JP3109223B2 - Polyphenylene sulfide resin composition - Google Patents

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 resin composition having high strength, elongation and impact strength, excellent toughness and excellent workability. It is.

[0002] Polyphenylene sulfide has attracted attention as a member for electric and electronic devices and a member for automobile devices by utilizing its excellent heat resistance and chemical resistance. Injection molding,
It can be formed into various molded parts, films, sheets, fibers, etc. by extrusion and the like, and is widely used in fields requiring heat resistance and chemical resistance.

[0003]

2. Description of the Related Art Polyphenylene sulfide

[0004]

Embedded image Is a polymer having a main structural unit, and a method for producing the same is to heat a dihalo aromatic compound and an alkali metal sulfide in a polar aprotic solvent as disclosed in Japanese Patent Publication No. 45-3368. , A method of reacting is known.

[0005] However, polyphenylene sulfide (hereinafter abbreviated as PPS) produced by such a method has a low molecular weight and cannot be used for injection molding or the like as it is. Therefore, to solve these problems, P
US Patent No. 3 discloses a method of oxidatively curing PS to increase the molecular weight.
No. 793256, for example. However, in this method, PPS obtained due to excessive oxidative cross-linking reaction due to oxygen is remarkably colored, and even if reinforced with a fiber reinforcing agent such as glass fiber, only a brittle molded product is obtained. I was

A method for increasing the molecular weight into a linear form by a polymerization reaction is disclosed in Japanese Patent Publication No. 52-12240. Although the PPS obtained by these methods is somewhat improved in toughness as compared with the PPS obtained by Japanese Patent Publication No. 45-3368, it 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, for example. According to these methods, the toughness can be improved by adding a large amount of the elastomer, but it is not preferable because the heat resistance, chemical resistance and flame retardancy inherent to PPS are lost.

JP-A-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, wherein the crystallinity is rapidly enhanced. Is disclosed.
However, this composition has a drawback that the molecular weight of the polyester used is low, so that the effect of improving the toughness of PPS is poor and the thermal stability is poor.

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

[0010]

SUMMARY OF THE INVENTION According to the present invention, a specific aliphatic polyester and a specific polyalkylene glycol are blended with PPS to maintain excellent properties such as heat resistance, chemical resistance, and flame retardancy inherent in PPS. It is an object of the present invention to provide a high toughness PPS resin composition which has improved brittleness, which is a drawback, and has excellent workability.

[0011]

That is, the present invention relates to a method of preparing a polyalkylene glycol represented by the following formula (I) and 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. Is 30 to 0.5% by weight

[0012]

Embedded image (Wherein R ′ is X when n = 1, and carbon number 1 when n ≧ 2)
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 one selected from an acid anhydride group and a carboxyl group
A group having 1 to 10 carbon atoms, m represents 2 to 25,000, and n represents an integer of 1 to 10).
Compared to a two-component composition in which a specific aliphatic polyester or a specific polyalkylene glycol is solely blended with PS,
Further, the present invention provides a three-component composition having improved elongation and impact strength and excellent moldability. Hereinafter, the present invention will be described in detail.

As the PPS used in the present invention, Japanese Patent Publication No. Sho 4
There is no particular limitation as long as it is obtained by a known method as shown in JP-A-5-3368.

[0014]

Embedded image Those containing 70 mol% or more of the repeating unit represented by are preferred. Further, PPS containing a p-phenylene sulfide unit as a repeating unit in an amount of 70 mol% or more 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 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 copolymer, and poly (p-phenylene sulfide) -polysulfone block copolymer. Polymers include poly (p-phenylene sulfide) -polyphenylene sulfide sulfone copolymer.

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

In order to increase the compatibility with the aliphatic polyester or polyalkylene glycol (hereinafter abbreviated as PAG) used in the present invention, a highly reactive functional group may be introduced into PPS. As the functional group to be introduced, amino group, carboxyl group, acid anhydride group, epoxy group, hydroxyl group and the like are suitable. As a method for introducing, a method of copolymerizing a halogenated aromatic compound containing these functional groups is preferable. And P
A method of introducing by a high molecular reaction between PS and a low molecular weight compound containing a functional group may be used.

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

The aliphatic polyester used in the present invention is represented by the following formula:

[0020]

Embedded image (Where R is an alkylene group having 2 to 16 carbon atoms, n
Is an integer of from 80 to 1000), and is a substantially linear polymer having a repeating unit of, for example, US Pat. No. 2,914,556, US Pat. No. 2,977,385, US Pat. No. 3,892,821. There is no particular limitation as long as it is obtained by a known method such as that described above, but it is necessary that the number average molecular weight is 10,000 or more in order to exert the effects of the present invention.
That is, when the number average molecular weight is less than 10,000, PPS
Not only is the effect of improving the toughness of the steel sheet insufficient, but also the heat resistance is lowered, such that a large amount of gas is generated at the time of molding.

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

The PAG used in the present invention is a PAG represented by the general formula (I). As preferred PAGs, R 'in the formula (I) contains an organic group having 1 to 20 carbon atoms, R represents an alkylene group having 2 to 4 carbon atoms, and X represents an amino group, an epoxy group, a vinyl group or an acid anhydride group. 1 to 1 carbon atoms
PAG wherein 0 is an organic group, m is 2 to 25,000, and n is 1 to 6. Here, R 'and X in the formula are referred to as organic groups, which include not only a hydrocarbon group but also a heteroatom-containing functional group such as ether, ketone, amide and sulfone in R' and X. It means that even if you can do it.

Some examples of the above PAG include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, bisphenol A, glycerin,
An addition polymer of a polyhydric alcohol such as pentaerythritol and sorbitol and an alkylene oxide is exemplified.

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

If the amount is less than 0.5% by weight, the effect of improving toughness is not sufficient, and if it exceeds 30% by weight, excellent properties such as heat resistance, chemical resistance and flame retardancy inherent in PPS disappear. Is not preferred.

As a method for producing the PPS composition of the present invention, a commonly used method 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 a 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 also has low melt viscosity, so it has excellent moldability. ing.

If necessary, the composition of the present invention may contain a reinforcing filler such as glass fiber, carbon fiber, ceramic fiber such as alumina fiber, aramid fiber, wholly aromatic polyester fiber, metal fiber, and potassium titanate whisker. Calcium carbonate, mica, talc, silica, barium sulfate, calcium sulfate, kaolin, clay, pyroferrite, bentonite, sericite, zeolite, nepheline cinite, 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 inorganic fillers such as gypsum, glass beads, glass powder, glass balloons, quartz and quartz glass, and organic and inorganic pigments.

Also, a release agent such as wax, a silane-based or titanate-based coupling agent, a lubricant, a heat-resistant stabilizer, a weather-resistant stabilizer, a foaming agent, a rust inhibitor, an ion trapping agent, a flame retardant, and a flame retardant assistant. Agents and the like may be added as necessary.

If necessary, polyethylene, polybutadiene, polyisoprene, polychloroprene, polystyrene, polybutene, polyα-methylstyrene, polyvinyl acetate, polyvinyl chloride, polyacrylate, polymethacrylate, polyacrylonitrile, Polyamides such as nylon 6, nylon 66, nylon 610, nylon 12, nylon 11, nylon 46, polyesters such as polyethylene terephthalate, polybutylene terephthalate, and polyarylate, polyurethane, polyacetal, polycarbonate, polyphenylene oxide, polysulfone, polyether sulfone,
One kind of homopolymer, random or block, graft copolymer of polyallyl sulfone, polyphenylene sulfide sulfone, polyether ketone, polyphenylene sulfide ketone, polyether ether ketone, polyimide, polyamide imide, silicone resin, phenoxy resin, fluororesin, etc. The above may be used in combination.

[0032]

EXAMPLES The present invention will be described below in detail 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 is described below.

N-methylpyrrolidone 11 was added to a 530-liter reactor equipped with a stirrer, dehydration tower and jacket.
0 l and sodium sulfide (purity: Na ₂ S 60.2
(Weight%), heated by a jacket under stirring, and dehydrated through a dehydration column until the internal temperature reached about 200 ° C. At this time, 13.5 l of a distillate mainly composed of water was distilled off. Next, 68.7 kg of p-dichlorobenzene and 48 l of N-methylpyrrolidone were added,
The temperature was raised to 225 ° C. over 2 hours, and reacted at 225 ° C. for 2 hours. Then, the temperature was raised to 250 ° C. over 30 minutes.
The reaction was performed at 50 ° C. for 3 hours. At this time, the pressure is 10.5k
g / cm ² .

After the completion of the reaction, the reaction mixture was transferred to a solvent recovery device equipped with a stirrer, a jacket and a vacuum line.
At this time, 30 l of N-methylpyrrolidone was added. Subsequently, the mixture 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 form a water slurry, which was heated and stirred at 80 ° C. for 15 minutes, and then centrifuged to recover a polymer.

Further, the polymer was returned to the solvent recovery device, and water 2
00l was added, and the mixture was heated and stirred at 180 ° C for 30 minutes.
After cooling, the polymer powder was recovered with 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 measured using a Koka type 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 is completed, 400 l of air is stirred.
The temperature was raised to 265 ° C. while flowing at a flow rate of / hour, and curing treatment was performed for 24 hours. The melt viscosity after curing was 20,000 poise. (However, diameter = 1.0 mm, length =
The melt viscosity measured at 300 ° C. under a load of 10 kg using a 2.0 mm die was 74000 poise. ) The PPS thus manufactured 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, Ltd.)
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)
The composition shown in Table 1 is polyethylene glycol ^# 6000 diglycidyl ether), terminal amino-modified polyethylene glycol (PEO amine ^# 6000 manufactured by Kawaken Fine Chemical), and terminal amino-modified polytetramethylene glycol (PTG DA-9 manufactured by Hodogaya Chemical Industry). And then kneaded and extruded at 300 ° C. with an extruder to produce pellets. Using the pellets, test pieces were prepared at a cylinder temperature of 330 ° C. and a mold temperature of 140 ° C. using an injection molding machine, 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 moldability (flowability) of the composition was 300 using a Koka type flow tester (die; diameter = 1.0 mm, length = 2.0 mm).
The evaluation was performed using the melt viscosity measured at 10 ° C. and a load of 10 kg. The results are summarized in Table 1.

Comparative Example 1 A test piece was prepared by kneading and pelletizing only the PPS-I obtained in the reference example in the same manner as in the example and performing injection molding.
The tensile strength, elongation and anti-notched Izod impact strength of the obtained test piece were measured, and each was 800 kg.
/ Cm ² , 10.2%, 40 kg · cm / cm.

As described above, it can be seen that when no aliphatic polyester or PAG is added, elongation and impact resistance are smaller than those of the examples.

Comparative Examples 2 and 3 The PPS-I obtained in the Reference Example and the aliphatic polyester or P
AG was independently compounded, kneaded, pelletized, and injection-molded in the same manner as in the examples, 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 (fluidity) as compared with the examples.
In addition, it can be seen that in the two-component system of PPS and PAG, only one having a lower impact strength than that of the example can be obtained.

[0043]

[Table 1]

[0044]

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

Claims (1)

(57) [Claims] 1. A polyphenylene sulfide resin 70 to 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. (Wherein R ′ is X when n = 1, and carbon number 1 when n ≧ 2)
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 one selected from an acid anhydride group and a carboxyl group
A polyphenylene sulfide resin composition comprising 1 to 10 carbon atoms, wherein m is 2 to 25,000, and n is an integer of 1 to 10, respectively.