JPH08134352A - Polyphenylenesulfide resin composition - Google Patents

Abstract

PURPOSE: To obtain the subject resin composition containing a specific polyphenylenesulfide and a specific esteramide copolymer in a specific ratio, having rapid crystallization rate, excellent in heat resistance, chemical resistance and frame resistance and useful for electrical and electron components, etc. CONSTITUTION: This resin composition is composed of (A) 70-99.5wt.% of a polyphenylenesulfide such as a poly(p-phenylenesulfide) having 10-50000 poise melting viscosity and (B) 0.5-30wt.% of an esteramide copolymer having 500-10000 number-average molecular weight and consisting of 10-90wt.% of an aromatic oligoamide chain expressed by the formula (R<1> and R<2> are each a 6-30 divalent aromatic) and 90-10wt.% of a polyalkyleneoxide chain having 500-10000 number average molecular weight.

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, and more particularly to a polyphenylene sulfide which has a fast crystallization rate, excellent toughness such as high strength and great elongation, and is thermally stable. The present invention relates to a resin composition.

Polyphenylene sulfide (hereinafter abbreviated as PPS) has been attracting attention as a member for electric / electronic equipment and a member for automobile equipment due to its excellent heat resistance and chemical resistance. In addition, various molding parts such as injection molding, extrusion molding,
Can be formed into films, sheets, pipes, fibers, etc.,
Widely used in fields where heat resistance and chemical resistance are required.

[0003]

2. Description of the Related Art PPS is a polymer containing -φ-S- (wherein φ represents a phenylene group; hereinafter the same) as a main constitutional unit, and its production method is described in JP-B-45-3368. U.S. Pat. No. 3,793,256 and Japanese Patent Publication No. 52-12240. However, it is generally known that PPS produced by these manufacturing methods is brittle and that it is necessary to raise the molding processing temperature (particularly the mold temperature).

As a method of imparting toughness to PPS, a method of adding a modified polyolefin is disclosed in JP-A-58-1547.
JP-A-59-113055 discloses a method of adding a thermoplastic elastomer such as a polyamide-based elastomer or a polyester-based elastomer to JP-A-57-1957.

As a method for improving the processability of PPS, a method of adding an oligomeric ester is disclosed in JP-A-62-45.
JP-A-62-23084 discloses a method of adding a monomeric carboxylic acid ester, and JP-A-62-23084 discloses a method of adding another thioether.
A method of adding a specific aromatic phosphoric acid ester to JP-A No. 9-93 is disclosed in JP-A-62-230850 and JP-A-1-
The method of adding polyalkylene glycol to JP-A-225660 is disclosed in JP-A-4-103661 and JP-A-4-103661.
No. 1036364, Japanese Unexamined Patent Publication No. 5-194848, and Japanese Unexamined Patent Publication No. 6-207102.

[0006]

However, when a modified polyolefin is used as a method of imparting toughness, it is possible to improve the toughness by adding a large amount of the modified polyolefin, but PPS originally has it. Heat resistance, chemical resistance, and flame retardance are lost, which is not desirable. In addition, in the method of adding the thermoplastic elastomer,
The described thermoplastic elastomers have a poor compatibility with PPS, a poor effect of improving toughness, and a problem of causing a defective appearance of a molded product.

Regarding any of the methods for improving the processability of PPS, the heat resistance of the additive is poor in any of the methods, so that an evaporative gas or a decomposed gas is generated during the molding process, or the additive has a low molecular weight. Move to the surface of the molded product,
The additive has a problem of contaminating the surface of the mold or the surface of the molded product.

Therefore, an object of the present invention is that PPS has excellent properties such as heat resistance, chemical resistance, and flame retardancy, a high crystallization rate, and an excellent toughness, and further has a thermal property. And a polyphenylene sulfide resin composition that solves various problems during molding and processing.

[0009]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have found that a composition comprising PPS and a specific esteramide copolymer can solve the above problems. The present invention has been completed.

That is, the present invention provides polyphenylene sulfides 70-9 having a melt viscosity of 10-50000 poise.
9.5% by weight and 10 to 90% by weight of an aromatic oligoamide chain represented by the following formula (I) —CO—R ¹ —NH—CO—R ² —CO—NH—R ¹ —CO— (I) (formula) R ¹ and R ² each represent a divalent aromatic group having 6 to 30 carbon atoms) Number average molecular weight 5000 consisting of 90 to 10% by weight of polyalkylene oxide chain having number average molecular weight 500 to 10,000
~ 500000 ester amide copolymer 0.5 to 30
The present invention relates to a polyphenylene sulfide resin composition containing 1% by weight and will be described in detail below.

The PPS used in the present invention is not particularly limited as long as it has a melt viscosity of 10 to 50000 poise, and it is not limited to Japanese Patent Publication No. 45-3368 and US Pat.
It can be obtained by a known method such as Japanese Patent Publication No. 56, Japanese Patent Publication No. 52-12240. And the structural unit is
Bonding unit: It is preferable that the repeating unit represented by -φ-S- contains 70 mol% or more, more preferably 90 mol% or more. Furthermore, 70 p-phenylene sulfide units are used as repeating units.
PPS containing at least mol% has high crystallinity and excellent heat resistance, and is therefore particularly preferably used.

The remaining repeating unit is not limited as long as it is a copolymerizable unit. For example, diphenyl sulfide ether unit, diphenyl sulfide sulfone unit, diphenyl sulfide ketone unit, biphenyl sulfide unit, naphthalene sulfide unit, trifunctional phenylene. Examples include sulfide units. These copolymerized units may be block copolymerized or random copolymerized.

Specific examples of preferred PPS include poly (p-phenylene sulfide), poly (p-phenylene sulfide) -poly (m-phenylene sulfide) block copolymers, poly (p-phenylene sulfide) -polysulfone block copolymers. Examples include polymers and poly (p-phenylene sulfide) -polyphenylene sulfide sulfone copolymers.

The PPS used in the present invention
Is a high-performance flow tester (die; inner diameter 0.5 mm,
It has a melt viscosity of 10 to 50,000 poises measured at 300 ° C. using a length of 2.0 mm and a load of 10 kg). If the melt viscosity is less than 10 poise, the melt viscosity is too low to use the melt molding method usually applied in PPS. On the other hand, when the melt viscosity exceeds 50,000 poise, the melt viscosity is too high and melt molding is difficult, which is not preferable. And 50 to which good moldability is shown
The range of 30,000 poise is more preferable. .

Further, the PPS may be linear, crosslinked with oxygen in the coexistence of oxygen, or may be heat-treated in an inert gas atmosphere, Further, it may be a mixture of these structures.

The PPS may be one in which sodium ions are reduced by performing deionization treatment (acid washing, hot water washing, etc.).

The ester amide copolymer used in the present invention is a copolymer consisting of a hard segment consisting of an aromatic oligoamide chain represented by the formula (I) and a soft segment consisting of a polyalkylene oxide chain. The polymer is described in detail in JP-A-6-207007, and exhibits a behavior as a thermoplastic elastomer. The ester amide copolymer that is particularly effective in adding various properties to PPS will be described below in detail.

The hard segment of the ester amide copolymer used in the present invention is an aromatic oligoamide chain represented by the formula (I), and R ¹ and R ² are for imparting heat resistance to the ester amide copolymer. Are each a divalent aromatic group having 6 to 30 carbon atoms. The ester-amide copolymer is particularly preferably used in which R ¹ and R ² are p-disubstituted benzene residues because the heat resistance and molding processability are well balanced.

On the other hand, the soft segment is a polyalkylene oxide chain having a number average molecular weight of 500 to 10,000, such as polyethylene oxide, polypropylene oxide, polytetramethylene oxide, polyhexamethylene oxide, a copolymer of ethylene oxide and propylene oxide. Examples include polyalkylene oxide chains such as copolymers of ethylene oxide and tetrahydrofuran, and ethylene oxide addition polymers of polypropylene oxide. Considering the thermal stability that can withstand the molding and processing conditions of PPS, polyethylene oxide and polytetramethylene oxide. , Polyhexamethylene oxide, and a copolymer of ethylene oxide and tetrahydrofuran are preferably used as the polyalkylene oxide chain. Further, when a polyalkylene oxide chain having a number average molecular weight of less than 500 or more than 10,000 is used, the resulting ester amide copolymer has poor properties as an elastomer, which is not preferable.

Further, in the ester amide copolymer used in the present invention, in order to achieve a higher molecular weight during the production of the ester amide copolymer, the ester amide copolymer is inhibited from being an elastomer. If necessary, it is possible to introduce a dicarboxylic acid unit as a chain extender within the range not specified. As the dicarboxylic acid unit which is a chain extender added as necessary, dicarboxylic acid units such as terephthalic acid, isophthalic acid, succinic acid, glutaric acid and adipic acid are used.

The method for producing the ester amide copolymer is not particularly limited, but for example, an aromatic oligo ester amide alkyl ester and a poly (alkylene oxide) glycol, which are precursors of the aromatic oligo amide chain, and necessary According to the method of producing a dicarboxylic acid diester by a melt reaction (JP-A-6-20
No. 7007), or a method of producing a poly (alkylene oxide) glycol by substituting the end of the poly (alkylene oxide) glycol with an aromatic aminocarboxylic acid compound and then reacting this with an aromatic dicarboxylic acid dichloride in an organic solvent (special (Japanese Patent Application No. 5-2056) or an aromatic oligoester amide alkyl ester and poly (alkylene oxide) glycol are reacted in a specific solvent to obtain a prepolymer, and then the solvent is removed to produce a melt reaction. (Japanese Patent Application No. 5-66716) and the like.

The added amount of the ester amide copolymer used in the present invention is 0.5 to 30% by weight based on the composition of PPS and the ester amide copolymer. Addition amount is 0.5
If it is less than 10% by weight, the effect of improving the crystallization rate and the improvement of toughness are not sufficient, and if it exceeds 30% by weight, the compatibility with PPS deteriorates and phase separation occurs, and the heat resistance and resistance to PPS inherently increase. It is not preferable because excellent properties such as chemical properties and flame retardancy are lost. 2 to 2 because the obtained composition is more excellent in toughness, heat resistance, chemical resistance, flame retardancy, etc.
0% by weight is more preferred.

As a method for producing the PPS / ester amide copolymer composition of the present invention, a commonly used method such as solution blending or melt blending can be used, but a batch type melt kneading device, a uniaxial or biaxial method. A method of melt blending with a shaft extruder or the like is preferable. The PPS / ester amide copolymer composition is produced under the following conditions: kneading temperature of 290 to 340 ° C. and shear rate of 10 to 500 sec ⁻¹ .
It is preferable to knead for 10 minutes, and by setting such conditions, it is possible to enhance the compatibility of PPS and the ester amide copolymer and impart good properties to the PPS / ester amide copolymer composition. .

The PPS / ester amide copolymer composition obtained as described above has excellent heat resistance inherent to PPS,
While maintaining chemical resistance and flame retardancy, it can greatly improve toughness such as elongation. Further, since the composition has a remarkably high crystallization rate as compared with the conventional PPS, it can be sufficiently crystallized by injection molding even when a low temperature mold is used to obtain a molded article having excellent heat resistance. It also solves various problems at the time of molding, which was a drawback of the PPS / polyalkylene glycol composition.

Further, in order to further improve the thermal stability of the PPS / ester amide copolymer composition of the present invention, a specific phenol-based stabilizer as described in JP-A-4-103664 or JP-A- In addition to the specific aromatic amine compounds described in JP-A-6-207102, phosphoric acid, phosphorous acid, hypophosphorous acid derivative, phenylphosphinic acid, polyphosphonate, dialkylpentaerythritol diphosphite, dialkyl. Phosphorus compounds such as bisphenol A diphosphite, thioether series,
A PPS composition 100 containing a sulfur-containing compound such as dithioacid salt-based, mercaptobenzimidazole-based, thiocarbanilide-based, thiodipropionate or tin-based compound such as tin malate or dibutyltin monoxide
0.01 to 5 parts by weight can be used with respect to parts by weight.

Further, the PPS composition of the present invention contains ceramic fibers such as glass fibers, carbon fibers and alumina fibers, aramid fibers, wholly aromatic polyester fibers, if necessary.
Metal fiber, reinforcing filler such as potassium titanate whiskers, calcium carbonate, mica, talc, silica, barium sulfate, barium sulfate, kaolin, clay, pyroferrite, bentonite, sericite, zeolite, nepheline sinite, attapulgite, wo Rastonite, PMF, ferrite, calcium silicate, magnesium carbonate, dolomite, antimony trioxide, zinc oxide,
Titanium oxide, magnesium oxide, iron oxide, molybdenum disulfide, graphite, gypsum, glass beads, glass powder,
It is also possible to blend an inorganic filler such as glass balloon, quartz, quartz glass, or an organic or inorganic pigment.

Further, a release agent such as wax, a silane-based or titanate-based coupling agent, a lubricant, a weather resistance stabilizer, a foaming agent, a rust preventive agent, an ion trap agent, a flame retardant or a flame retardant auxiliary agent is required. You may add according to.

Further, if necessary, polyethylene, polybutadiene, polyisoprene, polychloroprene, polystyrene, polybutene, poly α-methylstyrene, polyvinyl acetate, polyvinyl chloride, polyacrylic acid ester, polymethacrylic acid ester, polyacrylonitrile, Polyamide such as nylon 6, nylon 66, nylon 610, nylon 12, nylon 11, nylon 46, polyester such as polyethylene terephthalate, polybutylene terephthalate, polyarylate, polyurethane, polyacetal, polycarbonate, polyphenylene oxide, polysulfone, polyether sulfone,
One type of homopolymer, random, block or graft copolymer such as polyallyl sulfone, polyphenylene sulfide sulfone, polyether ketone, polyphenylene sulfide ketone, polyether ether ketone, polyimide, polyamide imide, silicone resin, phenoxy resin, fluororesin The above may be mixed and used.

[0029]

EXAMPLES The present invention will now be described in detail with reference to examples, but the present invention is not limited to these examples.

Synthesis Example 1 Internal volume 53 equipped with stirrer, dehydration tower and jacket
110 liters of N-methylpyrrolidone and sodium sulfide (purity: Na ₂ S 60.2 wt%) 6 in a 0 liter reactor 6
1.1 kg was charged and heated with a jacket while stirring,
Dehydration was performed through a dehydration tower until the internal temperature reached about 200 ° C. At this time, 13.5 l of a distillate mainly consisting of water was distilled off. Then, p-dichlorobenzene 68.0k
g and N-methylpyrrolidone 48l were added, the temperature was raised to 225 ° C over 2 hours, the reaction was performed at 225 ° C for 2 hours, the temperature was raised to 250 ° C over 30 minutes, and further 250 ° C for 3 hours. It was made to react. At this time, the pressure is 10.5 kg / cm
Rose to ² .

After the reaction was completed, the reaction mixture was transferred to a solvent collector equipped with a stirrer, a jacket and a decompression line.
At this time, 30 l of N-methylpyrrolidone was added. Subsequently, it was heated under reduced pressure to distill off 200 l of a distillate mainly composed of N-methylpyrrolidone. Next, water 200
1 was added to make a water slurry, and the mixture was heated and stirred at 80 ° C. for 15 minutes, and then centrifuged to collect a polymer.

Further, the polymer was returned to the solvent recovery unit, 200 l of water was added, the mixture was heated and stirred at 180 ° C. for 30 minutes, and after cooling, the polymer powder was recovered by a centrifuge.
This operation was repeated twice.

The obtained polymer was transferred to a ribbon blender with a jacket and dried. A part of this PPS was sampled, and the melt viscosity was increased to 300 using a high flow tester (die: diameter 0.5 mm, length 2.0 mm).
It was 820 poise when measured at a temperature of 10 ° C. and a load of 10 kg. After the completion of sampling, the temperature was raised to 265 ° C. while flowing air with stirring at a flow rate of 400 l / hour, and a curing treatment was performed for 5 hours. The melt viscosity after completion of curing was 4300 poise.

Synthesis Example 2 (Synthesis of Aromatic Oligoester Amide Alkyl Ester) A 10 l separable flask equipped with a nitrogen inlet tube and a stirring blade was completely dried and replaced with nitrogen, and then butyl aminobenzoate (hereinafter referred to as BAB). Abbreviated) 996.5 g (5 mol)
And dehydrated N-methylpyrrolidone (hereinafter abbreviated as NMP)
I charged 2 liters. BAB is dissolved in NMP and ice-cooled (0
~ 5 ° C). Next, 406.0 g (2 mol) of terephthalic acid dichloride (hereinafter abbreviated as TPC) was added to NMP2l.
Was added to the solution. After reacting at 0 to 5 ° C for 6 hours at room temperature for one day and night, it was precipitated in methanol, washed with acetone, and recrystallized with NMP / toluene, and the melting point was 305.
C. oligoester amide butyl ester 785.
1 g (yield 76%) was obtained.

(Synthesis of Esteramide Copolymer) 299.35 g of polytetramethylene glycol having a number average molecular weight of 1031 was placed in an autoclave of 10 l capacity equipped with a nitrogen inlet tube, a temperature sensor, a stirring device, a distillation device and a jacket type heating device. After charging 150 g of an aromatic oligoester amide butyl ester and 1.0 g of a phenol-based antioxidant (manufactured by Ciba-Geigy, trade name Irganox 1010), vacuum drying was performed at 100 ° C. Next, in an autoclave, 1.404 g of tetrabutyl titanate and NMP1
After charging 50 ml and making it react at 190 degreeC for 3.5 hours, the pressure reduction degree was gradually raised and it heated up to 250 degreeC over 1 hour. Then, the reaction was carried out at 250 ° C. under a reduced pressure of 1 mmHg for 4 hours, and a highly viscous pale yellow polymer was produced. When taken out under nitrogen, 398 g (yield 98%) of an elastomeric polymer was obtained. The number average molecular weight of the obtained polymer was 52000 in terms of polystyrene by GPC measurement. This ester amide copolymer is abbreviated as TPEA-1 below.

Synthesis Example 3 604.4 g of polytetramethylene glycol having a number average molecular weight of 2014 was used in place of polytetramethylene glycol having a number average molecular weight of 1031 and the amount of NMP to be added was 2
The same operation as in Synthesis Example 2 was repeated except that the amount was changed to 90 ml, and 6
76.3 g (94% yield) of elastomeric polymer was obtained. The number average molecular weight of the obtained polymer was 51,000 in terms of polystyrene by GPC measurement. This ester amide copolymer is abbreviated as TPEA-2 below.

Examples 1 to 4 PPS and TPEA-1 and TPEA-2 obtained in the synthesis examples
One kind of ester amide copolymer selected from the above was uniformly blended with the composition shown in Table 1, and then melt-kneaded at 300 ° C. for 10 minutes using a lab mixer (manufactured by Toyo Seiki Co., Ltd., trade name Labo Plastomill). After crushing the sample after kneading, use a small injection molding machine (Matsushita Electric Co., Ltd., trade name Panajection) to obtain a cylinder temperature of 300 ° C. and a mold temperature of 9
Injection molding was performed by injection molding under molding conditions of 0 ° C.
Tensile strength and elongation were measured according to TM D638. Further, 10 mg of the above-mentioned kneaded sample was placed in an Al DSC sample container, sealed, and heated and melted at 320 ° C. for 5 minutes, and then a rapidly cooled amorphous sample was used to obtain 10 by DSC (manufactured by Seiko Denshi). The glass transition temperature (Tg) and the crystallization temperature (T
c) was measured. The results are summarized in Table 1.

Comparative Example 1 Only the PPS obtained in the reference example was kneaded by the same operation as in the example, and the same evaluation was carried out. However, at the mold temperature of 90 ° C. when the test piece was prepared, it was impossible to mold due to poor flow, so the mold temperature was set to 120 ° C. The results are shown in Table 1,
It can be seen that when the ester amide copolymer is not added, the elongation is small and the crystallization rate is slow as compared with the examples.

Comparative Examples 2 and 3 PPS and PBT obtained in the synthesis examples are hard segments,
A polyester elastomer having polytetramethylene glycol as a soft segment (manufactured by Toyobo Co., Ltd., trade name Perprene P-70B) was uniformly blended in the composition shown in Table 1, and then kneaded in the same manner as in the example, and the same evaluation was performed. went. However, at the mold temperature of 90 ° C when creating the test piece,
Molding was impossible due to poor flow, so the mold temperature was 12
It was set to 0 ° C. The results are shown in Table 1. Perprene, which is a known polyester elastomer, was inferior in compatibility with PPS, the effect of improving elongation was small and the crystallization rate was slow as compared with the examples.

[0040]

[Table 1]

[0041]

As is apparent from the above description, the PPS composition of the present invention improves the brittleness and slow crystallization rate, which are the drawbacks of the conventional PPS, and is thermally stabilized. Therefore, various problems at the time of molding process which the conventional PPS / PAG composition has are solved, and it is extremely useful for use as electric / electronic parts and automobile parts.

Claims (1)

[Claims] 1. 70 to 99.5% by weight of polyphenylene sulfide having a melt viscosity of 10 to 50,000 poise and 10 to 90 of aromatic oligoamide chain represented by the following formula (I).
% By weight, —CO—R ¹ —NH—CO—R ² —CO—NH—R ¹ —CO— (I) (wherein R ¹ and R ² are each a divalent aromatic group having 6 to 30 carbon atoms). The number average molecular weight of the polyalkylene oxide chain having a number average molecular weight of 500 to 10,000 is 90 to 10% by weight.
~ 500000 ester amide copolymer 0.5 to 30
A polyphenylene sulfide resin composition comprising 10% by weight.