JP3112083B2 - Polyphenylene sulfide resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention allows the phase structure of a blend or alloy to be freely controlled, thereby improving the impact resistance of polyphenylene sulfide. It relates to a resin composition.

[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 equipment and automobile equipment. 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 major drawback of poor extension and fragility.

Conventionally, to improve the impact resistance of PPS, a filler such as glass fiber is blended, but it is not enough,
In particular, it is ineffective for applications requiring flexibility and for preventing the occurrence of stress distortion during sealing of electronic components. On the other hand, polymer blending with a flexible polymer is a promising method.
Methods described in JP-A-53-13468, JP-A-51-100150 and the like can be mentioned. However, these flexible polymers have insufficient compatibility with PPS, so it is difficult to control the phase structure of the alloy, and to obtain PPS with improved impact resistance and flexibility without impairing the characteristics of PPS. Not reached.

[Problems to be Solved by the Invention] The present invention has been made to solve the problems of the conventional processing method and the conventional technology described above, and in particular, freely controls the alloy phase structure and domain size. It was made in pursuit of a PPS alloy with improved impact resistance and flexibility without impairing the features of PPS.

[Means for Solving the Problems] That is, the present invention relates to a polyphenylene sulfide resin 5-95.
100% by weight of a resin consisting of 95% to 5% by weight of a polycarbonate resin, polyethylene glycol, polypropylene glycol, polytetramethylene glycol,
Polyethylene glycol-polypropylene glycol random or block copolymers and their diglycidyl ethers, trimellitic anhydride esters, glycerin,
The present invention relates to a polyphenylene sulfide resin composition containing 0.5 to 20 parts by weight of a compound selected from pentaerythritol, sorbitol and their monoalkyl ethers, monophenyl ethers and monobenzyl ethers, and the details thereof will be described below.

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. It may be united.

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 sulfate or sodium hydrogen sulfate and sodium hydroxide or hydrogen sulfide in a polar solvent. And the polymerization in the presence of sodium hydroxide or sodium aminoalkanoate, self-condensation of p-chlorothiophenol, etc., among which amide solvents such as N-methylpyrrolidone and dimethylacetamide and sulfones such as sulfolane A suitable method is to react sodium sulfide with p-dichlorobenzene in a solvent. These production methods are already known, for example, U.S. Patent No. 2513188, JP-B-44-27671,
JP-B-45-3368, JP-B-52-12240, JP-A-61-225217, and U.S. Pat.No. 3,274,165, U.S. Pat.No. 1,160,660, and JP-B-46-27255, Belgian patent No. 29439 No. etc.

PPS may be linear or branched, or may be a mixture of these structures. These melt viscosities are measured using a Koka type flow tester (die: 0.5 m inside diameter)
m; length: 2.0 mm; load: 10 kg) at a value measured at 300 ° C. of 10 to 100,000 poise, preferably 50 to 50,000 poise.
The range is 000 poise.

Further, in order to enhance the compatibility with the compound such as polyalkylene glycol used in the present invention, a highly reactive functional group is used.
May be introduced during 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, and a method of introducing the halogen-containing aromatic compound containing these functional groups is suitable. And a method of introducing PPS and a low-molecular compound containing a functional group by a polymer reaction.

Furthermore, the above PPS is deionized (acid cleaning, hot water cleaning, etc.)
By performing the above, sodium ions may be reduced.

As the polycarbonate (hereinafter abbreviated as PC) used in the present invention, a PC homopolymer or a PC copolymer based on one or more of the following bisphenols can be used.

Hydroquinone, resorcinol, dihydroxydiphenyl, bis- (hydroxyphenyl) -alkane, bis-
(Hydroxyphenyl) -cycloalkane, bis- (hydroxyphenyl) -sulfide, bis- (hydroxyphenyl) -ketone, bis- (hydroxyphenyl)
-Ether, bis- (hydroxyphenyl) -sulfoxide, bis- (hydroxyphenyl) -sulfone and α, α′-bis- (hydroxyphenyl) -diisopropylbenzene, and compounds having a nucleus substituted by alkyl or halogen. be able to.

Specific examples of preferred bisphenols among these include 4,4-dihydroxydiphenyl, 2,2-bis-
(4-hydroxyphenyl) -propane, 2,4-bis-
(4-hydroxyphenyl) -2-methylbutane, 1,1
-Bis- (4-hydroxyphenyl) -cyclohexane, α, α'-bis- (4-hydroxyphenyl) -p
-Diisopropylbenzene, 2,2-bis- (3-methyl-4-hydroxyphenyl) -propane, 2,2-bis-
(3-chloro-4-hydroxyphenyl) -propane,
Bis- (3,5-dimethyl-4-hydroxyphenyl)-
Methane, 2,2-bis- (3,5-dimethyl-4-hydroxyphenyl) -propane, bis- (3,5-dimethyl-4-
(Hydroxyphenyl) -sulfone, 2,4-bis- (3,5
-Dimethyl-4-hydroxyphenyl) -2-mercaptan, 1,1-bis- (3,5-dimethyl-4-hydroxyphenyl) -cyclohexane, α, α'-bis- (3,5-
Dimethyl-4-hydroxyphenyl) -p-diisopropylbenzene, 2,2-bis- (3,5-dichloro-4-hydroxyphenyl) -propane and 2,2-bis- (3,5-dibromo-4-hydroxy Phenyl) -propane and the like, preferably 2,2-bis- (4-hydroxyphenyl) -propane, 2,2-bis- (3,5-dimethyl-4-hydroxyphenyl) -propane, 2,2 -Bis- (3,5-dichloro-4-hydroxyphenyl) -propane, 2,2-
Bis- (3,5-dibromo-4-hydroxyphenyl)-
Propane and 1,1-bis- (4-hydroxyphenyl)
-Cyclohexane.

Preferred PCs are based on the preferred bisphenols described above. Particularly preferred PC copolymers are 2,2-bis-
Copolymers of (4-hydroxyphenyl) -propane with one of the above particularly preferred other bisphenols.

Other particularly suitable PCs are 2,2-bis- (4-hydroxyphenyl) -propane or 2,2-bis- (3,5-dimethyl-
4-hydroxyphenyl) -propane only.

Incidentally, PC can be produced by a known method, for example, a method of melt transesterification of bisphenol and diphenyl carbonate, a two-phase interfacial polymerization method of bisphenol and phosgene, and the like.

The compound to be blended with respect to 100 parts by weight of the resin consisting of 5 to 95% by weight of polyphenylene sulfide resin and 95 to 9% by weight of polycarbonate resin includes polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polyethylene glycol-polypropylene glycol random or block copolymer. Polymers and their diglycidyl ethers, trimellitic anhydride esters, glycerin, pentaerythritol, sorbitol and their monoalkyl ethers, monophenyl ethers,
Examples include compounds selected from monobenzyl ethers.

In the present invention, when the content of PPS is less than 5% by weight of the whole resin, the solvent resistance and heat resistance of PPS cannot be utilized. Also P
If the content of PS exceeds 95% by weight, the low-temperature properties and toughness of PC cannot be utilized. PR for 100 parts by weight of PPS and PC
If the amount of G is less than 0.5 parts by weight, the compatibility between PPS and PC is poor, and it becomes difficult to control the phase structure of the alloy by the molecular weight and structure of PRG. If it exceeds 20 parts by weight, the effect of PRG reaches saturation, and PRG itself may be thermally decomposed.

It is also possible to add a small amount of another polymer to the PPS resin composition of the present invention to impart other physical properties.

As the polymer to be added, for example, olefin-based, styrene-based, urethane-based, ester-based, fluorine-based, amide-based, acrylic-based thermoplastic elastomers, polybutadiene, polyisoprene, polychloroprene, polybutene, styrene-butadiene rubber and water Additives, acrylonitrile-butadiene rubber, rubber components such as ethylene-propylene copolymer, ethylene-propylene-ethylidene norbornene copolymer and polystyrene, poly-α-methylstyrene, polyvinyl acetate, polyvinyl chloride, polyacrylate, Resins such as polymethacrylic acid ester, polyacrylonitrile, polyolefin, nylon 6, nylon 66, nylon 610, nylon 12, nylon 1
1, polyamide resins such as nylon 46, polyethylene terephthalate, polybutylene terephthalate, polyester resins such as polyarylate, polyurethane, polyacetal, polyphenylene oxide, polysulfone, polyether sulfone, polyallylsulfone, polyphenylene sulfide sulfone, polyether ketone, Polyether ether ketone, polyphenylene sulfide ketone, polyamide imide, silicone resin, fluororesin,
Examples include homopolymers such as melt-processable resins that form an anisotropic melt phase, random or block, graft copolymers and mixtures thereof, 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, nephelinecinite, attapulgite, wollastonite, ferrite, 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.

Examples of the glass fiber include a chopped strand having a fiber length of 1.5 to 12 mm and a fiber diameter of 3 to 24 µ, a milled fiber having a fiber diameter of 3 to 8 µ, glass flakes and glass powder of 325 mesh or less.

In addition, plasticizers and release agents such as aromatic hydroxy derivatives, silane-based, 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 and pelletized again 3) A method in which each component is dissolved in a solvent and heated and stirred is used.

It is also possible to use a known device such as a Banbury, a kneader, or an autoclave 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 articles by vacuum molding, hetero-formed form, 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. In addition, 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).

REFERENCE EXAMPLE 1 N was placed in an autoclave with a volume of 15 L equipped with a stirrer.
- (hereafter, NMP) methyl-2-pyrrolidone 5000g 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 washed repeatedly 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, the PPS was cured at 250 ° C. for 5 hours in the air to reduce the melt viscosity to 2000 poise. The PPS thus obtained is referred to as PPS-I.

Reference Example 2 The same operation as in Reference Example 1 was performed, except that 14.35 mol of p-dichlorobenzene and 0.15 mol of 3,5-dichloroaniline were used instead of 14.5 mol of p-dichlorobenzene. The conversion of the polymer was 94%, and the melt viscosities before and after curing were 280 poise and 2800 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 0.15 mol of 2,5-dichlorobenzoic acid was used instead of 0.15 mol of 3,5-dichloroaniline. 96 polymer conversion
% And the melt viscosities before and after curing are 280 respectively.
Poise was 2600 poise. PP obtained in this way
Let S be PPS-III.

Reference Example 4 The same operation as in Reference Example 2 was performed, except that 0.15 mol of 3,5-dichloroaniline was used instead of 0.15 mol of 3,5-dichloroaniline. 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 In Reference Example 1, 1800 g of sodium benzoate and 48 g of sodium hydroxide were charged simultaneously with NMP, and the reaction time was set to 220 ° C.2
The operation was performed in the same manner as in Reference Example 1 except that the temperature was changed to 250 ° C. for 3 hours. The conversion of the polymer was 96%, and the melt viscosity after polymerization was 3,400 poise. The PPS obtained in this manner is designated as PPS-V.

Examples 1 to 8 Comparative Example 1 PPS obtained in Reference Examples 1 to 4 and polyethylene glycol (average molecular weight: 400, abbreviated as PEG-I), α, ω-dicrysidyl polyethylene glycol (Epolite 100E; manufactured by Kyoeisha Oil & Fats, average molecular weight 100, abbreviated as PEG-II), (Epolite 400E; average molecular weight 400, abbreviated as PEG-III), (Denacol EX-861; manufactured by Nagase Kasei Co., Ltd .; average molecular weight 1000, abbreviated as PEG-IV) and PC (manufactured by Teijin Chemicals Ltd.) And Panlite) were uniformly blended with the composition shown in Table 1 and then melt-blended at 300 ° C. for 10 minutes using a Labo Plastomill (manufactured by Toyo Seiki). The resin mass after blending was cooled with liquid nitrogen and then fractured, and the fractured surface was observed for phase structure with a scanning electron microscope. Further image processing was performed to determine the average particle diameter of the PC.

[Effect of the Invention] As described in detail above, the resin composition of the present invention comprises PPS and P
Even if C is blended with the same composition, it is possible to freely control the phase structure and PC domain size by changing the molecular weight and molecular structure of PEG, without further reducing the other physical properties of PPS. The toughness is improved and its industrial value is high.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ identification code FI C08L 69:00 71:02) (58) Investigated field (Int.Cl. ⁷ , DB name) C08L 81/00-81/02 C08L 69/00 C08L 71/00-71/03 C08K 5/04-5/06

Claims (1)

(57) [Claims] 1. A resin 10 comprising 5 to 95% by weight of a polyphenylene sulfide resin and 95 to 5% by weight of a polycarbonate resin.
With respect to 0 parts by weight, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polyethylene glycol-polypropylene glycol random or block copolymers or their diglycidyl ethers, trimellitic anhydride esters, glycerin, pentaerythritol, sorbitol and their derivatives A polyphenylene sulfide resin composition comprising 0.5 to 20 parts by weight of a compound selected from a monoalkyl ether, a monophenyl ether and a monobenzyl ether.