JPH0420565A - Polyphenylene sulfide resin composition - Google Patents

Abstract

PURPOSE:To improve impact resistance and flexibility without deteriorating excellent properties inherent in a polyphenylene sulfide resin by compounding a mixture of the resin with a polycarbonate resin in a specified ratio with a specific polyalkylene glycol. CONSTITUTION:100 pts.wt. resin mixture comprising 5-95wt.% polyphenylene sulfide resin and 95-5wt.% polycarbonate resin is compounded with 0.5-20 pts.wt. polyalkylene glycol of formula 1 and/or II, wherein R is H or a 1-24C org. group having at least one group selected from the group consisting of a terminal epoxy, acid anhydride, carboxyl, acid amide, imide, and amino group; R' is 2-6C alkylene; R'' is a 1-24 C org. group; m and l are each integer of 0-25000; and n is an integer of 1-10.

Description

[Detailed description of the invention] [Industrial application field] The present invention allows the phase structure to be freely controlled when blending or alloying, and as a result, the impact resistance of polyphenylene sulfide is improved. The present invention relates to a resin composition.

[Prior Art] Polyphenylene sulfide (hereinafter abbreviated as PPS) is attracting attention as a material for electrical and electronic equipment and automobile equipment due to its excellent heat resistance and chemical resistance. Furthermore, it can be molded into various molded parts, films, sheets, fibers, etc. by injection molding, extrusion molding, etc., and is widely used in fields where heat resistance and chemical resistance are required.

However, PPS has significant disadvantages of poor ductility and brittleness.

Conventionally, fillers such as glass fibers have been added to improve the impact resistance of PPS, but this has not been done enough.
In particular, it is not effective in applications that require flexibility or in preventing the occurrence of stress strain when sealing electronic components.

On the other hand, polymer blending with a flexible polymer is an effective method, and examples include methods described in Japanese Patent Publication No. 5B-13468 and Japanese Patent Application Laid-open No. 100150/1983. However, since the flexible polymers described in these documents have insufficient compatibility with PPS, it is difficult to control the phase structure of the alloy, and it is difficult to obtain PPS with improved impact resistance and flexibility without impairing the characteristics of PPS. Not yet reached.

[Problems to be Solved by the Invention] The present invention has been made to solve the problems of the conventional processing method and conventional technology described above, and in particular, it is possible to freely control the phase structure and domain size of the alloy, This was created in pursuit of a PPS alloy with improved impact resistance and flexibility without sacrificing the characteristics of PPS.

[Means for Solving the Problems] That is, the present invention provides polyphenylene sulfide resins 5 to 95
0.5 to 20 parts by weight of polyalkylene glycol represented by formulas (I) and (II) R-E-(: 0-R -±-0-R]
(1) m n R−O−+R−0+−fR″−−(−0−R−)−il
Tlo-R(II) (wherein R is an organic group having 1 to 24 carbon atoms or hydrogen having at least one of an epoxy group, an acid anhydride group, a carboxylic acid group, an acid amide group, an imide group, and an amino group terminal) , Ro is an alkylene group having 2 to 6 carbon atoms,
Ro is an organic group having 1 to 24 carbon atoms, m1g is 0 to 2500
0 and n each represent an integer from 1 to 10. ), and the details thereof will be explained below.

The PPS used in the present invention is a polymer containing 70 mol% or more, more preferably 90 mol% or more of repeating units represented by bonding units, and the following within the range of less than 30 mol% of the repeating units. It may also be a copolymer containing repeating units having a similar structure.

The above-mentioned method for producing PPS includes a method in which a halogen-substituted aromatic compound, such as p-dichlorobenzene, is polymerized in the presence of sulfur and sodium carbonate, and a method in which sodium sulfide or sodium hydrogen sulfide and sodium hydroxide or hydrogen sulfide are polymerized in a polar solvent. Examples include polymerization in the presence of sodium hydroxide or sodium aminoalkanoate, self-condensation of p-chlorothiophenol, and among others, amide solvents such as N-methylpyrrolidone and dimethylacetamide, and sulfolane A suitable method is to react sodium sulfide and p-dichlorobenzene in a sulfonic solvent. These manufacturing methods are already known, for example, U.S. Pat.
Publication No. 1, Special Publication No. 3368 of 1983, Publication of Special Publication of Publication No. 1982-
No. 12240, Japanese Unexamined Patent Publication No. 61-225217,
and U.S. Patent No. 3,274,165, U.S. Patent No. 116
No. 0660, Japanese Patent Publication No. 46-27255, Belgian Patent No. 29437, etc.

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

In addition, these melt viscosities were measured using a Koka type flow tester (Dice: inner diameter 0.5 mm; length = 2.0 mm; load: 10 k
g), the value measured at 300°C is 10 poise to 10
0,000 poise, preferably 50 poise to 50,00 poise
It is in the range of 0 poise.

Furthermore, in order to improve the compatibility with the polyalkylene glycol used in the present invention, highly reactive functional groups may be introduced into PPS. Suitable functional groups to be introduced include amino groups, carboxylic acid groups, hydroxyl groups, acid anhydride groups, epoxy groups, etc., and the method for introducing them is to copolymerize halogen-containing aromatic compounds containing these functional groups. Ya, PPS
Examples include a method of introducing a low molecular weight compound containing a functional group through a polymer reaction.

Furthermore, the above PPS is subjected to deionization treatment (acid cleaning, hot water cleaning, etc.)
The sodium ion content may be reduced by performing the above steps.

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

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.

Examples include α'-bis(hydroxyphenyl)-diisopropylbenzene and compounds thereof in which the nucleus is substituted with alkyl or halogen.

Among these, specific examples of preferable bisphenols include 4,4-dihydroxydiphenyl, 2,2-bis-(4-hydroxyphenyl)-propane, and 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-4hydroquinphenyl)-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-(
Examples include 3,5-dichloro-4-hydroxyphenyl)-propane and 2,2bis-(3,5-dibromo-4-hydroxyphenyl)-propane, preferably 2゜2-bis-(4-hydroxyphenyl)-propane. phenyl)-propane, 2
, 2-bis-(3,5-dimethyl-4-hydroxyphenyl)-propane, 2,2-bis=(3,5-dichloro-4-hydroxyphenyl)propane, 2,2-bis-
Mention may be made of (3,5-dibromo4-hydroxyphenyl)-propane and 11-bis-(4-hydroxyphenyl)-cyclohexane.

Preferred PCs are based on the preferred bisphenols described above. A particularly preferred PC copolymer is 2,2-bis-
A copolymer of (4-hydroxyphenyl)propane and one of the other particularly preferred bisphenols mentioned above.

Other particularly suitable PCs are those based solely on 2,2-bis-(4-hydroquinphenyl)-propane or 22-bis(3,5-dimethyl-4-hydroxyphenyl)-propane.

Note that PC can be produced by a known method, such as a melt transesterification reaction between bisphenol and diphenyl carbonate, or a two-phase interfacial polymerization method between bisphenol and phosgene.

Polyalkylene glycol (hereinafter referred to as PRG) used in the present invention
) is the following formula (I) and/or (II) R-++O-R'+-0-R] nm (I) R-0+R=o +TR"→0~R-→-, 0 -R(I
I) (wherein R is an organic group having 1 to 24 carbon atoms or hydrogen having at least one of an epoxy group, an acid anhydride group, a carboxylic acid group, an acid amide group, an imide group, and an amino group terminal),
Ro is an alkylene group having 2 to 6 carbon atoms, Ro is an alkylene group having 1 carbon number
~24 organic groups, m, 47 are O~25000, n is 1~
10, each represents an integer. ).

To explain in detail R in the compounds represented by formulas (I) and (I[) of the present invention, at least one of an epoxy group, an acid anhydride group, a carboxylic acid group, an acid amide group, an imide group, and an amino group terminal It is an organic group having 1 to 24 carbon atoms or hydrogen. R' refers to an alkylene group having 2 to 6 carbon atoms, specifically ethylene, propylene, butylene, isopropylene, etc. R' is an organic group having 1 to 24 carbon atoms. Here, RSR" in the formula is referred to as an organic group. This includes not only hydrocarbon groups and the above-mentioned terminal groups, but also heteroatom-containing functional groups such as ethers, ketones, amides, and sulfones in RSR". It means an alkyl group or an aryl group that can be used.

Some examples of the above PRG include, in formula (I), polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polyethylene glycol-polypropylene glycol random or block copolymer,
Polyhydric alcohols (glycerin, pentaerythritol,
sorbitol, etc.), addition polymers of these polyhydric alcohols and alkylene oxides, and their monoalkyl ethers, monophenyl ethers, monobenzyl ethers, and the like.

Examples of formula (II) include those obtained by coupling PRG shown by formula (I) with bisphenol or the like. Further, the terminal group R of the above PRG is an epoxy group, an acid anhydride group, a carboxylic acid group, an acid amide group, an imide group,
For those with amino groups, for example, epoxy-modified PRG can be obtained by reacting polyalkylene glycol with epichlorohydrin, and acid anhydride-modified PRG can be obtained by reacting trimellitic acid anhydride with acid chloride.

In the present invention, when the content of PPS is less than 5% by weight of the total resin, the solvent resistance and heat resistance of PPS are not utilized. Furthermore, if the PPS content exceeds 95% by weight, the low-temperature physical properties and toughness of PC will not be utilized. Furthermore, PPS and PC10
If the amount of PRG added is less than 0.5 parts by weight, the compatibility between PPS and PC will be poor, and it will become difficult to control the phase structure of the alloy based on the molecular weight and structure of PRG. If the amount exceeds 20 parts by weight, the effect of PRG reaches saturation, and there is a risk that PRG itself will be thermally decomposed.

It is also possible to add other polymers in small amounts to the PPS resin composition of the present invention to impart other physical properties.

Examples of the polymers to be added include thermoplastic elastomers such as olefin, styrene, urethane, ester, fluorine, amide, and acrylic elastomers, polybutadiene, polyisoprene, polychloroprene, polybutene,
Rubber components such as styrene/butadiene rubber and its hydrogenated products, acrylonitrile/butadiene rubber, ethylene/propylene copolymer, ethylene/propylene/ethylidenenorbornene copolymer, polystyrene, polyα-methylstyrene, polyvinyl acetate, polyvinyl chloride, Resins such as polyacrylic ester, polymethacrylic ester, polyacrylonitrile, polyolefin, nylon 6,
Polyamide resins such as nylon 66, nylon 610, nylon 12, nylon 11, and nylon 46, polyester resins such as polyethylene terephthalate, polybutylene terephthalate, and polyarylate, polyurethane,
Polyacetal, polyphenylene oxide, polysulfone, polyether sulfone, polyallyl sulfone, polyphenylene sulfide sulfone, polyether ketone,
Homopolymers, random or block, such as polyether ether ketone, polyphenylene sulfide ketone, polyamideimide, silicone resin, phenoxy resin, fluororesin, melt processable resin forming an anisotropic melt phase,
Examples include graft copolymers, mixtures thereof, and modified products thereof.

Furthermore, if necessary, reinforcing fillers such as glass fibers, carbon fibers, ceramic fibers such as alumina fibers, aramid fibers, wholly aromatic polyester fibers, metal fibers, potassium titanate whiskers, calcium carbonate, mica, talc, silica, etc. Barium sulfate, calcium sulfate, kaolin, clay, pyroferrite, bentonite, sericite, zeolite, nephelinsinite, acpargite, 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
Inorganic fillers such as glass balloons, quartz, and quartz glass, and organic and inorganic pigments can also be blended.

As the glass fiber, for example, the fiber length is 1.5 to 12 mm,
Chopped strand with fiber diameter 3~24μ, fiber diameter 3~
Examples include milled fibers of 8μ, glass flakes and glass powders of 325 mesh or less.

In addition, plasticizers and mold release agents such as aromatic hydroxy derivatives,
Add silane-based and titanate-based coupling agents, lubricants, heat-resistant stabilizers, weather-resistant stabilizers, crystal nucleating agents, foaming agents, rust preventive agents, ion trapping agents, flame retardants, flame retardant aids, etc. as necessary. You may.

Methods for obtaining the PPS resin composition of the present invention include 1) a method in which each component is mixed in a mixer etc., and then melt-kneaded using an extruder and then formed into pellets; 2) in addition to the pellets obtained by method 1); There is 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 stirred under heating.

It is also possible to use known equipment such as a Banbury, kneader, autoclave, etc. in each of the above methods.

The PPS resin molded product of the present invention can be produced by injection molding, sheet molding,
It can be processed into various molded products by vacuum forming, irregular shaping, foam molding, etc.

[Examples] The present invention will be specifically described below with reference to Examples, but the present invention is not limited only to these Examples. The melt viscosity of PPS was measured at 300° C. using a Koka type float tester (dice: inner diameter Q, 5 mm, length 2.0 mm; load: 10 kg).

Reference example 1 N- in an autoclave with an internal volume of 15L equipped with a stirrer
Methyl-2-pyrrolidone (hereinafter abbreviated as NMP) 500
0 g and sodium sulfide (N a S ・2,
9 H20) 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. Next, 2132 g of p-dichlorobenzene (
14.5 mol) was added thereto, and the reaction was carried out at 250°C for 3 hours. After the reaction was completed, the reaction product was cooled to room temperature and the polymer was isolated using a centrifuge. The conversion rate of dichlorobenzene was 98.5%. Wash the polymer repeatedly with warm water,
PPS with a melt viscosity of 300 poise was obtained by drying at 100°C under reduced pressure for one day.

Furthermore, this PPS was cured in air at 250° C. for 5 hours to give a melt viscosity of 2000 poise. The PPS obtained in this manner is referred to as PP5-1.

Reference Example 2 In Reference Example 1, instead of 14.5 moles of p-dichlorobenzene, 14.35 moles of p-dichlorobenzene and 3.5 moles of p-dichlorobenzene were used.
-Reference Example 1 except that 0.15 mol of dichloroaniline was used
The same operation was performed. The conversion rate of the polymer was 94%, and the melt viscosities before and after curing were 280 poise and 2800 poise, respectively. The PPS obtained in this manner is referred to as pps-n.

Reference Example 3 The same operation as in Reference Example 2 was performed except that 0.15 mole of 2.4-dichlorobenzoic acid was used instead of 0.15 mole of 3.5-dichloroaniline. The conversion rate of the polymer was 96%, and the melt viscosities before and after curing were 280 poise and 2600 poise, respectively. The PPS obtained in this manner is referred to as pps-m.

Reference Example 4 The same operation as in Reference Example 2 was performed except that 0.15 mole of 3.5-diaminochlorobenzene was used instead of 0.15 mole of 3.5-dichloroaniline. The conversion rate 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 referred to as P P 5-IV.

Reference Example 5 The same operation as in Reference Example 1 was performed, except that 1800 g of sodium benzoate and 48 g of sodium hydroxide were charged simultaneously with NMP, and the reaction time was changed to 220°C for 2 hours and then to 250°C for 3 hours. . The conversion rate of the polymer was 96%, and the melt viscosity after polymerization was 3400 poise. The PPS obtained in this manner is referred to as pps-v.

Examples 1 to 8 Comparative Example 1 PPS obtained in Reference Examples 1 to 4 and polyethylene glycol (
average molecular m 400, abbreviated as PEG-I) α,ω-diglycidyl polyethylene glycol (Epolite 100E
, Kyoeisha Yushi Co., Ltd. 6 average molecular weight 100, abbreviated as PEG-II) (Epolite 400E; average molecular weight 400, P
(abbreviated as EG-III), (Bunacol EX-861; manufactured by Nagase Kasei, average molecular weight 1000, abbreviated as PEG-IV) and PC (manufactured by Teijin Chemicals, Panlite) were uniformly blended with the composition shown in Table 1. The mixture was melt-blended at 300° C. for 10 minutes using a back laboplasto mill (manufactured by Toyo Seiki).

The blended resin mass was cooled with liquid nitrogen and then fractured, and the phase structure of the fractured surface was observed using a scanning electron microscope. Furthermore, image processing was performed to determine the average particle diameter of PC.

[Effects of the Invention] As detailed above, even if PPS and PC are blended with the same composition, the resin composition of the present invention can change the phase structure and PC domain size by changing the molecular weight and molecular structure of PEG. It can be controlled freely, and PPS
Toughness is improved without deteriorating other physical properties, and its industrial value is high.

Claims (1)

[Claims] (1) 5 to 95% by weight of polyphenylene sulfide resin,
Resin 10 consisting of 95 to 5% by weight of polycarbonate resin
0 parts by weight, 0.5 to 20 parts by weight of polyalkylene glycol represented by general formula (I) and/or (II) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼(II) (In the formula, R is an epoxy group, an acid anhydride group, a carboxylic acid group,
An organic group having 1 to 24 carbon atoms or hydrogen having at least one of an acid amide group, an imide group, and an amino group terminal, and R'
is an alkylene group having 2 to 6 carbon atoms, and R'' is an alkylene group having 1 to 24 carbon atoms.
organic group, m, l, 0 to 25000, n 1 to 10,
each represents an integer. ) A polyphenylene sulfide resin composition.