JP3044316B2 - 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 resin composition having improved toughness of polyphenylene sulfide.

[0002]

2. Description of the Related Art Polyphenylene sulfide (hereinafter PPS)
) Has attracted attention as a member of electric and 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. However, PPS has the significant drawback of poor ductility and fragility.

[0003] Conventionally, fillers such as glass fibers have been blended in order to improve the impact resistance of PPS, but the improvement is not yet sufficient for applications requiring flexibility.

On the other hand, a polymer blend with a polyolefin modified with a glycidyl group or an acid anhydride group has been attempted,
For example, Japanese Patent Application Laid-Open Nos.
It is disclosed in, for example, JP-A-151460. However, although these methods improve the impact strength, they do not lead to obtaining a good PPS molded product such as a decrease in tensile strength, an increase in melt viscosity and a decrease in moldability.

[0005]

SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned conventional processing method and technical problems, and a PPS having improved toughness without impairing the characteristics of PPS.
An object of the present invention is to provide a PS resin composition.

[0006]

That is, the present invention provides (a) a polyphenylene sulfide resin of 50 to 99.5% by weight,
(B) (Meth) acrylic acid ester copolymer 50 obtained by copolymerizing 50 to 99.9 mol% of (meth) acrylic acid ester and 50 to 0.1 mol% of unsaturated carboxylic anhydride.
And (c) a fibrous reinforcing material and / or (c) a total of 100 parts by weight of the polyphenylene sulfide resin and (b) the (meth) acrylate copolymer.
Alternatively, the present invention relates to a polyphenylene sulfide resin composition containing 0 to 200 parts by weight of a granular reinforcing material, and the details thereof will be described below.

The PPS used in the present invention is:

[0008]

Embedded image 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. It may be.

[0009]

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

These production methods are already known and are disclosed in US Pat. No. 2,513,188, JP-B-44-27671, JP-B-45-3368, and JP-B-52-122.
No. 40, JP-A-61-222517, U.S. Pat. No. 3,274,165, JP-B-46-27255 and Bergi-Japanese Patent 29437.

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

These melt viscosities are measured at 300 ° C. using a Koka type flow tester (die: 0.5 mm in inner diameter, 2.0 mm in length, load: 10 kg).
oise to 100000 poise, preferably 50p
oise to 50,000 poise.

Further, in order to enhance the reactivity with the (meth) acrylate copolymer of the present invention, a highly reactive P
PS, for example, a PPS containing a hydroxyl group or sodium alcoholate already filed by the present applicant (JP-A-64-4882).
No. 8, JP-A-64-48829), PPS containing a carboxyl group or a sodium carboxylate, PPS containing an amino group (Japanese Patent Application Nos. 1-1107369 and 1-1115982), terminal thiol It is preferable to use PPS containing thiol or sodium thiolate.

The (meth) acrylate copolymer used in the present invention is a (meth) acrylate ester 50
９９99.9 mol%, unsaturated carboxylic acid anhydride 50５０0.
It is a resin obtained by copolymerizing 1 mol%.

Examples of the (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, i- Butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, 2
-Ethylhexyl (meth) acrylate, decyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, and the like.

Examples of the unsaturated carboxylic anhydride include:
Maleic anhydride, itaconic anhydride, citraconic anhydride,
Hymic anhydride, bicyclo (2,2,2) octa-5
-Ene-2,3-dicarboxylic anhydride, 4-methylcyclohex-4-ene-1,2-dicarboxylic anhydride,
1,2,3,4,5,8,9,10-octahydronaphthalene-2,3-dicarboxylic anhydride, bicyclo (2,
2,1) oct-7-ene-2,3,5,6-tetracarboxylic acid-2,3,5,6-dianhydride, 7-octabicyclo (2,2,1) hept-5-ene -2,3-dicarboxylic acid and the like can be listed. Of these, maleic anhydride is particularly preferably used.

As a method for producing the (meth) acrylate copolymer used in the present invention, for example, a solution polymerization method can be used. It can be produced by reacting a (meth) acrylate and an unsaturated carboxylic anhydride in an organic solvent in the presence of a radical initiator at 0 ° C to 150 ° C for 30 minutes to 30 hours.

The total concentration of the raw materials is generally between 50 and 500
A range of g / l solvent is selected. The initiator concentration is generally selected from the range of 0.001 to 0.1 g / g of all raw materials.

As the organic solvent, various solvents can be used, for example, dimethylformamide, dimethylsulfoxide, tetrahydrofuran, benzene, toluene, xylene, 1,4-dioxane, p-ethylphenol, p-ethylphenol
Chlorophenol and the like can be mentioned.

The radical initiator is not particularly limited as long as it is used as a usual initiator for radical polymerization. For example, azobisisobutyronitrile, azobisisovaleronitrile, benzoyl peroxide, t-butylhydrogen Peroxide and the like can be mentioned.

As another production method, it can be produced by suspension polymerization or emulsion polymerization in water in the presence of an initiator, in the presence of a suspending agent or emulsifier.

Examples of the fibrous reinforcing material and / or granular reinforcing material used in the present invention include ceramic fibers such as glass fiber, carbon fiber, and alumina fiber, aramid fiber, wholly aromatic polyester fiber, metal fiber, and potassium titanate whisker. Fillers such as calcium carbonate, mica, talc, silica, barium sulfate, calcium sulfate, kaolin, clay, pyroferrite, bentonite, sericite, zeolite, nepheline cinite, attapulgite, wollastonite, ferrite, Calcium silicate, magnesium carbonate, dolomite, antimony trioxide, zinc oxide, titanium oxide, magnesium oxide, iron oxide, molybdenum disulfide, graphite, gypsum, glass beads, glass powder, glass balloon, quartz, quartz glass, etc. Inorganic fillers and organic and inorganic It can be blended fee.

As the glass fiber, for example, a fiber length of 1.5
Chopped strands having a fiber diameter of 3 to 24 μm, milled fibers having a fiber diameter of 3 to 8 μm, and glass flakes and powders having a size of 325 mesh or less can be mentioned.

In the present invention, the content of PPS is 50 to
It is 99.5% by weight, preferably 70 to 98% by weight.
When the content of PPS is less than 50% by weight, the solvent resistance and heat resistance of PPS decrease, and when the content of PPS exceeds 99.5% by weight, the toughness of PPS is not improved.

In the (meth) acrylate copolymer, the content of the (meth) acrylate is 50 to 99.9 mol%, preferably 70 to 93 mol%. If the content of the (meth) acrylate is less than 50 mol%, the moldability decreases due to an increase in the melt viscosity due to kneading, and if it exceeds 99.9 mol%, the reactivity of the (meth) acrylate copolymer decreases. Will drop.

In addition, if necessary, for example, olefin, styrene, urethane, ester, fluorine,
Amide-based, acrylic-based thermoplastic elastomers, polybutadiene, polyisoprene, polychloroprene, polybutene, styrene-butadiene rubber and its hydrogenated products, acrylonitrile-butadiene rubber, ethylene propylene copolymer, ethylene propylene ethylidene norbornene copolymer, etc. Rubber component, nylon 6, nylon 66, nylon 610, nylon 12, nylon 11, nylon 46
Polyamide resins such as polyethylene terephthalate,
Polyester resins such as polybutylene terephthalate, polyarylate, polystyrene, poly-α-methylstyrene, polyvinyl acetate, polyvinyl chloride, polyacrylate, polymethacrylate, polyacrylonitrile, polyolefin, polyurethane, polyaceta −
, Polycarbonate, polyphenylene oxide, polysulfone, polyether sulfone, polyallylsulfone, polyphenylene sulfide sulfone, polyether ketone, polyether terketone, polyphenylene sulfide ketone, polyamide imide, silicone resin, phenoxy resin, Homopolymers such as fluororesins and melt-processable resins that form an anisotropic melt phase, random or block, graft copolymers, and mixtures or modified products thereof can be added.

Also, plasticizers and release agents such as aromatic hydroxy derivatives, silane-based and titanate-based coupling agents, lubricants, heat stabilizers, weather resistance stabilizers, crystal nucleating agents, foaming agents, rust prevention An agent, an ion trapping agent, a flame retardant, a flame retardant auxiliary, etc. may be added as necessary.

The method for obtaining the PPS resin composition of the present invention is as follows: 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. A method of adding another component to the pellets obtained, melt-kneading and pelletizing again 3) A method of dissolving each component in a solvent and stirring with heating.

In each of the above methods, known devices such as Banbury, kneaders and autoclaves can be used alone or in combination.

The PPS resin molded product of the present invention is obtained by injection molding,
It can be processed into various molded products by sheet molding, vacuum molding, heterogeneous molding, foam molding and the like and used.

[0031]

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

Further, the melt viscosity of PPS is determined by the Koka type flow.
Tester (die: inner diameter 0.5 mm, length 2.0 mm;
The load was measured at 300 ° C. Reference Example 1 An autoclave equipped with a stirrer and having a capacity of 15 l
Methyl-2-pyrrolidone (hereinafter abbreviated as NMP) 50
00g and sodium sulfide (Na ₂ S · 2.9H ₂ O)
1898 g (14.8 mol) was added, the temperature was raised to 205 ° C., and 420 g of water and 5 g of NMP were distilled off. continue,
p-Dichlorobenzene (14.35 mol) and 3,5-dichloroaniline (0.15 mol) were added, and the mixture was added at 225 ° C.
The reaction was performed 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 the polymer was 98.5%. The polymer was repeatedly washed with warm water and dried under reduced pressure at 100 ° C. for 24 hours, resulting in a melt viscosity of 500 poise.
Of PPS was obtained. Further, this PPS is cured at 250 ° C. in air for 5 hours to obtain a melt viscosity of 7000 po.
ISE PPS was obtained. This is designated as PPS-I. Reference Example 2 3,5-dichloroaniline of Reference Example 1 (0.15 mol)
Instead of 2,4-dichlorobenzoic acid (0.15 mol)
The same operation as in Reference Example 1 was performed except that was used. The conversion of the polymer was 96%, and the melt viscosities before and after curing were 480 poise and 6500 pois, respectively.
e. This is designated as PPS-II. Reference Example 3 3,5-dichloroaniline of Reference Example 1 (0.15 mol)
Instead of 3,5-diaminochlorobenzene (0.15
(Mole), and the same operation as in Reference Example 1 was performed. The conversion of the polymer was 95%, and the melt viscosities before and after curing were 590 poise and 7600 p, respectively.
oise. This is designated as PPS-III. Reference Example 4 3,5-dichloroaniline of Reference Example 1 (0.15 mol)
In the same manner as in Reference Example 1, except that 3,5-dichlorophenol (0.15 mol) was used instead. The conversion of the polymer was 97% and the melt viscosities before and after curing were 400 poise and 6700 p, respectively.
oise. This is designated as PPS-IV. Reference Example 5 An NN was placed in an autoclave having an internal volume of 15 l equipped with a stirrer.
P5000g, sodium sulfide (Na ₂ S · 2.9H ₂
O) 1898 g (14.8 mol), 1800 g of sodium benzoate and 48 g of sodium hydroxide were added, and 205
C., and 418 g of water and 5 g of NMP were distilled off. Subsequently, 2131 g of p-dichlorobenzene (14.
5 mol), and reacted at 220 ° 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. Monomer
Was 96.0%. 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 3400 poise. This is designated as PPS-V. Reference Example 6 An NM was placed in an autoclave having an internal volume of 15 l equipped with a stirrer.
P5000g and sodium sulfide (Na ₂ S · 2.9H
₂ O) _1898g of (14.8 mol) was added, the temperature was raised to 205 ° C., was distilled NMP of water and 5g of 420 g. Subsequently, p-dichlorobenzene (14.5 mol) was added,
The reaction was performed at 225 ° C. for 3 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. Conversion of monomer is 98.
5%. The polymer was repeatedly washed with warm water and dried under reduced pressure at 100 ° C. for 24 hours to obtain a melt viscosity of 590.
Poise PPS was obtained. In addition, this PPS is 250
Melt viscosity 8 by curing in air at 5 ° C for 5 hours
300 poise PPS was obtained. This is called PPS-VI
And Reference Example 7 5000 equipped with a stirrer, thermometer, nitrogen inlet tube, and cooler
i-butyl acrylate 513 in a 4-ml four-necked flask.
g (4 mol) and maleic anhydride 118 g (1.2 mol)
And 4400 ml of 1,4-dioxane and stirred, and 8
After the temperature was raised to 0 ° C., 3.6 g of azobisisobutyronitrile was obtained.
(22 mmol) was added. After stirring for 6 hours, 3.6 g (22 mmol) of azobisisobutyronitrile was further added, and the mixture was stirred for 6 hours, cooled to room temperature, and then poured into a large amount of methanol to precipitate a polymer. The supernatant was removed, decanted and washed repeatedly with methanol, and then dried in vacuo at 100 ° C. for 24 hours to obtain a colorless and transparent viscous polymer. When the molecular weight and composition of the obtained polymer were measured, the weight average molecular weight was 1500.
0 and the molar ratio of i-butyl acrylate to maleic anhydride was 90:10. This is called iBA-co-M
Ah. Reference Example 8 i-butyl acrylate of Reference Example 7 513 g (4 mol)
Instead of n-butyl acrylate 513 g (4 mol)
The same operation as in Reference Example 7 was performed except that was used. The weight average molecular weight of the polymer was 19000, and the molar ratio of n-butyl acrylate to maleic anhydride was 89:11.
Met. This is designated as nBA-co-MAh. Reference Example 9 513 g (4 mol) of i-butyl acrylate of Reference Example 7
736 g of 2-ethylhexyl acrylate instead
The same operation as in Reference Example 7 was performed except that (4 mol) was used. The weight average molecular weight of the polymer was 17000, and the molar ratio of 2-ethylhexyl acrylate to maleic anhydride was 88:12. This is OA-co-M
Ah. Reference Example 10 513 g (4 mol) of i-butyl acrylate of Reference Example 7
In the same manner as in Reference Example 7, except that 1984 g (4 mol) of stearyl methacrylate was used instead. The weight average molecular weight of the polymer was 25,000, and the molar ratio of stearyl methacrylate to maleic anhydride was 8
9:11. This is SMA-co-MAh. Reference Example 11 513 g (4 mol) of i-butyl acrylate of Reference Example 7
In the same manner as in Reference Example 7, except that 400 g (4 mol) of ethyl acrylate was used instead. The weight average molecular weight of the polymer was 18,000, and the molar ratio of ethyl acrylate to maleic anhydride was 91: 9.
This is referred to as EA-co-MAh. Example 1 950 g of PPS-I obtained in Reference Example 1 was added to i obtained in Reference Example 7.
After dispersing an acetone solution in which 50 g of BA-co-MAh was dissolved and removing acetone at 100 ° C., the sample was pelletized at 300 ° C. using a Labo Plastomill (manufactured by Toyo Seiki), and then an in-line screw injection molding machine was used. (Toshiba IS-50EP) cylinder temperature 29
A molded product was obtained at 0 ° C. and a mold temperature of 140 ° C. ASTM D638 for tensile properties of molded products, AS for Izod impact test
The measurement was performed according to TM D256. The test results are shown in Table 1. Examples 2 to 6, Comparative Example 1 The same operation as in Example 1 was performed at the composition ratios shown in Table 1 to obtain molded articles. The test results are shown in Table 1. Example 7 Acetone solution obtained by dissolving 50 g of OA-co-MAh obtained in Reference Example 9 in 950 g of PPS-III obtained in Reference Example 3 was dispersed, acetone was removed at 100 ° C., and 60 g of chopped strand was added and dry blended. Thereafter, the sample was pelletized at 300 ° C., and then a molded product was obtained at a cylinder temperature of 290 ° C. and a mold temperature of 140 ° C. The molded article has a tensile strength of 1800 kg / cm ² and a tensile elongation of 4.5.
%, Izod impact strength (anti-notch) is 51kg ・ cm
/ Cm.

[0033]

[Table 1]

[0034]

As described in detail above, according to the present invention,
A PPS resin composition having improved toughness without lowering other physical properties of PPS can be obtained, and its industrial value is high.

Claims (1)

(57) [Claims] 1. A polyphenylene sulfide resin (a)
-99.5% by weight, (b) 50-99.9% by mole of (meth) acrylate, 50-unsaturated carboxylic anhydride
(Meth) acrylic acid ester copolymer obtained by copolymerizing 0.1 mol%: 50 to 0.5% by weight, and a total of (a) polyphenylene sulfide resin and (b) (meth) acrylic acid ester copolymer: 100 (C) for parts by weight
A polyphenylene sulfide resin composition comprising 0 to 200 parts by weight of a fibrous reinforcing material and / or a granular reinforcing material.