JPH05209124A - Polyphenylene sulfide resin composition - Google Patents

Abstract

PURPOSE:To obtain the subject composition having high strength, large elonga tion and high impact strength, excellent toughness and processability, comprising a polyphenylene sulfide resin, an aliphatic polyester having number-average molecular weight of >=a fixed value and a specific polyalkylene glycol. CONSTITUTION:The objective composition comprises (A) 70-99.5wt.% polyphenylene sulfide resin such as poly)p-phenylene sulfide) and (B) 30-0.5wt.% total amounts of (i) an aliphatic polyester (e.g. epsilon-caprolactone) having >=10,000 number-average molecular weight fixed value and a specific polyalkylene glycol and (ii) a polyalkylene glycol of the formula (R' is X when (n) is 1 and 1-24C organic group when (n) is >=2; R is 2-6C alkylene; X is H, amino group, etc.; (m) is 2-25,000; (n) is 1-10) and having improved brittleness.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a polyphenylene sulfide resin composition, and more particularly to a polyphenylene sulfide resin composition having high strength, elongation and impact strength, excellent toughness and excellent processability. Is.

Polyphenylene sulfide has been attracting attention as a member for electric / electronic equipment and a member for automobile equipment by taking advantage of its excellent heat resistance and chemical resistance. Also injection molding,
It can be molded into various molded parts, films, sheets, fibers, etc. by extrusion molding and is widely used in fields where heat resistance and chemical resistance are required.

[0003]

2. Description of the Related Art Polyphenylene sulfide is

[0004]

[Chemical 2] And a dihaloaromatic compound and an alkali metal sulfide are heated in a polar aprotic solvent as disclosed in JP-B-45-3368. ， The method of reacting is known.

However, the polyphenylene sulfide (hereinafter abbreviated as PPS) produced by such a method has a low molecular weight and cannot be used as it is for injection molding or the like. Therefore, in order to solve these problems, P in air
US Pat. No. 3 discloses a method of increasing the molecular weight by oxidatively hardening PS.
It is disclosed in Japanese Patent No. 793256. However, this method has a problem that the PPS obtained due to an excessive oxidative crosslinking reaction by oxygen is markedly colored and only a brittle molded product can be obtained even if it is reinforced with a fiber reinforcing agent such as glass fiber. Was there.

Further, a method of linearly increasing the molecular weight by a polymerization reaction is disclosed in Japanese Patent Publication No. 52-12240. The PPS obtained by these methods has a slightly improved toughness as compared with the PPS obtained by Japanese Patent Publication No. 45-3368, but has not yet reached a sufficiently satisfactory level.

On the other hand, a method of imparting toughness by adding an elastomer to PPS is disclosed in JP-A-58-15475.
No. 7, etc. According to these methods, it is possible to improve the toughness by adding a large amount of elastomer, but it is not preferable because the heat resistance, chemical resistance and flame retardancy that PPS originally has are lost.

Further, Japanese Patent Laid-Open No. 62-45654 discloses a composition comprising PPS and an oligomeric ester having a relatively low degree of polymerization of 2 to 60 and a maximum number average molecular weight of 6000 and having rapidly enhanced crystallinity. Is disclosed.
However, this composition has the drawbacks that the effect of improving the toughness of PPS is poor and the thermal stability is poor because the molecular weight of the polyester used is low.

[0009] Further, Japanese Patent Application No. 2-21 filed previously by us.
No. 9054 describes that the toughness of PPS can be improved by adding a specific polyalkylene glycol to a specific PPS. However, although this composition has a great effect of improving the elongation, it is insufficient in improving the impact strength.

[0010]

DISCLOSURE OF THE INVENTION According to the present invention, PPS is blended with a specific aliphatic polyester and a specific polyalkylene glycol to maintain excellent properties inherent to PPS such as heat resistance, chemical resistance and flame retardancy. As it is, the present invention provides a high toughness PPS resin composition which is improved in brittleness which is a defect and is also excellent in processability.

[0011]

That is, the present invention provides a total of an aliphatic polyester having a PPS resin content of 70 to 99.5% by weight and a number average molecular weight of 10,000 or more, and a polyalkylene glycol represented by the following formula (I). Is 30-0.5% by weight

[0012]

[Chemical 3] (In the formula, R ′ is X when n = 1, and has carbon number 1 to 1 when n ≧ 2.
24 is an organic group, R is an alkylene group having 2 to 6 carbon atoms, X is hydrogen or an amino group, an epoxy group, a vinyl group,
At least 1 selected from acid anhydride group and carboxyl group
C is an organic group having 1 to 10 carbon atoms, m is 2 to 25,000, and n is an integer of 1 to 10).
Compared to a two-component composition in which PS is blended with a specific aliphatic polyester or a specific polyalkylene glycol alone,
Further, the present invention provides a three-component composition having improved elongation and impact strength and excellent moldability. The present invention will be described in detail below.

As the PPS used in the present invention, Japanese Patent Publication No.
There is no particular limitation as long as it is obtained by a known method as shown in JP-A-5-3368, but the following formula

[0014]

[Chemical 4] Those containing 70 mol% or more of the repeating unit represented by Furthermore, PPS containing 70 mol% or more of p-phenylene sulfide unit as a repeating unit is particularly preferably used. At this time, the remaining repeating unit is not limited as long as it is a copolymerizable unit. For example, o-phenylene sulfide unit, m-phenylene sulfide unit, diphenyl sulfide ether unit, diphenyl sulfide sulfone unit, diphenyl sulfide ketone unit, Examples thereof include a biphenyl sulfide unit, a naphthalene sulfide unit and a trifunctional phenylene sulfide unit. These copolymers 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.

Further, the PPS preferably used in the present invention has a melt viscosity (diameter of 0.5 m at 300 ° C.).
The value measured using a Koka type flow tester with a load of 10 kg using a die of m and a length of 2.0 mm) is 10 to 10.
0000 poise, preferably 50 to 50000 poise,
More preferably, it is a PPS in the range of 500 to 40,000 poises, whether linear or linearly crosslinked with oxygen in the presence of oxygen, or subjected to heat treatment in an inert gas atmosphere. It may be one or a mixture of these structures.

Further, in order to enhance the compatibility with the aliphatic polyester and polyalkylene glycol (hereinafter abbreviated as PAG) used in the present invention, a highly reactive functional group may be introduced into PPS. Amino groups, carboxyl groups, acid anhydride groups, epoxy groups, hydroxyl groups, etc. are suitable as the introduced functional groups, and the introduction method is a method of copolymerizing a halogenated aromatic compound containing these functional groups. And P
Examples thereof include a method of introducing by a polymer reaction of PS and a low molecular weight compound having a functional group.

Further, the PPS may be one in which sodium ions are reduced by performing deionization treatment (such as acid cleaning or hot water cleaning).

The aliphatic polyester used in the present invention has the following formula

[0020]

[Chemical 5] (Here, R is an alkylene group having 2 to 16 carbon atoms, and n
Is a linear polymer having a repeating unit of 80 to 1000), and the production method thereof is described, for example, in US Pat. No. 2,914,556, US Pat. No. 2,977,385, and US Pat. No. 3,892,821. Although it is not particularly limited as long as it is obtained by a known method such as the above, it is necessary that the number average molecular weight is 10,000 or more in order to exert the effect of the present invention.
That is, when the number average molecular weight is less than 10,000, PPS
Not only is the toughness-improving effect of 1) not sufficient, but the heat resistance decreases, so that a large amount of gas is generated during molding, which is not preferable.

Some examples of the aliphatic polyester used in the present invention include poly (β-propiolactone), polypivalolactone, poly (ε-caprolactone) and their copolymers. The aliphatic polyester preferably used in the present invention is poly (ε-caprolactone).

The PAG used in the present invention is the PAG represented by the general formula (I). As a preferred PAG, R'in the formula (I) is an organic group having 1 to 20 carbon atoms, R is an alkylene group having 2 to 4 carbon atoms, X is an amino group, an epoxy group, a vinyl group or an acid anhydride group. 1 to 1 carbon atoms
PAG having an organic group of 0, m of 2 to 25,000 and n of 1 to 6 can be mentioned. Here, there is an expression that an organic group is represented by R'and X in the formula, but this means that not only a hydrocarbon group but also a functional group containing a hetero atom such as ether, ketone, amide or sulfone is contained in R ', X. It means that it does not matter even if there is.

Some examples of the above PAG include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, bisphenol A, glycerin,
Examples thereof include addition polymers of polyhydric alcohols such as pentaerythritol and sorbitol and alkylene oxides.

Specific examples of the PAG preferably used in the present invention have a molecular weight of 500 to 1,000,000 and have polyethylene glycol or polytetramethylene glycol having an amino group, an epoxy group or an acid anhydride group at the terminal and bisphenol in the main chain. Examples thereof include polyethylene glycol and polytetramethylene glycol having the structure A and having a vinyl group at the terminal.

The total amount of the aliphatic polyester and PAG used in the present invention is 0.5 to 30% by weight, preferably 1 to 20% by weight, based on the composition of PPS, aliphatic polyester and PAG. Is.

If the amount added is less than 0.5% by weight, the effect of improving the toughness is not sufficient, whereas if it exceeds 30% by weight, the excellent properties such as heat resistance, chemical resistance and flame retardancy inherent to PPS disappear. It is not preferable because it does.

As a method for producing the PPS composition of the present invention, a method generally used can be used, but a method of melt blending with an extruder or the like is preferable.

The PPS composition obtained as described above has P
In addition to maintaining the excellent heat resistance, chemical resistance, and flame retardancy inherent to PS, it can greatly improve toughness such as elongation and impact strength, and has a low melt viscosity, so it is also excellent in molding processability. ing.

If necessary, the composition of the present invention may be supplemented with reinforcing fillers such as glass fibers, carbon fibers, ceramic fibers such as alumina fibers, aramid fibers, wholly aromatic polyester fibers, metal fibers, potassium titanate whiskers, and the like. Calcium carbonate, mica, talc, silica, barium sulfate, calcium sulfate, kaolin, clay, pyroferrite, bentonite, sericite, zeolite, nepheline sinite, attapulgite, wollastonite, PMF,
Ferrite, calcium silicate, magnesium carbonate, dolomite, antimony trioxide, zinc oxide, titanium oxide,
Magnesium oxide, iron oxide, molybdenum disulfide, graphite,
It is also possible to mix an inorganic filler such as gypsum, glass beads, glass powder, glass balloons, quartz and quartz glass, and organic and inorganic pigments.

Further, a releasing agent such as wax, a silane-based or titanate-based coupling agent, a lubricant, a heat resistance stabilizer, a weather resistance stabilizer, a foaming agent, a rust preventive agent, an ion trap agent, a flame retardant, and a flame retardant aid. You may add agents etc. as needed.

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,
Polyallyl sulfone, polyphenylene sulfide sulfone, polyether ketone, polyphenylene sulfide ketone, polyether ether ketone, polyimide, polyamide imide, silicone resin, phenoxy resin, fluorine resin and other homopolymers, random or block, one type of graft copolymer The above may be mixed and used.

[0032]

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

Reference Example A method for producing PPS used in Examples and Comparative Examples of the present invention will be described below.

N-methylpyrrolidone 11 was placed in a reactor having an internal volume of 530 l equipped with a stirrer, a dehydration tower and a jacket.
0 l and sodium sulphide (purity: Na ₂ S 60.2
61.1 kg (wt%) was charged, the mixture was heated with a jacket under stirring, and dehydrated 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, 68.7 kg of p-dichlorobenzene and 48 l of N-methylpyrrolidone were added,
After raising the temperature to 225 ° C over 2 hours and reacting at 225 ° C for 2 hours, the temperature was raised to 250 ° C over 30 minutes, and further 2
The reaction was carried out at 50 ° C for 3 hours. At this time, the pressure is 10.5k
It rose to g / cm 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.

Subsequently, 200 l of water was added to make a water slurry, which was heated and stirred at 80 ° C. for 15 minutes and then centrifuged to recover the polymer.

Further, the polymer is returned to the solvent recovery unit, and water 2 is added.
001 was added and heated and stirred at 180 ° C. for 30 minutes,
After cooling, the polymer powder was collected by a centrifuge. This operation was repeated twice.

The obtained polymer was transferred to a ribbon blender with a jacket and dried. Part of this PPS was sampled and the melt viscosity was increased to 3 using a flow tester (die; diameter = 0.5 mm, length = 2.0 mm).
It was 570 poise when measured at 00 ° C. under a load of 10 kg. After sampling, add 400 l of air under stirring
The temperature was raised to 265 ° C. and the curing treatment was performed for 24 hours while flowing at a flow rate of / hour. The melt viscosity after the completion of curing was 20000 poise. (However, diameter = 1.0 mm, length =
The melt viscosity measured using a 2.0 mm die under a load of 10 kg at 300 ° C. was 74,000 poise. ) The PPS manufactured in this manner is hereinafter abbreviated as PPS-I.

Examples 1 to 12 PPS-I obtained in Reference Example and poly (ε-caprolactone)
(PCL) (Placcel H-1 manufactured by Daicel Chemical Industries)
P, H-4, H-7) and terminal methacryl-modified polyethylene glycol (NK ester B manufactured by Shin-Nakamura Chemical Co., Ltd.)
PE-500, BPE-1300, 23G), terminal epoxy modified polyethylene glycol (manufactured by Nagase Kasei Kogyo)
Compositions shown in Table 1 are polyethylene glycol ^# 6000 diglycidyl ether), terminal amino-modified polyethylene glycol (Kawaken Fine Chemicals PEO amine ^# 6000), terminal amino-modified polytetramethylene glycol (Hodogaya Chemical Co., Ltd. PTG DA-9). After being uniformly blended with, the mixture was kneaded and extruded at 300 ° C. by an extruder to produce pellets. Using these pellets, a test piece was prepared with an injection molding machine at a cylinder temperature of 330 ° C. and a mold temperature of 140 ° C., and tensile strength and elongation were measured according to ASTM D638, and anti-notched Izod impact strength was measured according to ASTM D256. On the other hand, the molding processability (fluidity) of the composition was 300 using a Koka type flow tester (die; diameter = 1.0 mm, length = 2.0 mm).
Evaluation was performed using the melt viscosity measured at a temperature of 10 ° C. and a load of 10 kg. The results are summarized in Table 1.

Comparative Example 1 Only the PPS-I obtained in the reference example was kneaded, pelletized and injection-molded in the same manner as in Example to prepare a test piece.
Tensile strength, elongation, and anti-notch Izod impact strength were measured using the obtained test pieces, and each was 800 kg.
/ Cm ² , 10.2%, 40 kg · cm / cm.

As described above, it is understood that when the aliphatic polyester or PAG is not added, the elongation and the impact resistance are smaller than those of the examples.

Comparative Examples 2 and 3 PPS-I obtained in Reference Example and aliphatic polyester or P
AG was blended individually, kneading, pelletizing and injection molding were carried out in the same manner as in the example, and physical properties were measured using the obtained test pieces. The results are shown in Table 1, and it can be seen that the two-component system of PPS and aliphatic polyester has a higher melt viscosity and is inferior in moldability (flowability) as compared with the examples.
Further, it can be seen that in the case of the two-component system of PPS and PAG, only those having a smaller impact strength than those of the examples can be obtained.

[0043]

[Table 1]

[0044]

As is clear from the above description, the PPS
The composition comprising a specific aliphatic polyester and a specific PAG improves elongation and low impact strength, which are the drawbacks of conventional PPS, and is excellent in moldability (fluidity). It is extremely useful for use as electric / electronic parts and automobile parts.

Claims (1)

[Claims] 1. A polyphenylene sulfide resin 70-9.
9.5% by weight, the total of the aliphatic polyester having a number average molecular weight of 10,000 or more and the polyalkylene glycol represented by the following formula (I) is 30 to 0.5% by weight. (In the formula, R ′ is X when n = 1, and has carbon number 1 to 1 when n ≧ 2.
24 is an organic group, R is an alkylene group having 2 to 6 carbon atoms, X is hydrogen or an amino group, an epoxy group, a vinyl group,
At least 1 selected from acid anhydride group and carboxyl group
A polyphenylene sulfide resin composition comprising one group having 1 to 10 carbon atoms, m is 2 to 25,000, and n is an integer of 1 to 10).