JPH04311763A - Polyphenylene sulfide resin composition - Google Patents

Abstract

PURPOSE:To provide the subject polyphenylene sulfide resin composition having an improved toughness. CONSTITUTION:A polyphenylene sulfide resin composition obtained by blending (a) 50-99.5wt.% polyphenylene sulfide resin with (b) 50-0.5wt.% methacrylate copolymer synthesized from 50-99.9mol% methacrylate and 50-0.1mol% compound represented by the general. formula (I) and/or (II) mentioned bellow and mixing (c) a fibrous reinforcing material and/or granular reinforcing material therewith in an amount of 0-200 pts.wt. based on 100 pts.wt. total amount between (a) the polyphenylene sulfide resin and (b) the methacrylate copolymer.

Description

[Detailed description of the invention]

0001

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin composition of polyphenylene sulfide with improved toughness.

0002

[Prior art] Polyphenylene sulfide (hereinafter referred to 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.

[0003] Conventionally, fillers such as glass fibers have been added to PPS to improve its impact resistance, but this improvement has not yet been sufficient for applications that require flexibility.

On the other hand, attempts have been made to blend polymers with polyolefins modified with glycidyl groups or acid anhydride groups.
For example, JP-A-58-154757, JP-A-62-
It is disclosed in JP 151460 and the like. However, although these methods improve impact strength, they have not resulted in good PPS molded products, such as decreased tensile strength, increased melt viscosity, and decreased moldability.

[0005]

[Problems to be Solved by the Invention] The present invention was made to solve the above-mentioned conventional processing methods and technical problems, and it is possible to produce PPS that has improved toughness without impairing the characteristics of PPS.
An object of the present invention is to provide a PS resin composition.

[0006]

[Means for Solving the Problems] That is, the present invention provides (a) P
PS resin 50-99.5% by weight, (b) methacrylic acid ester 50-99.9% by mole, the following general formula (I) and/
or a methacrylic acid ester copolymer obtained by copolymerizing 50 to 0.1 mol% of the compound represented by (II) -50 to 0
．． 5% by weight, and 100 parts by weight of the above (a) PPS resin and (b) methacrylic acid ester copolymer (
c) It relates to a PPS resin composition containing 0 to 200 parts by weight of a fibrous reinforcing material and/or a granular reinforcing material, and details thereof will be described below.

[0007]

[Formula R is C2 to C18 having an ethylenically unsaturated bond]
represents a hydrocarbon group. )

[0008]

[C5] (In the formula, R is the same as above, X is

[0009]

[C6] Or represents -O-. ) The PPS used in the present invention is

[
0010

A polymer containing 70 mol% or more, more preferably 90 mol% or more of repeating units represented by [Chemical 7], and containing repeating units having the following structure within a range of less than 30 mol% of the repeating units. It may also be a copolymer.

[0011]

[Chemical formula 8] The above-mentioned method for producing PPS includes a method of polymerizing a halogen-substituted aromatic compound, such as p-dichlorobenzene, in the presence of sulfur and sodium carbonate, a method of polymerizing a halogen-substituted aromatic compound, for example, p-dichlorobenzene, and a method of polymerizing a halogen-substituted aromatic compound, such as p-dichlorobenzene, in the presence of sulfur and sodium carbonate, and a method of polymerizing a halogen-substituted aromatic compound such as p-dichlorobenzene in the presence of sulfur and sodium carbonate. sodium,
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 Examples include a method of self-polycondensation of sodium sulfide and p-dichlorobenzene in an amide solvent such as N-methylpyrrolidone or dimethylacetamide, or a sulfonic solvent such as dimethylsulfoxide or sulfolane. preferable.

These manufacturing methods are already known, and are disclosed in US Pat.
40, Japanese Patent Application Laid-Open No. 61-225217, US Pat. No. 3,274,165, Japanese Patent Publication No. 46-27255, Belgian Patent No. 29437, and the like.

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

[0014] The melt viscosity of these was measured at 300°C using a Koka type flow tester (dice: inner diameter 0.5 mm, length 2.0 mm, load: 10 kg), and was 10 po.
ise~100000poise, preferably 50poise
It is in the range of 50000poise to 50000poise.

Furthermore, in order to increase the reactivity with the methacrylic acid ester copolymer of the present invention, highly reactive PPS,
For example, PPS containing hydroxyl group or sodium alcoholate (Japanese Unexamined Patent Application Publication No. 64-48828, JP 64-48829), PPS containing carboxyl group or sodium carboxylate, amino group Containing PPS (Japanese Patent Application No. 1-107369, Japanese Patent Application No. 1-1
15982), PPS containing terminal thiol or sodium thiolate, etc. are preferably used.

The methacrylic acid ester copolymer used in the present invention contains 50 to 99.9 mol% of methacrylic ester and 50 to 0.1 mol% of a compound represented by the following general formula (I) and/or (II). It is a resin formed by copolymerization.

Examples of methacrylic esters include:
Methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, i-butyl methacrylate, pentyl methacrylate, hexyl methacrylate, octyl methacrylate Examples include methacrylate, 2-ethylhexyl methacrylate, decyl methacrylate, lauryl methacrylate, and stearyl methacrylate.

Examples of the general formula (I) and/or (II) include glycidyl acrylate, glycidyl methacrylate, glycidyl ethacrylate, glycidyl itaconate,
Examples include butene carboxylic acid esters, allyl glycidyl ether, vinyl glycidyl ether, methallyl glycidyl ether, 2-methylallyl glycidyl ether, styrene-p-glycidyl ether, and the like.

As a method for producing the methacrylic acid ester copolymer used in the present invention, for example, a solution polymerization method can be used. It can be produced by reacting a methacrylic ester with general formula (I) and/or (II) in an organic solvent in the presence of a radical initiator at 0°C to 150°C for 30 minutes to 30 hours.

[0020] The total concentration of raw materials is generally between 50 and 500
A range of g/l solvent is selected. The initiator concentration is generally selected to be in the range of 0.001 to 0.1 g/g of total feed.

Various solvents can be used as the organic solvent, such as dimethylformamide, dimethylsulfoxide, tetrahydrofuran, benzene, toluene, xylene, 1,4-dioxane, p-ethylphenol, p-chlorophenol, etc. be able to.

The radical initiator is not particularly limited as long as it is used as an initiator for ordinary radical polymerization, such as azobisisobutyronitrile, azobisisovaleronitrile, benzoyl peroxide, t-butyl hydro Peroxide etc. can be mentioned.

[0023] As another method of production, it can be produced by suspension polymerization or emulsion polymerization in water in the presence of an initiator, suspending agent, or emulsifier.

The fibrous reinforcing material and/or the granular reinforcing material used in the present invention include, for example, glass fiber, carbon fiber, ceramic fiber such as alumina fiber, aramid fiber, wholly aromatic polyester fiber, metal fiber, potassium titanate whisker, etc. - Reinforcing fillers such as calcium carbonate, mica, talc, silica, barium sulfate, calcium sulfate, kaolin,
Clay, pyroferrite, bentonite, sericite, zeolite, nephelinsinite, attapulgite, wollastonite, ferrite, calcium silicate,
Inorganic fillers such as 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. Also, organic or inorganic pigments may be blended.

[0025] As the glass fiber, for example, the fiber length is 1.5.
12 mm, chopped strands with a fiber diameter of 3 to 24 μm, milled fibers with a fiber diameter of 3 to 8 μm, glass flakes and glass powder with a mesh size of 325 mesh or less.

[0026] In the present invention, the content of PPS is 50 to
99.5% by weight, preferably 70-98% by weight. If the PPS content is less than 50% by weight, the solvent resistance and heat resistance of PPS will decrease, and if the PPS content exceeds 99.5% by weight, the toughness of PPS will not be improved.

Further, in the methacrylic ester copolymer, the content of methacrylic ester is 50 to 99.
It is 9 mol%, preferably 70 to 93 mol%. If the content of methacrylic acid ester is less than 50 mol%, the molding processability will decrease due to an increase in melt viscosity due to kneading, and if it exceeds 99.9 mol%, the reactivity of the methacrylic ester copolymer will decrease.

Other thermoplastic elastomers such as olefin, styrene, urethane, ester, fluorine, amide, and acrylic elastomers, polybutadiene, polyisoprene, polychloroprene, polybutene, and styrene-butadiene rubber, as required. and hydrogenated products thereof, 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, nylon 46, etc. , polyester resins such as polyethylene terephthalate, polybutylene terephthalate, polyarylate, polystyrene, polyα-methylstyrene, polyvinyl acetate, polyvinyl chloride, polyacrylic ester, polymethacrylic ester, polyester Acrylonitrile, polyolefin, polyurethane, polyacetal, polycarbonate, polyphenylene oxide, polysulfone, polyethersulfone, polyallylsulfone,
Homopolymers such as polyphenylene sulfide sulfone, polyether ketone, polyether ether ketone, polyphenylene sulfide ketone, polyamideimide, silicone resin, phenoxy resin, fluororesin, and melt-processable resins forming an anisotropic melt phase. , random or block copolymers, graft copolymers, mixtures thereof, or modified products thereof, etc. can be added.

In addition, plasticizers and mold release agents such as aromatic hydroxy derivatives, silane-based and titanate-based coupling agents, lubricants, heat-resistant stabilizers, weather-resistant stabilizers, crystal nucleating agents, foaming agents, and rust preventive agents. A flame retardant, an ion trap agent, a flame retardant, a flame retardant aid, etc. may be added as necessary.

The method for obtaining the PPS resin composition of the present invention is as follows: 1) A method in which each component is mixed in a mixer or the like, and then melt-kneaded using an extruder and then pelletized. 2) The PPS resin composition obtained by the method 1) is Examples include a method in which other components are added to the pellets and melt-kneaded again to form pellets; 3) a method in which each component is dissolved in a solvent and stirred with heating; and the like.

[0031] In addition, Banbury, kneader, etc.
It is also possible to use known equipment such as , autoclave, etc. alone or in combination.

[0032] The PPS resin molded product of the present invention can be produced by injection molding,
It can be processed into various molded products by sheet molding, vacuum molding, irregularly shaped molding, foam molding, etc. and used.

[0033]

EXAMPLES The present invention will be specifically explained below with reference to Examples, but the present invention is not limited to these Examples.

[0034] The melt viscosity of PPS is
Tester (Dice: Inner diameter 0.5mm, length 2.0mm;
The measurement was carried out at 300° C. using a load of 10 kg). Reference example 1 N-
Methyl-2-pyrrolidone (hereinafter abbreviated as NMP) 50
00g and sodium sulfide (Na2S・2.9H2O)
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 heated at 225°C.
The reaction was then 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 polymer conversion rate was 98.5%. The polymer was repeatedly washed with hot water and dried under reduced pressure at 100° C. for a day and night to obtain PPS with a melt viscosity of 500 poise. Furthermore, by curing this PPS in air at 250°C for 5 hours, the melt viscosity reached 7000 poi.
The PPS of se was obtained. This will be referred to as PPS-I. Reference Example 2 3,5-dichloroaniline of Reference Example 1 (0.15 mol)
2,4-dichlorobenzoic acid (0.15 mol) instead
The same operation as in Reference Example 1 was performed except that . The conversion rate of the polymer was 96%, and the melt viscosity before and after curing was 480 poise and 6500 poise, respectively.
It was e. This will be referred to as PPS-II. Reference Example 3 3,5-dichloroaniline of Reference Example 1 (0.15 mol)
3,5-diaminochlorobenzene (0.15
The same operation as in Reference Example 1 was performed except that mol) was used. The conversion rate of the polymer was 95%, and the melt viscosity before and after curing was 590 poise and 7600 p, respectively.
It was oise. This will be referred to as PPS-III. Reference Example 4 3,5-dichloroaniline of Reference Example 1 (0.15 mol)
The same operation as in Reference Example 1 was performed except that 3,5-dichlorophenol (0.15 mol) was used instead. The conversion rate of the polymer was 97%, and the melt viscosity before and after curing was 400 poise and 6700 poise, respectively.
It was se. This will be referred to as PPS-IV. Reference example 5 NN in an autoclave with an internal volume of 15 liters equipped with a stirrer
P5000g, sodium sulfide (Na2S・2.9H2
O) 1898g (14.8 mol), 1800g of sodium benzoate and 48g of sodium hydroxide were added, and 205
The temperature was raised to 0.degree. C., and 418 g of water and 5 g of NMP were distilled off. Subsequently, 2131 g (14.5 g) of p-dichlorobenzene
mol) at 220°C for 2 hours, then at 250°C for 3 hours.
A time reaction was performed. After the reaction was completed, the reaction product was cooled to room temperature and the polymer was isolated using a centrifuge. The monomer conversion rate was 96.0%. By repeatedly washing the polymer with hot water and drying it under reduced pressure at 100°C overnight,
PPS with a melt viscosity of 3400 poise was obtained. P this
PS-V. Reference example 6 NM in an autoclave with an internal volume of 15 liters equipped with a stirrer
P5000g and sodium sulfide (Na2S・2.9H
1,898 g (14.8 mol) of 2O) was added, the temperature was raised to 205° C., and 420 g of water and 5 g of NMP were distilled off. Subsequently, p-dichlorobenzene (14.5 mol) was added,
The reaction was carried out at 225°C for 3 hours and then 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 monomer conversion rate was 98.
It was 5%. By repeatedly washing the polymer with hot water and drying it under reduced pressure at 100°C overnight, the melt viscosity was reduced to 590.
Poise's PPS was obtained. Furthermore, this PPS is 250
Melt viscosity of 8 by curing in air at ℃ for 5 hours.
A PPS of 300 poise was obtained. This is PPS-VI
shall be. Reference example 7 5000 equipped with a stirrer, thermometer, nitrogen introduction pipe, and cooler
57 ml of i-butyl methacrylate in a four-necked flask.
0 g (4 moles) and glycidyl methacrylate 57 g (0
．． 4 mol) and 4,400 ml of 1,4-dioxane were added thereto, the mixture was stirred, the temperature was raised to 80°C, and 3.6 g (22 mmol) of azobisisobutyronitrile was added. After stirring for 6 hours, 3.6 g of azobisisobutyronitrile (
22 mmol) was added thereto, 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, and the polymer was repeatedly decanted and washed with methanol, followed by vacuum drying 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 54,000, and the molar ratio of i-butyl methacrylate to glycidyl methacrylate was 91:9. This will be referred to as iBMA-co-GMA. Reference Example 8 The same operation as in Reference Example 7 was performed except that 570 g (4 moles) of n-butyl methacrylate was used instead of 570 g (4 moles) of i-butyl methacrylate in Reference Example 7. . The weight average molecular weight of the polymer is 53,000, and n-
The molar ratio of butyl methacrylate to glycidyl methacrylate was 89:11. This is nBMA-co-G
M.A. Reference Example 9 2-ethylhexyl methacrylate 7 instead of 570 g (4 mol) of i-butyl methacrylate in Reference Example 7
The same operation as in Reference Example 7 was performed except that 92 g (4 mol) was used. The weight average molecular weight of the polymer is 53,000
The molar ratio of 2-ethylhexyl methacrylate and glycidyl methacrylate was 90:10. This is referred to as OMA-co-GMA. Reference Example 10 1352 g (4 mol) of stearyl methacrylate was used instead of 570 g (4 mol) of i-butyl methacrylate in Reference Example 7.
The same operation as in Reference Example 7 was performed except that mol) was used. The weight average molecular weight of the polymer is 178,000,
The molar ratio of stearyl methacrylate to glycidyl methacrylate was 97:3. This is SMA-co-G
M.A. Reference Example 11 Using the apparatus of Reference Example 7, glycidyl methacrylate 6
25 g of homopolymerization was carried out. The weight average molecular weight of the polymer was 32,000. This is called PGMA. Reference Example 12 Using the apparatus of Reference Example 7, stearyl methacrylate 1
Polymerization was carried out in the same manner as in Reference Example 7, except that 352 g (2 mol) and 52 g (0.2 mol) of N-[4-(2,3-epoxypropoxy)-3,5-dimethylbenzyl]acrylamide were used. I did it. The weight average molecular weight of the polymer was 28,000, and it was composed of stearyl methacrylate and N-[
The molar ratio of 4-(2,3-epoxypropoxy)-3,5-dimethylbenzyl]acrylamide was 95:5. This is called SMA-co-EPDMA. Example 1 I obtained in Reference Example 7 was added to 950 g of PPS-I obtained in Reference Example 1.
After dispersing an acetone solution in which 50 g of BMA-co-GMA was dissolved and removing the acetone at 100°C, the sample was pelletized at 300°C using a Laboplast Mill (manufactured by Toyo Seiki), and then an in-line screw injection molding machine was used. (manufactured by Toshiba, IS-50EP) and cylinder temperature 29
A molded article was obtained at 0°C and a mold temperature of 140°C. The tensile properties of the molded product are ASTM D638, and the Izod impact test is A.
Measured according to STM D256. Table 1 shows the test results.
It was shown to. Examples 2 to 7, Comparative Examples 1 to 3 Molded articles were obtained by performing the same operations as in Example 1 using the composition ratios shown in Table 1. The test results are shown in Table 1. Example 8 An acetone solution containing 50 g of SMA-co-GMA obtained in Reference Example 10 was dispersed in 950 g of PPS-III obtained in Reference Example 3, and after removing acetone at 100°C, 60 g of chopped strands were added and dry blended. rear,
The sample was pelletized at 300°C, then cylinder
A molded article was obtained at a temperature of 290°C and a mold temperature of 140°C. The tensile strength of the molded product is 1830 kg/cm2, and the tensile elongation is 4.
7%, Izod impact strength (anti-notch) is 57kg・c
m/cm.

[0035]

[Table 1]

[0036]

[Effects of the Invention] As detailed above, according to the present invention,
A PPS resin composition with improved toughness can be obtained without deteriorating other physical properties of PPS, and its industrial value is high.

Claims (1)

[Claims] Claim 1: (a) Polyphenylene sulfide resin 50
~99.5% by weight, (b) methacrylic acid ester 50~
99.9 mol%, the following general formula (I) and/or (II)
50 to 0.5% by weight of a methacrylic acid ester copolymer obtained by copolymerizing 50 to 0.1 mol% of the compound represented by
and the (a) polyphenylene sulfide resin and (b)
(c) 0 to 20 parts by weight of fibrous reinforcement and/or granular reinforcement per 100 parts by weight of the methacrylic acid ester copolymer;
A polyphenylene sulfide resin composition containing 0 parts by weight. [Formula R is C2 to C18 having an ethylenically unsaturated bond]
represents a hydrocarbon group. ) [Chemical formula 2] (In the formula, R is the same as above, and X represents [Chemical formula 3] or -O-.)