JP3034569B2 - Polyphenylene sulfide resin composition - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a resin composition in which polyphenylene sulfide has improved impact resistance.

[Prior art] Polyphenylene sulfide (hereinafter abbreviated as PPS)
Utilizing its excellent heat resistance and chemical resistance, has attracted attention as a member for electric / electronic devices and a member for automobile devices. 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.

However, PPS has the significant drawback of poor ductility and fragility.

Conventionally, a filler such as glass fiber is blended in order to improve the impact resistance of PPS, but the improvement is not yet sufficient for applications requiring flexibility.

Polymer blends with modified polyolefin copolymers have also been tried, for example, JP-A-58-154757,
JP-A-59-152953 and JP-A-59-189166 are examples. However, when these modified polyolefin copolymers are blended with PPS, their viscosity has increased and short shots have occurred during injection molding, and satisfactory PPS molded articles have not yet been obtained.

On the other hand, a polymer alloy with a polyalkylene glycol has been previously studied by the present applicant, and it has been found that the tensile elongation and moldability of PPS have been improved. However, with these alloy products, a PPS molded product excellent in impact resistance has not yet been obtained.

[Problems to be Solved by the Invention] The present invention has been made to solve the above-mentioned conventional technical problems, and has improved formability, impact resistance, and flexibility without impairing the features of PPS. To provide a PPS resin composition.

[Means for Solving the Problems] That is, the present invention relates to (a) polyphenylene sulfide resin
70 to 99.5% by weight, (b) 30 to 0.5% by weight of a polyalkylene glycol represented by the general formula (I) and / or (II) RO-R _{1 m} OX] _n (I) X-OR ₁ -O _m R ₂ O—R _{1 mp OX} (II) (wherein R is an organic group having 2 to 6 carbon atoms when X = 1 and X when n = 1, and R ₁ is an organic group having 2 to 6 carbon atoms when n ≧ 2) An alkylene group having 1 to 6 carbon atoms, R ₂ is an organic group having 1 to 24 carbon atoms, X is an organic group having 1 to 10 carbon atoms containing at least one of an epoxy group, an acid anhydride group, a carboxyl group and a vinyl group, or hydrogen. And m is 5 to 25000,
n represents 1 to 10 and p represents an integer of 2 to 100) and a total of 100 to 100 parts by weight of the olefin-based copolymer comprising an α-olefin and a glycidyl ester of an α, β-unsaturated acid is 0.5 to 40 parts by weight. The present invention also relates to a polyphenylene sulfide resin composition obtained by adding a part.

 Hereinafter, the details will be described.

The PPS used in the present invention is a bonding unit: Is a polymer containing 70 mol% or more, more preferably 90 mol% or more of the repeating unit represented by the formula, and a copolymer containing a repeating unit having the following structure in a range of less than 30 mol% of the repeating unit. There may be.

Examples of the method for producing PPS include a method of polymerizing a halogen-substituted aromatic compound, for example, p-dichlorobenzene in the presence of sulfur and sodium carbonate, sodium sulfide, sodium hydrogen sulfide and sodium hydroxide in a polar solvent, or sulfide. A method of polymerizing p-dichlorobenzene with hydrogen and sodium hydroxide, preferably in the presence of sodium aminoalkanoate or an alkali metal salt of an organic carboxylic acid as a polymerization aid, a method of self-polycondensing p-chlorothiophenol, and the like However, a method of reacting sodium sulfide with p-dichlorobenzene in an amide solvent such as N-methylpyrrolidone or dimethylacetamide or a sulfone solvent such as dimethylsulfoxide or sulfolane is particularly preferred.

These production methods are already known and are described in U.S. Pat.
JP, JP-B-44-27671, JP-B-45-3368, JP-B-52-12240, JP-A-61-225217, U.S. Patent No. 3,274,165, U.S. Patent No. 1,160,660, JP-B-46 -27255 and Belgian Patent No. 29439.

Furthermore, the PPS may be linear or branched, or may be a mixture of these structures.

These melt viscosities were measured at 300 ° C using a Koka type flow tester (die: inner diameter 0.5 mm, length 2.0 mm, load: 10 kg).
10poise to 100000poise, preferably 50po
ise to 50000poise.

Further, in order to increase the compatibility with the polyalkylene glycol and the olefin-based copolymer used in the present invention, a highly reactive functional group may be introduced into the PPS. As the functional group to be introduced, a thiol group, an amino group, a carboxyl group, a hydroxyl group, an acid anhydride group, an epoxy group and the like are preferable. Considering the reactivity with the olefin copolymer and the polyalkylene glycol, an amino group and / or a carboxyl group is particularly preferable as the functional group introduced into the PPS.

Examples of the introduction method include a method of copolymerizing a halogen-containing aromatic compound having a functional group and a method of introducing PPS and a low-molecular compound having a functional group through a polymer reaction.

Furthermore, the above PPS is deionized (acid cleaning, hot water cleaning, etc.)
May be used to reduce sodium ions.

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 ga 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 greater than 25,000, the compatibility between the polyalkylene glycol and PPS will decrease.

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 and a terminal functional group being a hydroxyl group, an epoxy group, a carboxyl group or an acid anhydride group. .

The olefin copolymer used in the present invention is a copolymer composed of an α-olefin and a glycidyl ester of an α, β-unsaturated acid. Examples of the α-olefin include ethylene, propylene, butane-1 and the like. But ethylene is preferably used. Examples of the glycidyl ester of an α, β-unsaturated acid include glycidyl acrylate, glycidyl methacrylate, glycidyl ethacrylate and the like, and glycidyl methacrylate is particularly preferably used. The copolymerization amount of the glycidyl ester of an α, β-unsaturated acid in the olefin copolymer is preferably 1 to 50% by weight, particularly 3 to 30% by weight, and if it is less than 1% by weight, the toughness is not improved, and Beyond this, the effect remains unchanged and leads to increased costs.

The olefin-based copolymer is 40% by weight or less, and another copolymerizable unsaturated monomer such as vinyl ether, as long as the object of the present invention is not impaired.
Vinyl acetate, vinyl propionate, methyl acrylate,
Methyl methacrylate, acrylonitrile, styrene and the like may be copolymerized.

In the present invention, when the PPS content is less than 70% by weight, the heat resistance and chemical resistance of the PPS decrease, and when the polyalkylene glycol content is less than 0.5% by weight, the thickening of the alloy is suppressed. And the moldability decreases. If the content of the olefin-based copolymer is less than 0.5 part by weight based on 100 parts by weight of the total of PPS and polyalkylene glycol, the impact resistance of the blend is not improved, and if it exceeds 40 parts by weight, the flame retardancy is reduced. I do.

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. Examples of the polymer to be added include thermoplastic elastomers such as olefin-based, styrene-based, urethane-based, ester-based, fluorine-based, amide-based, and acrylic-based polymers, polybutadiene, polyisoprene, polychloroprene, polybutene, styrene butadiene rubber, and hydrogenated styrene. Components, rubber components such as acrylonitrile butadiene rubber, ethylene propylene copolymer, ethylene propylene ethylidene norbornene copolymer,
Polyamide resins such as nylon 6, nylon 66, nylon 610, nylon 12, nylon 11, and nylon 46; polyester resins such as polyethylene terephthalate, polybutylene terephthalate, and polyarylate; polystyrene, poly α-methylstyrene, polyvinyl acetate; Polyvinyl chloride, polyacrylate, polymethacrylate, polyacrylonitrile, polyolefin, polyurethane, polyacetal, polyphenylene oxide, polycarbonate, polysulfone, polyethersulfone,
Single weight of polyallyl sulfone, polyphenylene sulfide sulfone, polyether ketone, polyether ether ketone, polyphenylene sulfide ketone, polyamide imide, silicone resin, phenyl resin, fluororesin, and melt-processable resin that forms an anisotropic molten phase Examples include coalesced, random or block, graft copolymers and mixtures or modified products thereof.

Further, if necessary, glass fiber, carbon fiber, ceramic fiber such as alumina fiber, aramid fiber, wholly aromatic polyester fiber, metal fiber, reinforcing filler such as potassium titanate whisker and calcium carbonate, mica, talc, silica, Barium sulfate, calcium sulfate, kaolin, clay, pyroferrite, bentonite, sericite, zeolite, nepheline sinite, attapulgite, wollastonite, farite, calcium silicate, magnesium carbonate, dolomite, antimony trioxide, zinc oxide, titanium oxide Inorganic fillers such as magnesium oxide, iron oxide, molybdenum disulfide, graphite, 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.

The method of obtaining the PPS resin composition of the present invention includes: 1) a method of mixing the components with a mixer or the like, and then melt-kneading them using an extruder and then pelletizing them. 2) Other than the pellets obtained by the method of 1), A method in which the components are added, melt-kneaded again, and pelletized. 3) A method in which each component is dissolved in a solvent and heated and stirred can be used.

Known devices such as a banbury, a kneader, and an autoclave may be used alone or in combination for each of the above methods.

PPS resin molded product of the present invention, injection molding, sheet molding,
It can be processed into various molded products by vacuum molding, irregularly formed shapes, foam molding and the like and used.

EXAMPLES Hereinafter, the present invention will be described specifically with reference to Examples, but the present invention is not limited to these Examples.

The melt viscosity of the composition after PPS and alloying was measured at 300 ° C. using a Koka type flow tester (die: inner diameter 0.5 mm, length 2.0 mm; load: 10 kg).

Reference Example 1 An autoclave equipped with a stirrer and having a capacity of 15 l
Methyl-2-pyrrolidone (abbreviated as hereinafter NMP) 5000 g and sodium sulfide _{(Na 2 S · 2.9H 2 O} ) 1898g (14.8 moles)
Was added and the temperature was raised to 205 ° C., and 420 g of water and 5 g of NMP were distilled off. Subsequently, 2132 g (14.5 mol) of p-dichlorobenzene was added and reacted at 250 ° C. for 3 hours. At the end of the reaction, the reaction was cooled to room temperature and the polymer was isolated by centrifugation. The conversion of dichlorobenzene was 98.5%. The polymer was repeatedly washed with warm water and dried under reduced pressure at 100 ° C. for 24 hours to obtain PPS having a melt viscosity of 300 poise. Further, this PPS was cured at 250 ° C. in air for 5 hours to obtain PPS having a melt viscosity of 2,000 poise. The PPS thus obtained is referred to as PPS-I.

Reference Example 2 The same as Reference Example 1 except that p-dichlorobenzene (14.5 mol) was replaced with p-dichlorobenzene (14.35 mol) and 3,5-dichloroaniline (0.15 mol). Operation was performed. The conversion of the polymer is 94%, and the melt viscosities before and after curing are 280 poise and 2800 poise, respectively.
Met. The PPS thus obtained is referred to as PPS-II.

Reference Example 3 The same operation as in Reference Example 2 was carried out except that 2,4-dichlorobenzoic acid (0.15 mol) was used instead of 3,5-dichloroaniline (0.15 mol) in Reference Example 2. The conversion of the polymer was 96% and the melt viscosities before and after curing were 28% each.
0poise and 2600poise. PPS obtained in this way
Is PPS-III.

Reference Example 4 The same operation as in Reference Example 2 was performed except that 3,5-diaminochlorobenzene (0.15 mol) was used instead of 3,5-dichloroaniline (0.15 mol) in Reference Example 2. The conversion of the polymer was 95%, and the melt viscosities before and after curing were 110 poise and 2800 poise, respectively. The PPS thus obtained is designated as PPS-IV.

Reference Example 5 NNP50 in an autoclave equipped with a stirrer and having a capacity of 15 l
00g, sodium sulfide (Na ₂ S ・ 2.9H ₂ O) 1898g (14.8 mol), sodium benzoate 1800g and sodium hydroxide 4
8 g was added, the temperature was raised to 205 ° C., and 418 g of water and 5 g of NMP were distilled off. Then, 2109 g (14.35 mol) of p-dichlorobenzene
And 3,5-diaminochlorobenzene (0.15 mol)
The reaction was carried out at 20 ° C. for 2 hours and then at 250 ° C. for 3 hours. At the end of the reaction, the reaction was cooled to room temperature and the polymer was isolated by centrifugation. Dichlorobenzene conversion is 96.0
%Met. Wash the polymer repeatedly with warm water and remove
By drying at 0 ° C all day and night, the melt viscosity of 3400poise
I got PPS. The PPS obtained in this manner is designated as PPS-V.

Reference Example 6 200 g of α, ω-diglycidyl polyethylene glycol (Epolite 400E; manufactured by Kyoeisha Yushi 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. After cooling to room temperature, the mixture is added dropwise to a large amount of diethyl ether to remove excess bisphenol A, and dried under reduced pressure at room temperature for 24 hours to give an epoxy group-containing polyethylene glycol having an average molecular weight of 1200 [general formula (II) type]. ] Was obtained. This is abbreviated as PEG-V.

Examples 1 to 6, Comparative Examples 1 to 2 PPS obtained in Reference Examples 1 to 5 and commercially available polyethylene glycol (average molecular weight: 400, abbreviated as PEG-I), α, ω-diglycidyl polyethylene glycol [general formula (I ) Type] (Epolite 100E; Kyoeisha oil and fat, average molecular weight 100, P
Epolite 400E, abbreviated as EG-II, manufactured by Kyoeisha Oil & Fat, average molecular weight 400, abbreviated as PEG-III, Denacol EX-861; manufactured by Nagase Kasei, average molecular weight 1000, abbreviated as PEG-IV) or an acetone solution of PEG-V. Each was mixed and dried at 100 ° C., and then uniformly dry-blended with a commercially available olefin copolymer (Bond First; manufactured by Sumitomo Chemical Co., Ltd.) at the composition ratio shown in Table 1. After pelletizing the sample at 300 ° C using Labo Plast Mill (manufactured by Toyo Seiki), cylinder temperature was measured using an in-line screw injection molding machine (manufactured by Toshiba, IS-50EP).
A molded product was obtained at 90 ° C. and a mold temperature of 140 ° C. The Izod impact test of the molded article was measured according to ASTM D256. The test results are shown in Table 1.

[Effects of the Invention] As described in detail above, according to the present invention, a PPS resin composition having improved impact resistance and flexibility without lowering other physical properties of PPS is obtained, and its industrial value is high.

Continued on the front page (58) Fields surveyed (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 (a)
99.5% by weight, (b) 30 to 0.5% by weight of a polyalkylene glycol represented by the general formula (I) and / or (II) RO-R _{1 m} OX] _n (I) X-OR ₁ -O _m R ₂ O—R _{1 mp OX} (II) (wherein R is an organic group having 2 to 6 carbon atoms when n = 1, X when n = 1, and R ₁ is an organic group having 2 to 6 carbon atoms when n ≧ 2) R ₂ is an organic group having 1 to 24 carbon atoms, X is an organic group having 1 to 10 carbon atoms containing at least one of an epoxy group, an acid anhydride group, a carboxyl group and a vinyl group, or hydrogen. , M is 5 to 25000,
n is 1 to 10 and p is an integer of 2 to 100), and 100 to 100 parts by weight of the total weight of the olefin-based copolymer of α-olefin and glycidyl ester of α, β-unsaturated acid is 0.5 to 40 parts by weight. And a polyphenylene sulfide resin composition.