers, polycarbonates, polyacetals, polysulfone,
Polyether sulfone, polyaryl sulfone, polyarylate, polyphenylene ether, polyether ketone, polyether ether ketone, polyether imide, polyimide, polyamide imide, silicone resin, epoxy resin, phenoxy resin, fluororesin, polyaryl ether, etc. Examples include homopolymers, random copolymers, block copolymers, and graft copolymers.

The composition of the present invention can be prepared by various known methods. For example, after uniformly mixing the raw materials in advance with a mixer such as a tumbler or Henschel mixer,
There is a method in which the mixture is fed into a screw or twin screw extruder, melt-kneaded at 230 to 400°C, and then prepared as pellets.

[0020] The present invention will be specifically explained below with reference to Examples, but the present invention is not limited to these Examples.

[0021]

[Example] Reference example 1 (Synthesis of PPS resin) 50
In a scale autoclave, N-methylpyrrolidone was added at a molar ratio of 70, sodium sulfide nonahydrate was added at a molar ratio of 0.99, and sodium benzoate was added at a molar ratio of 0.99. 60, sodium hydroxide 0.15
(50 molar scale) and heated to 210° C. in a nitrogen stream to perform dehydration to a dehydration rate of 110%.

After the system was cooled to 160° C., P-dichlorobenzene was charged at a molar ratio of 10 and the system was sealed, and the internal pressure was increased to 25 kg/cm 2 with nitrogen. The temperature was controlled while taking into consideration the heat generated by polymerization, and the temperature was raised to 270° C., and polymerization was carried out with stirring for 5 hours. Internal pressure is 17Kg/
It had risen to cm2.

Next, after the system was cooled, the pressure was released, and the contents were poured into a large amount of water to recover the flaky polymer. polymer
was washed repeatedly with hot water and acetone, and finally 7
It was in the form of white flakes with a yield of 0%. This PPS resin powder was put into a ribbon blender, stirred at 270° C. while blowing air, and heated to partially crosslink the PPS in the powder state until the intrinsic viscosity reached 0.3.

Examples 1 to 4 and Comparative Examples 1 to 3 Using the PPS synthesized in Reference Example 1, the raw materials shown in Table 1 were uniformly mixed in the proportions shown in the table, and then heated to 290°C in a vented 3
The mixture was kneaded and pelletized using a 5 mm twin-screw extruder. The crystallization rate was measured using this pellet. Further, the pellets were molded into test pieces for measuring mechanical properties using an in-line screw injection molding machine at a cylinder temperature of 290°C, a mold temperature of 135°C, an injection pressure of 1000 kgf/cm2, and an injection speed of medium speed. was evaluated. The results are shown in Table-1.

[0025]

[Table 1]

The symbols in the table are as follows. PPS-A: PPSPA-A synthesized according to Reference Example 1,
B, C: Polycondensate of adipic acid and hexamethylene diamine PA-D, E: Polycondensate of adipic acid and metaxylylene diamine PA-F, G: Ring-opening polymer of ε-caprolactam tSA
, tPA: Crystallization start temperature and peak temperature of each polyamide single item tSP, tPP: Crystallization start temperature and peak temperature of each PPS single item TSA, TPA: Crystallization start temperature and peak temperature of polyamide in the composition TSP, TPP: Crystallization initiation temperature and peak temperature of polyamide in the composition

Examples 5 to 6 and Comparative Example 4 Using the PPS synthesized in Reference Example 1, the raw materials shown in Table 2 were uniformly mixed in the proportions shown in the table, and then heated to 290°C in a vented 35 m
The mixture was kneaded and pelletized using a twin-screw extruder. Furthermore, the pellets were molded using an in-line screw injection molding machine with a cylinder temperature of 290°C and a mold temperature of 135°C.
℃, an injection pressure of 1000 Kgf/cm2, and an injection speed of medium speed to form test pieces for surface state observation and mechanical property measurement, and the properties were evaluated. The results are shown in Table-2.

[0028]

[Table 2]

The evaluation items are as follows.

(Crystallization rate) THE manufactured by Shimadzu Corporation
Measured using RMAL ANALYZERDT-30. (Sample weight approximately 8 mg) Measurement was performed at a heating rate of 30°C/min.
The temperature was raised from 23°C to 330°C, held at 330°C for 3 minutes, and then heated at 5°C/min. The temperature decreases. At this time, read the crystallization start temperature and peak temperature.

(Surface condition) 50mm x 100mm x 2m
Judgment was made by visually observing the surface condition of the molded test piece using the film gate of m.

[0032] No cloudiness
…○ Cloudy over the whole area.
…×

(Mechanical properties) Bending properties (ASTM
D-790 compliant) Izod impact strength (ASTM D-256 compliant) However, both were measured in an absolutely dry state.

[0034]

Effects of the Invention The present invention can provide a composition having a high crystallization rate, high mechanical properties, and good surface condition by blending a specific polyamide resin with PPS.

Claims (1)

[Claims] [Claim 1] Polyphenylene sulfide resin (A)
and at least one polyamide resin (B) selected from the following in a ratio of (A)/(B) = 95/5 to 5/95, and the relative viscosity of the polyamide resin ηr
el. However, ηrel. ≧2.8 (96% H2SO4,
A thermoplastic resin composition having a concentration of 1 g/dl at 25°C. Polyamide 1: Polyamide obtained by ring-opening polymerization of caprolactam or laurolactam. Polyamide 2: Polyamide produced by polycondensation of aminoundecanoic acid. Polyamide 3: dicarboxylic acid selected from adipic acid, sebacic acid, or dodecanoic acid and tetramethylene diamine, hexamethylene diamine, dodecane diamine, or m
- A polyamide obtained by polycondensation with a diamine selected from xylylene diamine.