JPH06179817A - Poly@(3754/24)phenylene sulfide) resin composition - Google Patents

Abstract

PURPOSE:To obtain a resin composition which is reduced in gas generation at a molding temp. while retaining toughness and heat resistance and is excellent in long-term mechanical stability at a high temp. by mixing a specific poly (phenylene sulfide) with a specific ethylene copolymer. CONSTITUTION:The resin composition comprises 60-99.5wt.% poly (phenylene sulfide) having a melt viscosity of 400 P or higher before curing and 500-30,000 P after heat curing and containing amino groups in an amount of 0.05-5mol% based on the phenylene sulfide units and 40-0.5wt.% ethylene copolymer containing 0.5-30wt.% comonomer units derived from an epoxy compound represented by the formula (wherein R<1>, R<2>, and R<3> each is hydrogen or a 1-12C hydrogen group and m is an integer of 1-4).

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyphenylene sulfide resin composition which has excellent toughness, long-term mechanical stability at high temperatures and heat resistance, and which produces a small amount of gas at a molding temperature.

[0002]

2. Description of the Related Art Polyphenylene sulfide has heat resistance,
It is known as a high-performance resin that exhibits excellent properties such as flame retardancy, solvent resistance, moldability, and electrical characteristics, and has been widely used in recent years in applications such as electric / electronic parts and automobile parts. However, polyphenylene sulfide is nylon,
Compared with engineering plastics such as polycarbonate, polybutylene terephthalate, and polyacetal, it has a serious drawback such as poor ductility and brittleness. Therefore, application to many uses is limited.

Conventionally, as a technique for improving the toughness and impact resistance of polyphenylene sulfide, blending of a flexible polymer has been often performed. For example, a method of incorporating a polymer rubber into a polyphenylene sulfide resin (JP-A-60-120753, etc.) is disclosed. However, the effect of improving impact properties is not sufficient just by blending the flexible polymer.

Therefore, in order to further improve the impact properties, a composition having improved adhesion at the interface between polyphenylene sulfide and a flexible polymer is disclosed. For example, a method of incorporating an ethylene-glycidyl methacrylate copolymer into a polyphenylene sulfide resin (Japanese Patent Application Laid-Open No. Sho 5)
No. 8-154757) or amino group and / or amide group-containing polyphenylene sulfide and an epoxy group-containing olefin copolymer or a carboxyl group-containing olefin copolymer (JP-A-61-20).
No. 7462) is disclosed. However, when a conventional epoxy group (for example, glycidyl methacrylate) or a flexible polymer containing an unsaturated carboxylic acid or an anhydride thereof is used as in the composition described in the above publication,
Although it has the effect of improving impact properties, it is said that the amount of gas generated at the molding temperature increases and the long-term mechanical stability at high temperatures is inferior (the toughness and strength decrease rate after standing for a long time at high temperatures is large). It has problems, and its long-term mechanical stability at high temperature is inferior, which limits its applications, and if the amount of gas generated at the molding temperature is large, the surface appearance of the molded product deteriorates and mechanical Degradation of properties occurs.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide a resin composition which retains toughness and heat resistance while reducing the amount of gas generated at the molding temperature and has excellent long-term mechanical stability at high temperatures. To provide.

[0006]

Means for Solving the Problems The present invention adjusts melt viscosities before and after curing, and further, a specific polyphenylene sulfide resin modified with an amino group is copolymerized with a specific epoxy compound to obtain a polyethylene-based copolymer. The present invention relates to a resin composition containing a combination.

That is, the present invention (A) has a melt viscosity of 400 poise or more before curing and a melt viscosity of 50 after heating and curing.
60 to 99.5 wt% of polyphenylene sulfide having 0 to 30,000 poise and containing 0.05 to 5 mol% of amino groups per phenylene sulfide unit, and (B) an epoxy compound represented by the following general formula (1) The polyphenylene sulfide resin composition is characterized by comprising 40 to 0.5% by weight of a polyethylene-based copolymer obtained by copolymerizing 0.5 to 30% by weight of

[0008]

[Chemical 2] (R ¹ , R ² , and R ³ are hydrogen atoms or hydrocarbon groups having 1 to 12 carbon atoms, m is an integer of 1 to 4) Content of amino group of amino group-containing polyphenylene sulfide used in the present invention Is 0.05-per phenylene sulfide unit.
5 mol% is preferable. Particularly preferably 0.1 to 3 mol%
Is. If the amino group content of the polyphenylene sulfide is less than 0.05 mol%, the effect of containing the amino group in the polyphenylene sulfide is small, and if it exceeds 5 mol%, the mechanical strength decreases, which is not preferable.

The amino group-containing polyphenylene sulfide used in the present invention has a melt viscosity (measurement temperature of 30) before curing.
Under conditions of 0 ° C and load of 10 kg, diameter 0.5 mm, length 2
The porosity is 400 poises or more, particularly preferably 500 poises or more, and the melt viscosity after heat curing is 500 to 30,000 poises, particularly preferably 1000 to 20,000 poises. If the melt viscosity before heat curing is less than 400 poise or the melt viscosity after heat curing is less than 500 poise, the effect of improving toughness is poor, and the melt viscosity after heat curing is 30,000.
If it exceeds the poise, the molding process may become difficult.

The method for producing the amino group-containing polyphenylene sulfide used in the present invention is not particularly limited, but a preferable method is to react the alkali metal sulfide with dihalobenzene in an organic amide solvent. , And a method of polymerizing in the presence of an amino group-containing aromatic halide.

Alkali metal sulfides include lithium sulfide, sodium sulfide, potassium sulfide, rubidium sulfide,
Mention may be made of cesium sulphide and mixtures thereof, which may be used in the hydrated form. These alkali metal sulfides are obtained by reacting an alkali metal hydrosulfide with an alkali metal base, and may be prepared in situ prior to the addition of dihalobenzene into the polymerization system or outside the system. It doesn't matter even if you use the ones.

Further, the amino group-containing polyphenylene sulfide used in the present invention has, as its constitutional unit,

[0013]

[Chemical 3] Content of 70 mol% or more, preferably 90 mol% or more is preferable.

If the constituent unit is less than 30 mol%, preferably less than 10 mol%, the m-phenylene sulfide unit shown below,

[0015]

[Chemical 4] o-phenylene sulfide unit,

[0016]

[Chemical 5] Phenylene sulfide sulfone unit,

[0017]

[Chemical 6] Phenylene sulfide ketone unit,

[0018]

[Chemical 7] Phenylene sulfide ether unit,

[0019]

[Chemical 8] Diphenylene sulfide unit,

[0020]

[Chemical 9] It does not matter even if it contains a copolymerized unit such as.

The amino group-containing aromatic halide has the general formula

[0022]

[Chemical 10] (X is halogen, Y is hydrogen, -NH ₂ group or halogen,
R is a hydrocarbon group having 1 to 12 carbon atoms, and n is an integer of 0 to 4).

Some examples thereof are m-fluoroaniline, m-chloroaniline, 3,5-dichloroaniline, 3,5-diaminochlorobenzene and 2-amino-4.
-Chlorotoluene, 2-amino-6-chlorotoluene,
4-amino-2-chlorotoluene, 3-chloro-m-phenylenediamine, m-bromoaniline, 3,5-dibromoaniline, m-iodoaniline and mixtures thereof. Particularly, 3,5-diaminochlorobenzene and 3,5-dichloroaniline are preferable.

As dihalobenzene, p-dichlorobenzene, p-dibromobenzene, p-diiodobenzene, m-dichlorobenzene, m-dibromobenzene, m-diiodobenzene, 1-chloro-4-bromo. Examples include benzene.

The amounts of the alkali metal sulfide and (dihalobenzene + amino group-containing aromatic halide) charged are molar ratios of (alkali metal sulfide) :( dihalobenzene + amino group-containing aromatic halide) = 1. 00:
The range of 0.90 to 1.10 is preferable.

The polymerization solvent is preferably a polar solvent,
In particular, an organic amide which is aprotic and stable to alkali at high temperature is a preferable solvent. Some examples of organic amides are N, N-dimethylacetamide, N, N-dimethylformamide, hexamethylphosphoramide, N-
Methyl-ε-caprolactam, N-ethyl-2-pyrrolidone, N-methyl-2-pyrrolidone, 1,3-dimethylimidazolidinone, dimethylsulfoxide, sulfolane, tetramethylurea and the like and mixtures thereof can be mentioned.

The amount of the organic amide used as the solvent is 150 to 3 with respect to the polymer produced by the polymerization.
It can be used in an amount of 500% by weight, preferably 250 to 1500% by weight. Polymerization is 200-300
C., preferably 220 to 280.degree. C., for 0.5 to 30 hours, preferably 1 to 15 hours with stirring.

The obtained polymer can be washed after being treated with hot water or an acid.

The polymer obtained by the above method can be cured by heat treatment in an oxygen atmosphere and / or an inert gas, or heat treatment with addition of a peroxide or the like to increase the degree of polymerization. it can. For example, the treatment is performed in an air atmosphere at a temperature range of 200 to 280 ° C. for 1 to 24 hours. Here, examples of the non-oxidizing inert gas include helium, argon, nitrogen, carbon dioxide, water vapor and the like, or a mixture thereof, but nitrogen is preferable from an economical point of view.

The polyethylene copolymer used in the present invention contains 0.5 to 0.5 of a specific epoxy compound in polyethylene.
Copolymerized at 30% by weight.

The polyethylene used in the present invention refers to at least one of high-density polyethylene, low-density polyethylene, linear low-density polyethylene and the like, preferably low-density polyethylene.

The specific epoxy compound is a compound represented by the general formula (1). The copolymerization amount of the epoxy compound in the polyethylene-based copolymer is preferably 0.5 to 30% by weight, particularly preferably 3 to 20% by weight. If it exceeds the range, gelation occurs during melt-kneading with the polyphenylene sulfide resin, and moldability and mechanical properties are deteriorated, which is not preferable.

As a method for copolymerizing this epoxy compound with polyethylene, polyethylene, an epoxy compound and a radical generator such as a peroxide are mixed and copolymerized by a melt extrusion method, or a suspension in an appropriate solvent is carried out. Alternatively, a known method such as a method of adding an epoxy compound and a radical initiator to dissolved polyethylene and copolymerizing by heating is mentioned.

The blending amount of the above-mentioned polyethylene copolymer is 0.5 to 40% by weight, particularly 5 to 30% by weight,
If less than 0.5% by weight, the effect of improving toughness cannot be obtained, and
If it exceeds 5% by weight, the excellent heat resistance and solvent resistance of the polyphenylene sulfide resin itself deteriorate, which is not preferable.

The resin composition of the present invention can be manufactured by various known methods. As the raw material resin, a dry powder is mixed in advance with a mixer such as a tumbler, a Henschel mixer, a ball mill, a ribbon blender, or the resin is further cured by heat treatment. The dry powder or pellets thus prepared are mixed in a blender or the like, and the resin used is further melt-mixed to produce a resin composition. Alternatively, the raw material resins may be separately supplied to a melt mixer and melt-mixed to produce a resin composition. The melt mixing can be performed by a method such as melt kneading at a temperature of 250 to 350 ° C. with a kneader, Banbury mixer, extruder or the like. Although there is no particular limitation, it is preferable to use an extruder in consideration of operability.

With respect to the resin composition of the present invention, conventionally known fibrous and inorganic powdery fillers, that is, glass fiber, carbon fiber, silica fiber, alumina fiber, to the extent that the object of the present invention is not impaired, Fibrous fillers such as silicon carbide fibers, zirconia fibers, calcium titanate fibers, wollastonite, calcium sulfate fibers, aramid fibers, wholly aromatic polyester fibers, calcium carbonate, magnesium carbonate, talc, mica, clay, silica, Alumina, kaolin, zeolite, gypsum, calcium silicate, magnesium silicate, calcium sulfate, titanium oxide, magnesium oxide, carbon black, graphite, iron oxide, zinc oxide, copper oxide, glass beads, glass powder, glass balloon, quartz, An inorganic filler such as quartz glass can also be blended. Further, these fillers can be used in combination of two or more, and if necessary, they can be used after being pretreated with a coupling agent such as silane type and titanium type.

Further, the resin composition of the present invention is a conventionally known release agent, lubricant, heat stabilizer, antioxidant, ultraviolet absorber, crystal nucleating agent, foaming agent within the range not impairing the object of the present invention. , A rust preventive, an ion trap agent, a flame retardant, a flame retardant aid, a coloring agent such as a dye or a pigment, an additive such as an antistatic agent, a wax, and a small amount of another kind of polymer may be used in combination of one or more kinds. .

The additive may be added by any method. For example, it may be added to each resin before or during the formation of the composition, after the formation of the composition, or when the composition is melted.

[0039]

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

Reference Example 1 (Synthesis 1 of Polyphenylene Sulfide Containing Amino Group) 5 l of N-methyl-2-pyrrolidone (hereinafter abbreviated as NMP) was charged into a 15 l autoclave and heated to 120 ° C., and then Na ₂ S. 1866 g of 2.8H ₂ O was charged, and the temperature was gradually raised to 205 ° C. with stirring over about 2 hours to distill 407 g of water. After cooling this system to 140 ° C., 2080 g of p-dichlorobenzene was added, the temperature was raised to 225 ° C., polymerization was performed for 3 hours, and then 250 ° C.
The temperature was raised to. When the temperature reaches 250 ° C, NMP5
20.2 g of 3,5-diaminochlorobenzene in 0 ml
A solution in which (about 1 mol% was added to the total amount of p-dichlorobenzene and 3,5-diaminochlorobenzene was added) was pressed into the system, and further polymerized at 250 ° C. for 3 hours.

After completion of the polymerization, a part of the slurry cooled to room temperature was sampled, filtered, and unreacted 3,5-diaminochlorobenzene remaining in the filtered solution was analyzed by gas chromatography (Shimadzu Corporation GC-12A). It was measured.
The conversion of 3,5-diaminochlorobenzene was 38%. Also, the remaining slurry is poured into a large amount of water to precipitate the polymer, and after filtering and washing with pure water,
The polymer was isolated by heating and vacuum drying overnight. Melt viscosity of the obtained PPS (die; diameter 0.5 m
m, length 2 mm, measured at 300 ° C., 10 kg load with a Koka type flow tester) was 500 poise.
Further, this polymer was heated and cured at 235 ° C. for 2 hours in an air atmosphere to obtain a polymer having a melt viscosity of 8000 poise. The polyphenylene sulfide thus obtained is called PPS-A.

Reference Example 2 (Synthesis 2 of polyphenylene sulfide containing amino group) 2080 g of p-dichlorobenzene and 22.9 g of 3,5-dichloroaniline (total amount of p-dichlorobenzene and 3,5-dichloroaniline) (About 1 mol% addition) to 250 ° C., and the temperature is raised to 250 ° C. over 1 hour and 20 minutes.
An amino group-containing polyphenylene sulfide was produced in the same manner as in Reference Example 1, except that the polymerization was conducted for 3 hours. The melt viscosity of the obtained polymer was 480 poise. When unreacted 3,5-dichloroaniline remaining in the filtrate was measured by gas chromatography, the conversion of 3,5-dichloroaniline was 75%. Further, this polymer was heat-cured at 235 ° C. for 2 hours in an air atmosphere to obtain a polymer having a melt viscosity of 7800 poise. The polyphenylene sulfide thus obtained is called PPS-B.

Reference Example 3 (Synthesis 3 of amino group-containing polyphenylene sulfide) 2080 g of p-dichlorobenzene, 18.4 g of m-chloroaniline (about 1 mol based on the total amount of p-dichlorobenzene and m-chloroaniline) % Addition), 2
An amino group-containing polyphenylene sulfide was produced by the same procedure as in Reference Example 1, except that the temperature was raised to 50 ° C. over 1 hour and 20 minutes and the polymerization was performed at 250 ° C. for 3 hours. The viscosity of the obtained polymer was 480 poise. Also,
When unreacted m-chloroaniline remaining in the filtrate was measured by gas chromatography, the conversion rate of m-chloroaniline was 35%. Further, this polymer was heated and cured at 235 ° C. for 2 hours in an air atmosphere to obtain a polymer having a melt viscosity of 8000 poise. The amino group-containing polyphenylene sulfide thus obtained was treated with PPS.
-C.

Reference Example 4 (Synthesis 4 of Polyphenylene Sulfide Containing Amino Group) p-dichlorobenzene 2009 g, 3,5-diaminochlorobenzene 19.0 g (p-dichlorobenzene and 3,
Reference Example 1 except that about 1 mol% of the total amount of 5-diaminochlorobenzene was added), the temperature was raised to 250 ° C. over 1 hour and 20 minutes, and the polymerization was performed at 250 ° C. for 3 hours. An amino group-containing polyphenylene sulfide was produced by the same operation as described above. The viscosity of the obtained polymer was 110 poise. In addition, unreacted 3,5 remaining in the filtrate
When diaminochlorobenzene was measured by gas chromatography, the conversion of 3,5-diaminochlorobenzene was 36%. Further, this polymer was heat-cured at 235 ° C. for 2 hours in an air atmosphere to obtain a melt viscosity of 80.
A polymer of 00 poise was obtained. The amino group-containing polyphenylene sulfide thus obtained is designated as PPS-D.

Reference Example 5 (Synthesis of polyphenylene sulfide) 2080 g of p-dichlorobenzene (without addition of an amino group-containing aromatic halide) was added, and the other reference example 1
Polymerization was carried out in the same manner as in. The viscosity of the obtained polymer was 550 poise. The polymer thus obtained is heated and cured at 235 ° C. for 2 hours in an air atmosphere,
A polymer having a melt viscosity of 8000 poise was obtained. The polyphenylene sulfide thus obtained is referred to as PPS-E.

Reference Example 6 (Synthesis of Polyphenylene Sulfide Containing Large Amount of Amino Group) 1789 g of p-dichlorobenzene and 280 g of m-chloroaniline (about 15 relative to the total amount of p-dichlorobenzene and m-chloroaniline). Mol% addition), 250
An amino group-containing polyphenylene sulfide was produced by the same procedure as in Reference Example 1, except that the temperature was raised to 1 ° C over 1 hour and 20 minutes and the polymerization was performed at 250 ° C for 3 hours. The viscosity of the obtained polymer was too low to be measured. Further, when unreacted m-chloroaniline remaining in the filtrate was measured by gas chromatography, the conversion rate of m-chloroaniline was 38%. Further, this polymer was heated and cured at 235 ° C. for 10 hours in an air atmosphere to obtain a polymer having a melt viscosity of 6600 poise. The amino group-containing polyphenylene sulfide thus obtained was treated with PPS.
-F.

Examples 1 to 5 Various polyphenylene sulfides (PP) obtained in Reference Examples
S-A, B, C), ethylene-epoxy compound (with epoxy compound N- [4- (2,3-epoxypropoxy))
-3,5-dimethylbenzyl] acrylamide is used,
A copolymer (referred to as a copolymer I) having a weight ratio of 90/10) and glass fibers were mixed in a ratio shown in Table 1 and melt-kneaded at 300 ° C. by a twin-screw extruder to form pellets. The pellets obtained were injection molded at 300 ° C. to prepare test pieces, and the Izod impact strength (measured according to ASTM D-256, with notch) was measured. Further, the long-term mechanical stability at high temperature is shown by the retention rate of Izod impact strength after standing for 1000 hours at a temperature of 180 ° C. (ratio to the Izod impact strength of the test piece not left at high temperature). As a measure of heat resistance, the Vicat softening temperature (JIS K7206) of the test piece obtained by injection molding was measured. The amount of gas generated was obtained by drying the obtained pellets at 150 ° C. for 2 hours and then using a thermogravimetric analyzer to obtain a nitrogen flow rate of 50.
ml / min, heating rate from room temperature at a heating rate of 10 ° C./min, 3
The weight reduction amount per 1 g of the sample when reaching 50 ° C. was obtained. The results are shown in Table 1. In Examples 1 to 5, the toughness and the long-term mechanical stability at high temperature are excellent, and the gas generation amount is small.

Comparative Examples 1 and 2 PPS-A obtained in Reference Example 1 and glass fiber were mixed at a ratio shown in Table 1 and the same experiment as in Example 1 was conducted. The results are shown in Table 1.

Comparative Examples 3 to 5 Various polyphenylene sulfides (PPS-D, E and F) obtained in Reference Examples 4 to 6 and the copolymer I were mixed at the ratio shown in Table 1, and the same as in Example 1. An experiment was conducted. The results are shown in Table 1.
Shown in.

Comparative Examples 6 to 7 PPS-A obtained in Reference Example 1 and an ethylene-epoxy compound copolymer (Copolymer I) were mixed in the composition shown in Table 1 and the same experiment as in Example 1 was conducted. It was The results are shown in Table 1. In the experiment of long-term stability at high temperature of Comparative Example 7, one test piece was used.
When left at 80 ° C. for 1000 hours, the test piece was deformed.

Comparative Examples 8 to 9 PPS-A obtained in Reference Example 1, ethylene-glycidyl methacrylate (weight ratio 90/10) copolymer (referred to as copolymer II), and glass fiber are blended as shown in Table 1. Then, the same experiment as in Example 1 was performed. The results are shown in Table 1.

Comparative Example 10 PPS-A obtained in Reference Example 1 and the glycidyl methacrylate-modified ethylene-propylene copolymer (glycidyl methacrylate modification amount 10% by weight, referred to as copolymer III) are blended in Table 1. After mixing, the same experiment as in Example 1 was performed.
The results are shown in Table 1.

[0053]

[Table 1]

[0054]

INDUSTRIAL APPLICABILITY According to the present invention, a polyethylene copolymer obtained by adjusting the melt viscosity before and after curing and further copolymerizing a specific epoxy compound with a specific polyphenylene sulfide resin modified with an amino group is provided. By blending, it is possible to obtain a polyphenylene sulfide resin composition which retains the original heat resistance of the polyphenylene sulfide resin, has improved toughness and long-term mechanical stability at high temperatures, and has a small gas generation amount.

Claims (1)

[Claims] 1. (A) The melt viscosity before curing is 400 poise or more, the melt viscosity after heat curing is 500 to 30,000 poise, and 0.05 to 5 mol% of amino groups are contained per phenylene sulfide unit. 60 to 99.5% by weight of polyphenylene sulfide, and (B) 0.5 to 30% by weight of the epoxy compound represented by the following general formula (1).
Copolymerized polyethylene-based copolymer 40 to 0.5% by weight
A polyphenylene sulfide resin composition comprising: [Chemical 1] (R ¹ , R ² , and R ³ are hydrogen atoms or hydrocarbon groups having 1 to 12 carbon atoms, and m is an integer of 1 to 4)