JP3030464B2 - Polyphenylene sulfide resin composition - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a polyphenylene sulfide resin composition, and more particularly, to a polyphenylene sulfide resin composition having a remarkably high crystallization rate.

Polyphenylene sulfide has attracted attention as a member of electric / electronic equipment and a member of automobile equipment by utilizing its excellent heat resistance and chemical resistance.

Further, it can be molded into various molded parts, films, sheets, fibers and the like by injection molding, extrusion molding and the like, and is widely used in fields requiring heat resistance and chemical resistance.

[Prior Art] As disclosed in Japanese Patent Publication No. 45-3368, polyphenylene sulfide is prepared by combining a dihalo aromatic compound with an alkali metal sulfide such as sodium sulfide in a polar aprotic solvent such as N-methylpyrrolidone. Is obtained by reacting

However, polyphenylene sulfide obtained by this method, in particular, poly (p-phenylene sulfide) (hereinafter abbreviated as PPS) which is crystalline has a glass transition temperature of about 90%.
° C, and the crystallization speed is slow, so when trying to obtain a molded product in injection molding, the mold temperature should be 130-150.
Unless set to ° C., good products having excellent heat resistance and dimensional stability could not be obtained. This is a major drawback of PPS in the molding process compared to the fact that other general-purpose engineering plastics, such as nylon and PBT, can be molded at a mold temperature of 100 ° C. or less, and is considered to be a hindrance factor in expanding the use of PPS.

In order to solve this problem, as a prior art, an oligomeric ester having a maximum molecular weight of 6000 is added to PPS having a melt viscosity of at least 5 Pa · S (JP-A-62-45654). (Japanese Unexamined Patent Publication No. Sho 62-230848), adding another thioether (Japanese Unexamined Patent Publication No. Sho 62-230849), and adding a specific aromatic phosphate ester (Japanese Unexamined Patent Publication No. Sho 62-230850). And JP-A-1-225660). However, in any of the methods, the heat resistance of the additive is poor, so that evaporative gas or decomposition gas is generated at the time of molding, or the additive has a low molecular weight, and migrates to the surface of the molded product, and the additive causes the surface of the molded product to be removed. There were problems such as contamination.

[Problems to be Solved by the Invention] The present invention solves the above-mentioned conventional drawbacks by blending a specific polyalkylene glycol with PPS, and sufficiently crystallizes even in a low-temperature mold in which the crystallization rate is remarkably increased. The present invention provides a PPS resin composition to be obtained.

[Means for Solving the Problems] Specifically, the present invention, PPS resin 70 to 95 wt%, the polyalkylene glycol represented by the following formula (I) 30 to 5 _{wt% RO-R 'm O-} X] n (I Wherein R is X when n = 1, an organic group having 1 to 6 carbon atoms when n ≧ 2, R ′ is an alkylene group having 2 to 6 carbon atoms, X is an epoxy group, an acid anhydride An organic group having 1 to 10 carbon atoms containing at least one of a group and a carboxyl group, or hydrogen;
m represents an integer of from 5 to 25000, and n represents an integer of from 1 to 10.) The following is a detailed description of the polyphenylene sulfide resin composition.

The PPS used in the present invention is not particularly limited as long as it is obtained by a known method as shown in JP-B-45-3368. 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, an orthophenylene sulfide unit, a metaphenylene 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) and poly (p-phenylene sulfide)-
Poly (m-phenylene sulfide) block copolymer,
Examples thereof include a poly (p-phenylene sulfide) -polysulfone block copolymer and a poly (p-phenylene sulfide) -polyphenylene sulfide sulfone copolymer.

Further, the PPS preferably used in the present invention has a melt viscosity (a value measured using a die having a diameter of 0.5 mm and a length of 2 mm at 300 ° C. under a load of 10 kg using a Koka type flow tester) of 10 to 100,000. Poise, preferably PPS in the range of 50 to 50,000 poise, whether linear or crosslinked with oxygen in the presence of oxygen, and subjected to heat treatment in an inert gas atmosphere. Or a mixture of these structures.

Further, in order to enhance the compatibility with the polyalkylene glycol used in the present invention, a highly reactive functional group may be introduced into PPS. As the functional group to be introduced, an amino group, a carboxylic acid group, a hydroxyl group, an acid anhydride group, an epoxy group, and the like are suitable. As a method for introducing the functional group, a halogenated aromatic compound containing these functional groups is copolymerized. Ways and PPS
And a low molecular weight compound having a functional group.

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

The polyalkylene glycol used in the present invention is a polyalkylene glycol represented by the general formula (I). As a preferred polyalkylene glycol for use in the present invention, R in the formula is an organic group having 1 to 9 carbon atoms having an epoxy group, a carboxyl group or an acid anhydride group;
R 'is an alkylene group having 2 to 4 carbon atoms, X is an epoxy group,
An organic group having 1 to 9 carbon atoms or a hydrogen having a carboxyl group or an acid anhydride group or hydrogen, a polyalkylene glycol having m of 10 to 15,000 and n of 1 to 5 can be mentioned. Where
There is an expression of an organic group for R and X, which means not only a hydrocarbon group but also an ether, ketone, amide,
It means that a hetero atom-containing functional group such as sulfone may be included. Also, m in the formula indicates the degree of polymerization of the polyalkylene glycol segment. If m is less than 5, heat resistance is poor and a large amount of gas is generated during molding, which is not preferable. On the other hand, m
Is greater than 25000, polyalkylene glycol and P
This is not preferable because the compatibility of PS is reduced and the effect of increasing the crystallization rate is reduced.

Some examples of the above polyalkylene glycols include addition polymers of polyhydric alcohols such as polyethylene glycol, polypropylene glycol, polytetramethylene glycol, glycerin, pentaerythritol, sorbitol and alkylene oxide.

Further, an epoxy group or an acid anhydride group can be introduced into the polyalkylene glycol by utilizing the reactivity of the terminal hydroxyl group of the polyalkylene glycol. For example, an epoxy-modified polyalkylene glycol can be obtained by reacting epichlorohydrin, and an acid anhydride-modified polyalkylene glycol can be obtained by reacting trimellitic anhydride chloride.

Specific examples of the polyalkylene glycol preferably used in the present invention include polyethylene glycol and polytetramethylene glycol having a molecular weight of 300 to 100,000,000 and having a terminal functional group of a hydroxyl group, an epoxy group, a carboxyl group or an acid anhydride group. Can be

The addition amount of the polyalkylene glycol used in the present invention is 5 to 30% by weight based on the composition of PPS and the polyalkylene glycol. When the addition amount is less than 5% by weight, the effect of increasing the crystallization rate is reduced. Therefore, it is not preferable.
On the other hand, if it exceeds 30% by weight, further improvement of the crystallization rate cannot be recognized, and furthermore, physical properties decrease, which is not preferable.

As a method for producing the PPS / polyalkylene glycol 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.

When a nucleating agent is used in combination with the composition of the present invention, the crystallization rate is further increased. Therefore, the addition of an appropriate amount of the nucleating agent is not essential, but gives a favorable result. Crystal nucleating agents include silica, carion, talc, hydrotalcite,
In addition to inorganic substances such as wollastonite and boron nitride, organic carboxylic acids such as calcium stearate, aluminum stearate, dipotassium succinate, calcium benzoate, disodium phthalate, trisodium trimellitate, tetrapotassium pyromellitate, etc. Polymers with a higher melting point than PPS, such as metal salts, polyphenylene sulfide ketone, and nylon 46 are effective. The amount of these nucleating agents is 0.05 to 10% by weight, preferably 0.1 to 5% by weight, based on the PPS composition of the present invention.

Since the crystallization rate of the PPS resin composition obtained as described above is significantly higher than that of conventional PPS, a molded article excellent in heat resistance can be sufficiently crystallized by injection molding even when using a low-temperature mold. Obtainable.

The above composition, if necessary, glass fiber, carbon fiber, ceramic fiber such as alumina fiber, aramid fiber,
Reinforcing fillers such as wholly aromatic polyester fibers, metal fibers, potassium titanate whiskers, 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, Inorganic fillers such as gypsum, glass beads, glass powder, glass balloon, quartz, quartz glass, and organic and inorganic pigments can also be blended.

As the glass fiber, for example, a chopped strand having a fiber length of 1.5 to 12 mm and a fiber diameter of 3 to 24 μm, a fiber diameter of 3 to 8 μm
m milled fiber, glass flakes and glass powder of 325 mesh or less.

Also, plasticizers and release agents such as aromatic hydroxy derivatives, silane-based and titanate-based coupling agents, lubricants,
A heat stabilizer, a weather resistance stabilizer, a foaming agent, a rust inhibitor, an ion trapping agent, a flame retardant, a flame retardant auxiliary, and the like may be added as necessary.

Further, it is also possible to add a small amount of another polymer to the resin composition of the present invention to impart other physical properties. As the polymer to be added, for example, polyethylene, polybutadiene,
Polyisoprene, polychloroprene, polybutene, polystyrene, poly α-methylstyrene, nylon 6, nylon 66, nylon 610, ninelon 12, nylon 11, nylon 4
6, such as polyamide resins, polyester resins such as polyethylene terephthalate, polybutylene terephthalate, and polyarylate, polyvinyl acetate, polyvinyl chloride, polyacrylate, polymethacrylate, polyacrylonitrile, polyurethane, polyacetal, polyphenylene oxide, Homopolymers such as polycarbonate, polysulfone, polyether sulfone, polyallyl sulfone, polyphenylene sulfide sulfone, polyether ketone, polyether ether ketone, polyphenylene sulfide ketone, polyimide, polyamide imide, silicone resin, phenoxy resin, and fluororesin, random or Examples include block, graft copolymers, mixtures thereof, and modified products thereof.

[Examples] Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited to these examples.

The crystallization rate of the PPS resin composition used in the following examples was determined by using an amorphous sample obtained by quenching a molten sample, and increasing the temperature by DSC at a rate of 10 ° C./min. The evaluation was performed by measuring the crystallization rate at the time of the above.

Reference Example The production method of PPS used in Examples of the present invention and Comparative Examples is shown below.

Reference Example 1 0.60 mol of sodium sulfide (Na ₂ S · 2.9H ₂ O) and 150 g of N-methyl-2-pyrrolidone (hereinafter abbreviated as NMP) were added to an autoclave equipped with a stirrer and having a capacity of 500 ml, and stirred under a nitrogen stream. The temperature was raised to 200 ° C., and 21.2 g of a distillate mainly composed of water was distilled off. After cooling the system to 170 ° C., 0.60 mol of p-dichlorobenzene (hereinafter abbreviated as p-DCB) was added to NMP50.
g, add the system under a nitriding gas flow, raise the temperature to 250
Polymerization was carried out at ℃ for 3 hours. After the polymerization, cool the system,
After the content was poured into water to precipitate the polymer, the precipitated polymer was collected by a glass funnel, washed with about 5 warm water, filtered repeatedly, and heated and vacuum-dried overnight to isolate the polymer. The obtained polymer was 61.5 g, yield 95%,
The melt viscosity (value measured with a Koka flow tester at 300 ° C using a die with a diameter of 0.5 mm and a length of 2 mm at a load of 10 kg) is
250 poise. This polymer was placed in an oven set at 250 ° C. in the air and cured for 5 hours to obtain PPS having a melt viscosity of 2800 poise. The PPS thus obtained is referred to as PPS-I.

Reference Example 2 In Example 1, p-DCB was used instead of 0.60 mol of p-DCB.
The same operation as in Reference Example 1 was performed except that 0.594 mol and 0.006 mol of 3,5-dichloroaniline were used. The obtained polymer was 61.2 g and the yield was 94%, and the melt viscosities before and after curing were 120 poise and 3300 poise, respectively. The PPS thus obtained is referred to as PPS-II.

Reference Example 3 The same operation as in Reference Example 2 was performed, except that 0.006 mol of 2,4-dichlorobenzoic acid was used instead of 0.006 mol of 3,5-dichloroaniline in Reference Example 2. The resulting polymer is 6
The melt viscosity before and after curing was 240 poise and 2600 poise, respectively. The PPS thus obtained is referred to as PPS-III.

Reference Example 4 The same operation as in Reference Example 2 was performed except that 0.006 mol of 2,4-dichlorophenol was used instead of 0.006 mol of 3,5-dichloroaniline in Reference Example 2. The resulting polymer is
The yield was 60.7 g, the yield was 93%, and the melt viscosities before and after curing were 110 poise and 3400 poise, respectively. The PPS thus obtained is designated as PPS-IV.

Examples 1 to 7 PPS obtained in Reference Examples 1 to 4 and polyethylene glycol (average molecular weight 2000, abbreviated as PEG-I), α, ω-diglycidyl polyethylene glycol (Epolite 400E; manufactured by Kyoeisha Oil & Fats, average molecular weight 400, PEG) -II) and one kind selected from polytetramethylene glycol (PTG1000; manufactured by Hodogaya Chemical Co., Ltd., average molecular weight: 1,000, abbreviated as PTMG-I) with the composition shown in Table 1 and then uniformly blended. (Toyo Seiki Co., Ltd.) and melt-kneaded at 300 ° C. for 10 minutes.
10 mg of the kneaded sample is weighed and placed in a DSC measurement pan.
Glass transition temperature (Tg), crystallization temperature (Tc), and melting point (Tm) were measured by SC. The results are summarized in Table 1.

Example 8 95 parts by weight of PPS, 5 parts by weight of PEG-I, and 67 parts by weight of glass fiber (chopped strand having a cut length of 3 mm) obtained in Reference Example 3 were mixed in a V-blender, then kneaded and extruded by an extruder. Pellets were produced. Next, a test piece was prepared using an injection molding machine at a cylinder temperature of 310 ° C. and a mold temperature of 80 ° C., and the heat distortion temperature (18.6 kg / cm ² ) was measured according to ASTM D648. As is apparent from the results, by adding polyethylene glycol, a molded article having excellent heat resistance can be obtained even if a low-temperature mold having a mold temperature of 80 ° C. is used.

Comparative Examples 1-4 Only the PPS obtained in Reference Examples 1-4 was melt-kneaded in the same manner as in the Examples, and then Tg, Tc, and Tm were measured by DSC. In each case, only those having a higher crystallization temperature and a lower crystallization rate than those of the examples were obtained. (See Table 1) Comparative Examples 5, 6 PPS-II and one selected from ethylene glycol diglycidyl ether (abbreviated as EG-I) and tetramethylene glycol diglycidyl ether (abbreviated as TMG-I) were used as examples. When melt-kneaded under the same conditions, a large amount of gas was generated, and the sample significantly foamed. When Tc was measured by DSC, the PPS / EG-I blend was 108 ° C, PPS / TMG
Although the crystallization temperature of the -I blend was reduced to 111 ° C, generation of gas during the melt-kneading process was remarkably impractical. Comparative Example 7 Comparative Example 7 Except that 95 parts by weight of PPS obtained in Reference Example 3 and 100 parts by weight of PPS obtained in Reference Example 3 were used instead of 5 parts by weight of PEG-I,
A test piece was prepared in the same manner as in Example 8, and the heat distortion temperature (18.6 kg / cm ² ) was measured in accordance with ASTM D648.
Met. This value is remarkably lower than that of Example 8, and shows that only a material having poor heat resistance can be obtained without adding polyethynylene glycol.

[Effects of the Invention] As is clear from the above description, according to the present invention, a PPS composition having a remarkably high crystallization rate can be obtained, and a molded article sufficiently crystallized even in injection molding using a low-temperature mold. Not only can be obtained, but also the workability such as insert molding can be remarkably improved.

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Claims (1)

(57) [Claims] 1. A polyphenylene sulfide resin 70 to 95 wt%, the polyalkylene glycol 30-5 _{wt% RO-R 'm O-} X] n (I) ( wherein R represented by the following formula (I), n When X = 1, X is an organic group having 1 to 6 carbon atoms when n ≧ 2, R ′ is an alkylene group having 2 to 6 carbon atoms, X is at least one of an epoxy group, an acid anhydride group, and a carboxyl group. Is an organic group having 1 to 10 carbon atoms or hydrogen,
m represents 5 to 25000 and n represents an integer of 1 to 10).