JP3034573B2 - 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 and electronic devices and a member of automobile devices by utilizing its excellent heat resistance and chemical resistance. Further, it can be formed 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] Polyphenylene sulfide can be obtained by heating and reacting a dihalo aromatic compound and an alkali metal sulfide as disclosed in JP-B-45-3368 in a polar aprotic solvent.

However, polyphenylene sulfide produced by this method, particularly poly (p-phenylene sulfide) (hereinafter abbreviated as PPS) which is crystalline, has a glass transition temperature of about 9%.
0 ° C. is relatively high, and the crystallization speed is slow.
Unless set at 50 ° C, good products with excellent heat resistance and dimensional stability could not be obtained. This means that compared to other general-purpose engineering plastics, such as nylon and PBT, which can be molded at a mold temperature of 100 ° C or less, the PPS on the molding process
This is a major drawback of PPS, and is considered to be a hindrance to 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 improves the above-mentioned conventional disadvantages by blending a specific polyalkylene glycol with a specific PPS,
It is still another object of the present invention to provide a PPS resin composition that can sufficiently crystallize even in a low-temperature mold having a remarkably increased crystallization rate.

[Means for Solving the Problems] That is, the present invention relates to a PPS resin of 10 to 50,000 poise, 70 to 99.5% by weight, a polyalkylene glycol represented by the general formula (I) and / or (II) 30 to 0.5% by weight RO _{-R 1 m O-X] n} (I) X-OR 1 -O m R 2 OR 1 m p O-X (II) ( wherein R is, X when n = 1, the of n ≧ 2 Is an organic group having 1 to 6 carbon atoms, R ₁ is an alkylene group having 2 to 6 carbon atoms, R ₂ is an organic group having 1 to 24 carbon atoms, X is an epoxy group, an acid anhydride group, a carboxyl group, vinyl An organic group having 1 to 10 carbon atoms or hydrogen containing at least one of the groups, m is 5 to 25,000,
n represents an integer of 1 to 10 and p represents an integer of 2 to 100), and at least one selected from the group consisting of talc, silica, kaolin, and hydrotalcite having an average particle size of 4 μm or less.
The present invention relates to a polyphenylene sulfide resin composition containing 0.1 to 2 parts by weight of a different type of crystal nucleating agent.

 Hereinafter, the details will be described.

The PPS used in the present invention is not particularly limited as long as it has a melt viscosity of 10 to 50,000 poise, and can be obtained by a known method such as Japanese Patent Publication No. 45-3368. The one containing 70 mol% or more, more preferably 90 mol% or more of the repeating unit represented by is preferred. Further, 70 mol% of p-phenylene sulfide unit was used as a repeating unit.
The PPS contained above is particularly preferably used. The remaining repeating unit is not limited as long as it is a copolymerizable unit. For example, orthophenylene sulfide unit, metaphenylene sulfide unit, diphenyl sulfide ether unit, diphenyl sulfide sulfone unit, diphenyl sulfide ketone unit, biphenyl sulfide unit, Examples include 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,
Poly (p-phenylene sulfide) -polysulfone block copolymer, poly (p-phenylene sulfide)-
And polyphenylene sulfide sulfone copolymer.

Further, the melt viscosity of the PPS used in the present invention,
Koka type flow tester (die: 0.5mm inside diameter, 2.0mm length)
The value measured at 300 ° C. using a load of 10 kg) is in the range of 10 to 50,000 poise, preferably 50 to 30,000 poise.

Further, the PPS may be a linear one, an oxygen-crosslinked one in the presence of oxygen, or an overheat-treated one under an inert gas atmosphere. It may be a mixture of structures.

In order to increase 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) or (II). As a preferred polyalkylene glycol used 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, and R ₁ is an alkylene group having 2 to 4 carbon atoms. , R ₂ is an organic group having 1 to 15 carbon atoms, X is an organic group having 1 to 9 having an epoxy group, a carboxyl group or an acid anhydride group, and m is 10 to 1500.
0, n is 1 to 5, and p is 3 to 50. Here, R, R ₂ , and X in the formula are referred to as organic groups, which are not only hydrocarbon groups, but also organic groups.
It means that R, R ₂ and X may contain a heteroatom-containing functional group such as ether, ketone, amide and sulfone. 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, if m is larger than 25,000, the compatibility between the polyalkylene glycol and PPS is reduced, and the effect of increasing the crystallization rate is undesirably 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 0.5 to 30% by weight, preferably 1 to 20% by weight, based on the composition of the PPS and the polyalkylene glycol. If the amount is less than 0.5% by weight, the effect of increasing the crystallization rate is reduced, which is not preferable. On the other hand, 30
If the content is more than 10% by weight, further improvement of the crystallization rate cannot be recognized, and furthermore, physical properties are deteriorated.

The nucleating agent used in the present invention is talc, silica, kaolin or hydrotalcite having an average particle size of 4 μm or less. By combining these nucleating agents with a specific polyalkylene glycol, it became possible to remarkably accelerate the crystallization of PPS.

It is important that the nucleating agent used in the present invention has an average particle size of 4 μm or less, and if the average particle size exceeds 4 μm, it is necessary to add a large amount of the nucleating agent to promote crystallization, It is not preferable because physical properties are deteriorated. The particle size of the crystal nucleating agent more preferably used is 2 μm or less.

The amount of these nucleating agents added to the PPS / polyalkylene glycol composition is usually 0.1 to 2 parts by weight, preferably 0.2 to 1 part by weight, per 100 parts by weight of the PPS / polyalkylene glycol composition. If the addition amount is less than 0.1 part by weight, the effect as a nucleating agent is not sufficient.
If the amount is more than 10 parts by weight, further improvement of the crystallization speed cannot be recognized, and furthermore, physical properties are deteriorated.

There is no problem even if two or more types of nucleating agents are used in the present invention.

As a method for producing the PPS / polyalkylene glycol / crystal nucleating agent 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.

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 crystal nucleating agent, 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, nylon 12, nylon 11, nylon 46
Polyamide resins such as polyethylene terephthalate,
Polyester resins such as polybutylene terephthalate and polyarylate, polyvinyl acetate, polyvinyl chloride, polyacrylate, polymethacrylate, polyacrylonitrile, polyurethane, polyacetal,
Homopolymers such as polyphenylene oxide, 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 block, a graft copolymer, a mixture thereof, or a modified product 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 melt viscosity of PPS is measured using a Koka type flow tester (die:
The measurement was performed at 300 ° C. using an inner diameter of 0.5 mm, a length of 2.0 mm, and a load of 10 kg).

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 N was added to an autoclave with an internal volume of 500 ml equipped with a stirrer.
- (hereinafter referred to as NMP) methyl-2-pyrrolidone 150g and sodium sulfide _{(Na 2 S · 2.9H 2 O} ) 0.60 mol was added, and stirred under a nitrogen gas stream temperature was raised to 200 ° C., distillate consisting mainly of water 21.2 g of a liquid was distilled off. After cooling the system to 170 ° C, p-
0.60 mol of dichlorobenzene (hereinafter abbreviated as p-DCB) is NMP
Add with 50g, enclose the system under a nitrogen stream, raise the temperature to 2
Polymerization was performed at 50 ° C. for 3 hours. After the polymerization, the system was cooled, the content was poured into water, and the polymer was precipitated.The precipitated polymer was collected with a glass funnel, washed with about 5 liters of warm water, filtered repeatedly, and heated and dried overnight under vacuum. To isolate the polymer. The obtained polymer was 61.5 g, the yield was 95%, and the melt viscosity was 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 3,5-aminochlorobenzene 0.006 mol were used. The obtained polymer was 61.4 g and the yield was 95%. The melt viscosities before and after curing were 180 poise and 3150 poise, respectively. The PPS thus obtained is referred to as PPS-II.

Reference Example 3 200 g of α-ω-diglycidyl polyethylene glycol (Epolite 400E; manufactured by Kyoeisha Oil & Fat Co., Ltd., average molecular weight 400) and 107 g of bisphenol A were heated and stirred at 200 ° C. for 2 hours using a separable flask under a nitrogen stream. Then, after cooling to room temperature, the mixture was added dropwise to a large amount of diethyl ether to remove excess bisphenol A, and dried at room temperature for 24 hours to give a terminal epoxy group-containing polyethylene glycol having a molecular weight of 12000 [general formula (II) type]. Obtained. this
Abbreviated as PEG-III.

Examples 1 to 8 PPS obtained in Reference Examples 1 and 2 and polyethylene glycol [general formula (I) type] (average molecular weight: 2,000, abbreviated as PEG-I), α-ω-diglycidyl polyethylene glycol [general formula (I ) Type] (Epolite 400E; manufactured by Kyoeisha Oil & Fat Co., Ltd., average molecular weight 400, abbreviated as PEG-II), P obtained in Reference Example 3
EG-III, polytetramethylene glycol [general formula (I) type] (PTG1000; manufactured by Hodogaya Chemical, average molecular weight 10
00, abbreviated as PTMG-I) and talc (Microace P-4; manufactured by Nippon Talc, average particle size 1.5 μm, abbreviated as talc-I), silica (Nip Seal E-220A; manufactured by Nippon Silica Industry) , Average particle size 1.4μm), kaolin (ASP-10
0; Tsuchiya Kaolin Industries, average particle size 1.3 μm), hydrotalcite (KW-2000; Kyowa Chemical Industry, average particle size 1.0 μm)
m) and one of them is uniformly blended with the composition shown in Table 1, and then using a Labo Plast Mill (manufactured by Toyo Seiki).
The mixture was melt-kneaded at 300 ° C. for 10 minutes. 10mg of sample after kneading
It was weighed and placed in a DSC measurement pan, and the Gatas transition temperature (Tg), crystallization temperature (Tc), and melting point (Tm) were measured by DSC. The results are summarized in Table 1.

Example 9 95 parts by weight of PPS, 5 parts by weight of PEG-I, 1 part by weight of talc-I, and 67 parts by weight of glass fiber (chopped strand having a cut length of 3 mm) obtained in Reference Example 2 were mixed in a V-blender and then extruded. And extruded to produce pellets. 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 and 2 Only the PPS obtained in Reference Examples 1 and 2 were 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. Comparative Example 3 Melting and kneading in the same manner as in Example except that only two components of PPS-II and PEG-II were used and no nucleating agent was used, and then Tg, Tc, Tm by DSC. Was measured. Tg, T compared to PPS alone
Although a decrease in c was observed, both Tg and Tc were higher than those in the example in which the nucleating agent was added, indicating that the crystallization rate was not sufficiently increased. (See Table 1) Comparative Example 4 Talc having an average particle size of 4 μm or more (Simgon; manufactured by Nippon Talc, average particle size: 6 μm, talc-II)
), And then Tg, Tc, and Tm were measured by DSC. Both the obtained Tg and Tc are higher than those of the examples, and thus it is shown that talc having a large average particle size has a small crystallization promoting effect. (See Table 1) Comparative Example 5 The procedure was performed except that 100 parts by weight of the PPS obtained in Reference Example 2 was used instead of 95 parts by weight of PPS, 5 parts by weight of PEG-I, and 1 part by weight of talc-I obtained in Reference Example 2. 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 according to ASTM D648. This value is remarkably lower than that of Example 8, and indicates that only polyethylene glycol and a crystal nucleating agent having poor heat resistance can be obtained.

[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.

Continuation of the front page (51) Int.Cl. ⁷ identification code FI C08L 71:02) (58) Investigated field (Int.Cl. ⁷ , DB name) C08L 81/02 C08L 71/00-71/02 CA ( STN) REGISTRY (STN)

Claims (1)

(57) [Claims] 1. A polyphenylene sulfide resin having a melt viscosity of 10 to 50,000 poise 70 to 99.5% by weight, a polyalkylene glycol represented by the general formula (I) and / or (II) 30 to 0.5% by weight RO-R _{1 m} OX] _n (I) X—OR ₁ —O _m R ₂ O—R _{1 mp OX} (II) (wherein R is X when n = 1, carbon number 1 when n ≧ 2 and carbon number 1 R ₁ is an alkylene group having 2 to 6 carbon atoms, R ₂ is an organic group having 1 to 24 carbon atoms, and X is at least one of an epoxy group, an acid anhydride group, a carboxyl group, and a vinyl group. One containing 1 to 10 carbon atoms or hydrogen, m is 5 to 25000,
n is an integer of 1 to 10 and p is an integer of 2 to 100) in total, and at least one selected from the group consisting of talc, silica, kaolin and hydrotalcite having an average particle size of 4 μm or less. A polyphenylene sulfide resin composition comprising 0.1 to 2 parts by weight of a different kind of crystal nucleating agent.