JPH1053705A - Resin composition - Google Patents

Abstract

[PROBLEMS] To provide a polyarylene sulfide resin composition having excellent impact resistance and capable of obtaining various extruded products having extremely small residual stress by extrusion molding. SOLUTION: The mixing ratio of each component is 98 to 50% by mass of a polyarylene sulfide (a), 1 to 25% by mass of a polyolefin (b), and 1 to 25 of an epoxy group-containing α-olefin-based copolymer (c). % By mass, and the polyolefin (b) is at least one polyethylene resin selected from the group consisting of linear low-density polyethylene and ultra-low-density polyethylene, and the polyolefin (b)
And the mass ratio (b: c) of the epoxy group-containing α-olefin-based copolymer (c) is 1: 5 to 5: 1, and these are contained in the polyarylene sulfide (a), respectively. A resin composition characterized by being dispersed as fine particles having an average particle size of 0.10 to 3.00 μm. Extruded articles and tubular articles made of the resin composition.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a polyarylene sulfide resin composition, and more particularly, to a polyarylene sulfide resin composition having excellent impact resistance and moldability. The polyarylene sulfide resin composition of the present invention is particularly excellent in impact resistance by extrusion molding, and it is possible to obtain extruded products having various shapes such as a tubular shape, a plate shape, a rod shape and the like having an extremely small residual stress.

[0002]

2. Description of the Related Art Polyphenylene sulfide (hereinafter referred to as PP)
Polyarylene sulfide (hereinafter abbreviated as PAS) represented by S) is an engineering plastic excellent in heat resistance, chemical resistance, flame retardancy, electrical properties, dimensional stability, etc., and is used for electric parts and automobiles. Used in a wide range of fields such as parts. However, in general, PAS
However, they have a drawback that they are inferior in impact resistance and not always sufficient in moldability, and are sometimes limited depending on the use. Conventionally, various proposals have been made to improve the impact resistance of PAS. For example, it is known that when a fibrous filler such as glass fiber or carbon fiber is mixed with PAS, impact resistance, rigidity, toughness, dimensional stability, and the like are improved. However, PAS is still brittle even when a fibrous filler is blended, and a sufficient effect of improving physical properties cannot be obtained. In addition, a resin composition containing a large amount of a fibrous filler is limited in its use and molding method.

[0003] Therefore, α-olefin and α,
Resin compositions comprising an olefin copolymer comprising a glycidyl ester of β-unsaturated acid have been proposed (JP-A-59-152953, JP-A-59-18).
9166, JP-A-62-153345).
However, when an olefin copolymer is blended with PAS, the melt viscosity increases and moldability decreases, and it is difficult to obtain a sufficient effect of improving impact resistance. In PPS,
A resin composition containing an epoxy group-containing olefin polymer and an elastomer has been proposed (Japanese Patent Publication No. 4-24).
388). However, although this resin composition is improved in melt fluidity, it contains an elastomer, so that the swell at the time of compounding becomes large, a strand cannot be formed stably, and pelletization is difficult. is there. Moreover, it is difficult to obtain an extruded product such as a tubular molded product from the resin composition for the same reason as described above.

Further, (I) 99-1% by weight of polyolefin, (II) 1-99% by weight of PAS, (I) + (I
I) per 100 parts by weight, (III) 5 to 95% by weight of an olefin (co) polymer and 95 to 5% by weight of a vinyl (co) polymer obtained from at least one vinyl monomer, One (co) polymer has a particle size of 0.001
A thermoplastic resin composition comprising 0.1 to 100 parts by weight of a multilayered thermoplastic resin having a dispersion layer of 10 to 10 μm has been proposed (JP-A-2-129245). The publication discloses that at least one vinyl monomer and a radical (co) as a multilayer thermoplastic resin (III).
Grafting precursor (A) obtained by copolymerizing polymerizable organic peroxide in olefin (co) polymer particles (A) 1 to 100% by weight, olefin (co) polymer (B) 0 to 99% by weight, and vinyl A mixture or grafted product comprising 0 to 99% by weight of the system (co) polymer (C) is disclosed, and it is also described that an epoxy group-containing ethylene copolymer is used as the olefin (co) polymer. . However, in the resin composition described in this publication, low-density polyethylene, polypropylene, or the like is used as the polyolefin (I), but the resin composition containing these polyolefins has no effect of improving the impact resistance. When it is sufficient, and when it is used as an extruded product such as a tubular molded product, there is a problem that the residual stress is large and deformation and stress cracks are easily generated.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide a PAS resin composition having excellent impact resistance and moldability. Another object of the present invention is to provide a PAS resin composition having excellent impact resistance and capable of obtaining various extruded products having extremely small residual stress, such as tubular, plate, and rod shapes, by extrusion. It is in. The present inventors have conducted intensive studies to overcome the problems of the prior art, and as a result, PAS is blended with a polyolefin and an epoxy group-containing α-olefin-based copolymer at a specific ratio. At least one polyethylene resin selected from the group consisting of linear low-density polyethylene and ultra-low-density polyethylene is selected and used, and the blending ratio of the polyolefin and the epoxy group-containing α-olefin copolymer is within the selected range. Further, by setting the dispersion state of each of the polyolefin and the epoxy group-containing α-olefin copolymer in the PAS matrix within the range of a specific selected average particle diameter, impact resistance and moldability are improved. It has been found that an excellent resin composition can be obtained. An extruded product such as a tubular molded product using this resin composition has a feature that the residual stress is extremely small. The present invention has been completed based on these findings.

[0006]

Thus, according to the present invention, there is provided a resin composition containing a polyarylene sulfide (a), a polyolefin (b), and an epoxy group-containing α-olefin copolymer (c). The mixing ratio of each component is 98 to 50% by mass of polyarylene sulfide (a) and 1 to 2 of polyolefin (b).
5 mass%, and 1 to 25 mass% of an epoxy group-containing α-olefin copolymer (c), wherein the polyolefin (b) is at least one selected from the group consisting of linear low-density polyethylene and ultra-low-density polyethylene Wherein the mass ratio (b: c) of the polyolefin (b) and the epoxy group-containing α-olefin copolymer (c) is 1: 5 to 1: 5.
5: 1, and the polyolefin (b) and the epoxy group-containing α-olefin-based copolymer (c) contained in the polyarylene sulfide (a) had an average particle diameter of 0.10 to 3.00 μm, respectively.
and m is dispersed as fine particles of m.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION Polyarylene sulfide (PAS) The PAS used in the present invention is a repeat of an arylene sulfide represented by the formula [-Ar-S-] (where Ar is an arylene group). It is an aromatic polymer whose main component is a unit. Repeating unit [-Ar-S
When-] is defined as 1 mol (basic mol), the PAS used in the present invention contains this repeating unit in a proportion of usually at least 50 mol%, preferably at least 70 mol%, more preferably at least 90 mol%. Polymer. Examples of the arylene group include a p-phenylene group, an m-phenylene group, a substituted phenylene group (the substituent is preferably an alkyl group having 1 to 6 carbon atoms, or a phenyl group),
p, p'-diphenylene sulfone group, p, p'-biphenylene group, p, p'-diphenylenecarbonyl group, p,
p'-diphenylene ether group, naphthylene group and the like. As the PAS, a polymer having mainly the same arylene group can be preferably used, but from the viewpoint of processability and heat resistance, a copolymer containing two or more arylene groups can also be used.

Among these PASs, PPS having a repeating unit of p-phenylene sulfide as a main constituent element
However, it is particularly preferable because it has excellent workability and is easily available industrially. Preferred specific examples of the copolymer include a repeating unit of p-phenylene sulfide and m-
Random or block copolymers having phenylene sulfide repeating units, random or block copolymers having phenylene sulfide repeating units and arylene ketone sulfide repeating units, random or block copolymers having phenylene sulfide and arylene sulfone repeating units, and the like. . These PASs are preferably crystalline polymers. Further, PAS is preferably a linear polymer from the viewpoint of melting properties, toughness, and strength.

The PAS used in the present invention is prepared by a known method (for example, Japanese Patent Publication No. 45-3368) in which a polymerization reaction of an alkali metal sulfide and a dihaloaromatic compound is carried out in a polar container solvent.
JP, JP-B-52-12240, JP-B-63-
No. 33775). Examples of the alkali metal sulfide include sodium sulfide, potassium sulfide, lithium sulfide, rubidium sulfide, cesium sulfide, and a mixture thereof. The alkali metal sulfide may be generated in situ in a reactor by a conventional method. The alkali metal sulfide can be used in the form of a hydrate, an aqueous mixture, or an anhydride. A small amount of alkali metal hydroxide is added to react with alkali metal hydrosulfide or alkali metal thiosulfate which is present in trace amounts in alkali metal sulfide, or these impurities are removed or converted to sulfide. May be. Among them, sodium sulfide is industrially preferable because it is the cheapest.

Examples of the dihalo aromatic compound include, for example, p
Dihalobenzenes such as -dichlorobenzene, m-dichlorobenzene, o-dichlorobenzene and p-dibromobenzene; 2,5-dichlorotoluene, 1-methoxy-2,5
Substituted dihalobenzenes such as dichlorobenzene; 1,4-
Dihalonaphthalene such as dichloronaphthalene; 4,4′-
Dihalobiphenyls such as dichlorobiphenyl and 3,3'-dichlorobiphenyl; dihalobenzoic acids such as 3,5-dichlorobenzoic acid; dihalobenzophenones such as 4,4'-dichlorobenzophenone;4,4'-dichlorodiphenyl sulfone And dihalophenyl ethers such as 3, -dichlorodiphenyl ether; and the like. These can be used alone or in combination of two or more. Among these, dihalobenzene is preferred from the viewpoints of economy and physical properties, and p-dihalobenzene such as p-dichlorobenzene is more preferred. In particular, as a dihalo aromatic compound, p-dihalobenzene is preferably 70% by weight or more, more preferably 80% by weight.
Preferably, the content is at least 90% by weight, more preferably at least 90% by weight.

A small amount of a polyhaloaromatic compound having three or more halogen substituents per molecule can be used in order to introduce a slight branched or crosslinked structure into the PAS. Such polyhalo aromatic compounds include, for example, 1,2,3-trichlorobenzene, 1,2,3-
Tribromobenzene, 1,2,4-trichlorobenzene, 1,2,4-tribromobenzene, 1,3,5-trichlorobenzene, 1,3,5-tribromobenzene,
Examples include trihalobenzenes such as 1,3-dichloro-5-bromobenzene, alkyl-substituted trihalobenzenes, and mixtures thereof. Among them, 1,2,4-trichlorobenzene, 1,3,5-trichlorobenzene, and 1,2,3
-Trichlorobenzene is preferred.

As a method for producing PAS, a method is preferred in which a polycondensation reaction is carried out between an alkali metal sulfide and a dihaloaromatic compound in a polar organic solvent containing water, optionally in the presence of a polyhaloaromatic compound. . As the water, for example, a hydrate of an alkali metal sulfide, added water, reaction water,
Water of an alkali metal sulfide aqueous solution and the like can be mentioned. Examples of the organic amide solvent include amide compounds such as N, N-dimethylformamide and N, N-dimethylacetamide; N-methyl-ε-caprolactam and N-methyl-2.
N-alkylpyrrolidone compounds such as -pyrrolidone and N-cyclohexyl-2-pyrrolidone or N-cycloalkylpyrrolidone compounds; N, N-dialkylimidazolidinone compounds such as 1,3-dialkyl-2-imidazolidinone; tetramethyl Tetraalkyl urea compounds such as urea; hexaalkyl phosphate triamide compounds such as hexamethyl phosphate triamide; and the like. These organic amide solvents may be used alone or in combination of two or more. Among these organic amide solvents, NMP is particularly desirable from the viewpoint of economy and stability.

The ratio a / b of the number of moles a of the charged dihaloaromatic compound to the number of moles b of the charged alkali metal sulfide is usually 0.95 to 1.10, preferably 0.98 to 1.0.
8, more preferably in the range of 1.00 to 1.06. When a polyhalo aromatic compound having three or more halogen substituents per molecule is used, it is usually used in an amount of 0.0 to 1 mol of the charged alkali metal sulfide.
002-0.01 mol, preferably 0.0004-0.
009 mol, more preferably 0.0005 to 0.00
It is adjusted to be within the range of 7 mol and added to the polymerization reaction system. The addition of the polyhaloaromatic compound to the polymerization reaction system may be at the early stage or late stage of the polymerization, but in the initial stage, the addition of a small amount is more effective.

[0014] The polymerization method is not particularly limited, and a conventionally known method can be employed.
For example, 0.5 mol per mol of the charged alkali metal sulfide.
150-235 ° C. in the presence of ~ 2.4 mol of water
Then, 2.5 to 7.0 moles of water per mole of the charged alkali metal sulfide is introduced into the reaction system, and the temperature is raised to a temperature of 245 ° C. to 280 ° C. to carry out the reaction. There are ways to continue. The amount of the polar solvent to be used is generally 0.2 to 1 mol per mol of the alkali metal sulfide.
2.0 kg, preferably 0.3 kg to 1.0 kg. The PAS used in the present invention is preferably a linear polymer. However, a small amount of a dihaloaromatic compound and a polyhaloaromatic compound having three or more halogen substituents per molecule are used in combination with the dihaloaromatic compound to reduce the degree of branching. A PAS into which a structure or a crosslinked structure has been introduced can also be used. However, a crosslinked polymer obtained by oxidative crosslinking (curing) of a low molecular weight PAS in the presence of air is not preferred because it has poor processability and low strength and toughness. The PAS used in the present invention generally has a melt viscosity measured at 310 ° C. and a shear rate of 1200 / sec of 1 to 200.
The polymer is in a range of 0 Pa · s, preferably 10 to 500 Pa · s. If the melt viscosity of PAS is too low, the strength such as impact resistance will be low, and if the melt viscosity is too high, for example, extrudability will be poor, and neither is preferable.

Polyolefin In the present invention, at least one polyethylene resin selected from the group consisting of linear low-density polyethylene (hereinafter abbreviated as LLDPE) and ultra-low-density polyethylene (hereinafter abbreviated as VLDPE) is used as the polyolefin. The LLDPE used in the present invention is an ethylene unit having 3 to 18, preferably 4 to 12, more preferably 6 to 12, carbon atoms.
It is a substantially linear copolymer containing 10 α-olefin units. The content of the α-olefin unit in LLDPE is usually 1 to 20% by weight, preferably 2 to 17% by weight, and more preferably 3 to 15% by weight. LL
Density of DPE is 0.880 g / cm ³ excess, preferably 0.885~0.950g / cm ^3, more preferably in the range of 0.890~0.930g / cm ^3. Since the LLDPE and the VLDPE partially overlap in terms of density, their boundaries are not always clear, but in the present invention, a linear and low-density ethylene-α-olefin copolymer is referred to as LLDPE.

Specific examples of LLDPE include, for example, ethylene / propylene copolymer, ethylene / 1-butene copolymer, ethylene / 1-hexene copolymer, and ethylene / propylene copolymer.
4-methyl-1-pentene copolymer, ethylene / 1-octene copolymer and the like can be mentioned. As the LLDPE, not only those produced using a multi-site catalyst such as a Ziegler-type catalyst or a Phillips-type catalyst but also those produced using a single-site catalyst such as a metallocene catalyst can be suitably used. If a specific example of LLDPE manufactured using a multi-site catalyst is shown by a trade name,
For example, Unipole (UCC), Dourex (Dow Chemical), Scrair (DuPont Canada), Mitsubishi Poly-LL (Mitsubishi Chemical), Marrex (Philips), Ultzex (Mitsui Petrochemical) and the like can be mentioned. . LLDP produced using single-site catalyst
If a specific example of E is indicated by a trade name, for example, AFFINIT
Y (Dow Chemical), EXACT (Exxon) and the like.

The structure of LLDPE has a linearity as compared with conventional low-density polyethylene, and is more branched than high-density polyethylene, and an alkyl side chain based on an α-olefin is present in some parts of the main chain. Many have short-chain branching. LLDPE also includes those modified without essentially altering the above structure, for example, graft copolymers and the like. VLD used in the present invention
PE has a density exceeding 0.880 g / cm ^{3 and} 0.915 g
/ Cm ³ or less, preferably 0.885 to 0.915 g /
It is a copolymer of cm ³ ethylene and an α-olefin having 3 to 12 carbon atoms. As mentioned above, LLDPE and VLD
PE partially overlaps in terms of density and is not always clearly distinguished, but in the present invention, a material having a clear linearity (linearity) is referred to as LLDPE. LLD
The lower limit of the density of PE and VLDPE is 0.880 g / c.
m ³ , preferably 0.885 g / cm ³ or more.
The density is a value measured according to ASTM D-1238.

The ethylene-α-olefin copolymer having a density of 0.880 g / cm ³ or less is generally an elastomer. In the resin composition of the present invention, LLDPE or VL
When such an elastomer is used instead of DPE,
The swell at the time of compounding becomes large, the strand cannot be formed stably, and pelletization is difficult. Moreover, it is difficult to obtain an extruded product such as a tubular molded product from a resin composition containing such an elastomer. LLDPE and VLDPE each independently,
Alternatively, two or more kinds can be used in combination. Among these, LLDPE is particularly preferred in terms of impact resistance, moldability, and residual stress.

Epoxy Group-Containing α-Olefin Copolymer The epoxy group-containing α-olefin copolymer used in the present invention comprises at least a repeating unit derived from α-olefin (ie, α-olefin unit) and a glycidyl group. Repeating units derived from the unsaturated monomer containing (ie,
(Glycidyl group-containing unsaturated monomer unit). Representative examples of the epoxy group-containing α-olefin copolymer include (1) a copolymer of an α-olefin and a glycidyl group-containing unsaturated monomer, and (2) a copolymer of an α-olefin and a glycidyl group-containing unsaturated monomer. A grafting precursor obtained by polymerizing at least one ethylenically unsaturated monomer and a radical (co) polymerizable organic peroxide in the presence of a copolymer with a monomer can be exemplified. . The grafting precursor may be grafted at the time of melt-kneading with other components, or may be melt-kneaded and grafted before blending with other components.

Examples of the copolymer of an α-olefin and a glycidyl group-containing unsaturated monomer include, in addition to a binary copolymer of the two, an α-olefin, a glycidyl group-containing unsaturated monomer and another unsaturated monomer. A ternary or more multi-component copolymer with a monomer unit is also included. The α-olefin unit in the copolymer is usually 50 units.
-99.5% by mass, preferably 60-99% by mass, more preferably 70-98% by mass. The content of the glycidyl group-containing unsaturated monomer unit is usually 0.5 to 50% by mass, preferably 1 to 40% by mass, more preferably 2 to 30% by mass. Other unsaturated monomer units are usually 0 to 40% by mass,
Preferably it is 0-30 mass%, more preferably 0-20 mass%. The polymerization form of the epoxy group-containing α-olefin copolymer may be any of a random copolymer, a block copolymer, a graft copolymer, and the like.

Examples of the α-olefin monomer include ethylene, propylene, 1-butene, 1-hexene, 1-octene, and 4-methyl-1-pentene. Of these, ethylene is particularly preferably used. Can be As the glycidyl group-containing unsaturated monomer, for example, glycidyl acrylate, glycidyl methacrylate, monoglycidyl itaconate, monoglycidyl butenetricarboxylate, diglycidyl butenetricarboxylate, triglycidyl butenetricarboxylate, maleic acid Glycidyl esters such as monoglycidyl ester, crotonic acid monoglycidyl ester and fumaric acid monoglycidyl ester; glycidyl ethers such as vinyl glycidyl ether, allyl glycidyl ether, glycidyloxyethyl vinyl ether, styrene-p-glycidyl ether; p-glycidyl styrene And the like. Among these, α, β-
It is a glycidyl ester of an unsaturated acid.

Other unsaturated monomers include, for example, vinyl ester monomers such as vinyl acetate and vinyl propionate, vinyl ether monomers, and vinyl aromatic monomers such as (meth) acrylonitrile, styrene and α-methylstyrene. Monomers, carbon monoxide and the like can be mentioned. Specific examples of the copolymer of an α-olefin and a glycidyl group-containing unsaturated monomer include ethylene / glycidyl methacrylate copolymer, ethylene / vinyl acetate / glycidyl methacrylate copolymer, ethylene / ethyl acrylate / Glycidyl methacrylate copolymer, ethylene / glycidyl acrylate copolymer, ethylene / vinyl acetate / glycidyl acrylate copolymer and the like can be mentioned. Preferred among these are ethylene / glycidyl methacrylate copolymer, ethylene / ethyl acrylate / glycidyl methacrylate copolymer, and ethylene / vinyl acetate / glycidyl methacrylate copolymer. These copolymers can be used alone or in combination of two or more.

The copolymer of the above-mentioned α-olefin and a glycidyl group-containing unsaturated monomer is composed of 50 to 9 α-olefins.
9.5 mass%, glycidyl group-containing unsaturated monomer 0.5 to 0.5
A monomer mixture containing 50% by mass and 0 to 40% by mass of another unsaturated monomer is prepared by adding 0.0001 to 1% by mass of a radical polymerization initiator based on the total mass of all monomers. It can be obtained by high-pressure polymerization under the following conditions. The polymerization pressure is usually 5 to 40 kPa, preferably 10 to 35 kPa
It is. The reaction temperature is usually 50 to 400C, preferably 100 to 350C. Under these reaction pressure and reaction temperature conditions, in the presence of a chain transfer agent and, if necessary, an auxiliary,
A polymerization reaction is carried out by a method of contacting and polymerizing the monomer mixture simultaneously or stepwise.

Examples of the radical polymerization initiator include general-purpose initiators such as peroxides, hydroperoxides, azo compounds, amine oxide compounds, and oxygen. As the chain transfer agent, methane, ethane, butane, isobutane, n
-Saturated aliphatic hydrocarbons such as hexane, n-heptane and chloroform, and halogen-substituted hydrocarbons thereof; saturated aliphatic alcohols such as methanol, ethanol, propanol and isopropanol; saturated aliphatic carbonyl compounds such as acetone and methyl ethyl ketone; Aromatic compounds such as diethylbenzene and xylene; and hydrogen. When the α-olefin is not propylene or 1-butene, these can also be used in combination as a chain transfer agent.

In the presence of a copolymer of an α-olefin and a glycidyl group-containing unsaturated monomer, at least one ethylenically unsaturated monomer is polymerized with a radical (co) polymerizable organic peroxide. The grafting precursor obtained by, for example,
JP-A-1-131220, JP-A-1-13821
No. 4, JP-A-2-129245 and the like. This grafting precursor is
It is easily grafted by heating to 100 to 300 ° C. Grafting is a process in which a polymer of an ethylenically unsaturated monomer is grafted to a copolymer of an α-olefin and an unsaturated monomer containing a glycidyl group, a grafting reaction, a crosslinking reaction, and a reaction in which these are mixed. Means to combine. The fact that they are chemically bonded can be revealed, for example, by the fact that two (co) polymers cannot be separated by a solvent that dissolves one (co) polymer. The copolymer of the α-olefin and the glycidyl group-containing unsaturated monomer also includes a terpolymer or higher copolymer obtained by copolymerizing another unsaturated monomer, as described above.

In the grafting precursor, the proportion of the copolymer of the α-olefin and the glycidyl group-containing unsaturated monomer is usually 5 to 95% by mass, preferably 20 to 90% by mass.
It is. If the proportion of this copolymer is too small, the compatibility with PAS becomes insufficient, while if it is too large, the heat resistance and dimensional stability of the resin composition may be reduced. The proportion of the glycidyl group-containing unsaturated monomer unit in this copolymer is usually 0.5 to 50% by mass, preferably 1 to 4% by mass.
0 mass%, more preferably 2 to 30 mass%. When the glycidyl group-containing unsaturated monomer unit is contained in the polymer of the vinyl monomer, the proportion of the glycidyl group-containing unsaturated monomer unit in the copolymer is determined according to the copolymerization ratio. Can be reduced.

Examples of the ethylenically unsaturated monomer used for producing the graft precursor include, for example, styrene, α-
Vinyl aromatic monomers such as methylstyrene and chlorostyrene; (meth) acrylate monomers such as alkyl esters of (meth) acrylic acid having 1 to 7 carbon atoms; α, β
Glycidyl ester monomers of unsaturated acids; unsaturated nitrile monomers such as (meth) acrylonitrile; vinyl ester monomers such as vinyl acetate; Among these, glycidyl ester monomers of α, β-unsaturated acids,
It is preferable that the main component be either a vinyl aromatic monomer or an unsaturated nitrile monomer. In addition, (meth) acrylic acid represents acrylic acid or methacrylic acid.

A polymer of an ethylenically unsaturated monomer is chemically bonded to a copolymer of an α-olefin and a glycidyl group-containing unsaturated monomer by a grafting reaction, a crosslinking reaction, or a mixed reaction of these. The epoxy group-containing α-olefin copolymer can be obtained by copolymerization by a chain transfer method, an ionizing radiation irradiation method, or the like. Most preferably, however, the grafting precursor is a radical (co) polymerized such as t-butyl peroxymethacryloyloxyethyl carbonate in the presence of a copolymer of an α-olefin and a glycidyl group-containing unsaturated monomer. It can be obtained by (co) polymerizing at least one kind of ethylenically unsaturated monomer using a volatile organic peroxide.

More specifically, in order to produce a grafting precursor, an aqueous suspension obtained by suspending 100 parts by mass of a copolymer of an α-olefin and a glycidyl group-containing unsaturated monomer in water is used. Prepare. On the other hand, 5 to 400 parts by mass of at least one ethylenically unsaturated monomer and 0.1 to 0.1 parts by mass of at least one radical (co) polymerizable organic peroxide are added to 100 parts by mass of the ethylenically unsaturated monomer. 10 parts by mass and a radical polymerization initiator having a decomposition temperature of 40 to 90 ° C. for obtaining a half-life of 10 hours were added to a total of 100 parts of an ethylenically unsaturated monomer and a radical (co) polymerizable organic peroxide. A solution is prepared by dissolving 0.01 to 5 parts by mass with respect to parts by mass. The solution is added to the aqueous suspension, and the mixture is heated under the condition that decomposition of the radical polymerization initiator does not substantially occur, and the ethylenically unsaturated monomer, the radical (co) polymerizable organic peroxide, and the radical After impregnating the polymerization initiator with the copolymer of the α-olefin and the glycidyl group-containing unsaturated monomer, the temperature of the aqueous suspension is increased, and the ethylenically unsaturated monomer and the radical (co) The polymerizable organic peroxide is copolymerized in the copolymer to produce a grafted precursor.

The grafting precursor is 100 to 300
When kneaded under melting at a temperature of ° C., an epoxy group-containing α- having a structure in which a copolymer of an α-olefin and a glycidyl group-containing unsaturated monomer and a polymer of an ethylenically unsaturated monomer are chemically bonded. An olefin-based copolymer can be obtained. The grafting precursor may be grafted when melt-kneaded with PAS and other components. Preferably, α
-Preparing an epoxy group-containing α-olefin copolymer having a structure in which a copolymer of an olefin and a glycidyl group-containing unsaturated monomer and a polymer of an ethylenically unsaturated monomer are chemically bonded, This is melt-kneaded with PAS and other components. Examples of the radical (co) polymerizable organic peroxide used in the production of the grafting precursor include a compound represented by the following formula (1).

[0031]

Embedded image

[Wherein, R ₁ is a hydrogen atom or carbon atom 1
An alkyl group, R ₂ is a hydrogen atom or a methyl group,
R ₃ and R ₄ each represent an alkyl group having 1 to 4 carbon atoms;
₅ represents an alkyl group having 1 to 12 carbon atoms, a phenyl group, an alkyl-substituted phenyl group, or a cycloalkyl group having 3 to 12 carbon atoms, and m is 1 or 2. ] The compound represented by this can be mentioned. In addition, radical (co)
As another example of the polymerizable organic peroxide, a compound represented by the following formula (2) can be given.

[0033]

Embedded image Wherein R ₆ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R ₇ is a hydrogen atom or a methyl group, R ₈ and R
₉ is an alkyl group having 1 to 4 carbon atoms, R ₁₀ is an alkyl group having 1 to 12 carbon atoms, a phenyl group, an alkyl-substituted phenyl group, or a cycloalkyl group having 3 to 12 carbon atoms, and n is 0, 1 or 2. ]

Examples of the radical (co) polymerizable organic peroxide represented by the above formula (1) include t-butylperoxy (meth) acryloyloxy (ethoxy) ethyl carbonate, t-amylperoxy (meth) allylloyxy (ethoxy). Ethyl carbonate, t-hexylperoxy (meth) acryloyloxy (ethoxy) ethyl carbonate, cumylperoxy (meth) acryloyloxy (ethoxy) ethyl carbonate, p-isopropylperoxy (meth) acryloyloxy (ethoxy) ethyl carbonate and the like can be exemplified. . As the radical (co) polymerizable organic peroxide represented by the formula (2),
Examples thereof include t-butyl peroxy (meth) allyl carbonate, cumyl peroxy (meth) allyl carbonate, t-butyl peroxy (meth) allyloxyethyl carbonate, and the like. Among these, preferred are t-butylperoxyacryloyloxyethyl carbonate, t-butylperoxymethacryloyloxyethyl carbonate, t-butylperoxyallylcarbonate, t-butylperoxyallylcarbonate,
And t-butyl peroxymethacrylic carbonate.

Resin Composition The resin composition of the present invention is a resin composition containing PAS (a), polyolefin (b), and an epoxy group-containing α-olefin copolymer (c). The mixing ratio of each component is 98 to 50% by mass of PAS (a), 1 to 25% by mass of polyolefin (b), and 1 to 25% by mass of epoxy group-containing α-olefin copolymer (c). As the polyolefin (b), at least one polyethylene resin selected from the group consisting of LLDPE and VLDPE is used. If the proportion of PAS is too small, PA
S inherent excellent properties such as heat resistance, chemical resistance, flame retardancy, electrical properties, and dimensional stability are impaired. If the proportion of PAS is too large, the effect of improving physical properties such as impact resistance becomes insufficient. The mixing ratio of PAS is preferably 95 to 60% by mass, and more preferably 90 to 70% by mass.

The above-mentioned polyethylene resin and epoxy group-containing α-olefin copolymer are combined in a specific mixing ratio and blended into PAS to obtain a resin composition having excellent impact resistance and moldability. Further, an extruded product such as a tubular molded product having extremely small residual stress can be obtained. If only one of a polyethylene resin and an epoxy group-containing α-olefin copolymer is blended with PAS, a resin composition excellent in impact resistance and moldability cannot be obtained. When polypropylene or low-density polyethylene is used as the polyolefin (b), the effect of improving impact resistance is insufficient, and when molded into a tubular molded article, residual stress increases. When an elastomer is used as the polyolefin (b), good extrusion moldability cannot be obtained.

As described above, since the combined use of the polyethylene resin and the epoxy group-containing α-olefin copolymer has a remarkable effect, even if the mixing ratio thereof is reduced, the resin composition having good properties can be obtained. It is possible to obtain a product, thereby maintaining the original properties of the PAS at a high level. The blending ratio of the polyethylene resin as the component (b) is preferably 2 to 20% by mass, and more preferably 3 to 15% by mass. The compounding ratio of the epoxy group-containing α-olefin copolymer (c) is preferably 2 to 20% by mass, and more preferably 3 to 15% by mass. In the present invention, the mass ratio (b: c) of the polyolefin (b) (that is, the ethylene resin) to the epoxy group-containing α-olefin copolymer (c) is 1: 5 to 5: 1.
It is necessary to adjust within the range of 5: 1. By using the two components in combination within the range of the mass ratio, a resin composition having remarkably excellent properties such as impact resistance can be obtained. If this mass ratio is outside the above range,
Particularly, impact resistance is reduced. This mass ratio (b: c) is preferably 1: 3 to 4: 1, more preferably 1: 2 to 2.
3: 1.

In the resin composition of the present invention, the polyolefin (b) (that is, the above-mentioned ethylene resin) and the epoxy group-containing α-olefin copolymer (c) are each contained in the PAS matrix in a PAS matrix having an average particle size of 0.1. 10-3.00
It must be dispersed as fine particles of μm. The average particle diameter is a value determined by a transmission electron microscope.
By dispersing these two components as fine particles in the PAS, a resin composition having excellent properties such as impact resistance and moldability can be obtained. A molded product or the like can be obtained. The average particle size of the ethylene resin is preferably 0.1
0 to 3.00 μm, more preferably 0.13 to 2.00
μm, most preferably 0.16 to 1.00 μm.
The average particle size of the epoxy group-containing α-olefin copolymer is preferably 0.10 to 3.00 μm, more preferably 0.13 to 2.00 μm, and most preferably 0.16 to
1.00 μm.

As at least one ethylene resin selected from the group consisting of LLDPE and VLDPE, an epoxy group-containing α-olefin copolymer, in particular, an epoxy group-containing α-olefin copolymer is the grafting precursor. (Ie, epoxy having a structure in which a copolymer of an α-olefin and a glycidyl group-containing unsaturated monomer and a polymer of an ethylenically unsaturated monomer are chemically bonded to each other) When a molded product made of a resin composition, for example, a tubular molded product or a solid-phase extruded product, is used when the adhesive strength with the group-containing α-olefin copolymer) is 30 N / 20 mm or more. Has very low residual stress and is excellent in impact resistance. Thus, the outer diameter of 115 m was obtained using the obtained resin composition.
m, when a 6.2 mm thick pipe is extruded, the residual stress of the pipe is 4 MPa or less, preferably 3 MPa or less,
More preferably, it can be reduced to 1 MPa or less. In many cases, the residual stress can be reduced to 0.5 MPa or less. Details of the method for measuring the adhesive strength will be described in the section of Examples.

The resin composition of the present invention may optionally contain other resins and various additives as long as the object of the present invention is not impaired. Suitable examples of other resins include aromatic polyester resins, polyamide resins, and polysulfone resins. Examples of the additive include an ultraviolet absorber, a coloring agent, an antioxidant, a filler, and the like. As the filler, an inorganic filler in the form of powder, granules, a flat plate, or a fiber can be blended. The inorganic filler is blended in an amount of usually 0 to 150 parts by mass, preferably 0 to 100 parts by mass with respect to 100 parts by mass of the resin composition of the present invention. As the inorganic filler, for example, calcium sulfate, calcium silicate, clay, diatomaceous earth, talc, alumina, silica sand, glass powder, iron oxide, metal powder, graphite, silicon carbide, silicon nitride, silica, boron nitride, aluminum nitride, carbon Powdered or granular material such as black; metal foil such as mica, sericite, pyroflight, aluminum flake; flat or scaly material such as graphite; hollow material such as glass balloon, metal balloon, shirasu balloon, pumice stone; glass Mineral fibers such as fibers, carbon fibers, graphite fibers, whiskers, metal fibers, silicon carbide fibers, asbestos, and wollastonite; The inorganic filler is preferably surface-treated using stearic acid, oleic acid, palmitic acid, or a metal salt thereof, paraffin wax, organic silane, organic titanate, or the like.

In the resin composition of the present invention, each component is (PAS
Can be obtained by melting and kneading in a temperature range of from 350 ° C, preferably from (the crystalline melting point of PAS) to 320 ° C. As for the order of melt kneading, all components may be melt mixed at the same time, or the components (b) and (c) may be melt kneaded in advance and then melt kneaded with PAS. Among them, a method of mechanically mixing in advance with a tumbler, a Henschel mixer or the like and then melt-kneading with an extruder is preferable. The resin composition of the present invention, a sheet by a general melt molding method such as injection molding or extrusion molding,
It can be formed into various molded products such as films, tubes, pipes, plates and rods. The resin composition of the present invention is obtained by extrusion molding of a pipe (tubular molded product), a plate-like body,
When formed into an extruded product such as a rod, a molded product having extremely small residual stress can be obtained.

[0042]

EXAMPLES Hereinafter, preferred embodiments of the present invention will be described more specifically with reference to Production Examples, Examples, and Comparative Examples. The measuring method of the physical properties is as follows. (1) Average particle size A transmission electron micrograph was taken using a sample cut from a test piece obtained by injection molding, and the particle size of each dispersed particle was measured from this photograph (n = 30). The average was determined. (2) Izod impact strength Using a test piece obtained by injection molding, ASTM D-
The Izod impact strength (with notch) was measured according to 256. (3) Adhesive strength The adhesive strength between the polyolefin (b) and the epoxy group-containing α-olefin copolymer (c) was measured by the following method. Each of 6 to 7 g of each polymer was sandwiched between ferro-plates provided with a polytetrafluoroethylene sheet and pressed to produce a sheet of each polymer. The pressing temperature was 150 ° C. The press was performed for 1 minute without load and then for 5 seconds with load of 2 MPa, and then the sheet was taken out of the press machine and allowed to cool in air. The polyolefin (b) sheet obtained above and the epoxy group-containing α
-An olefin-based copolymer (c) sheet was put together, and an aluminum foil coated with a release agent (trade name: DAI-FREE manufactured by Daikin Co., Ltd.) was sandwiched between the sheets so as to become 1/3 of the sheet area. Next, the combined sheet was placed in a frame having a thickness of 0.5 mm, pressed between ferro plates provided with a polytetrafluoroethylene sheet (thickness: 300 μm), and pressed. The pressing temperature was 200 ° C. Pressing was performed for 2 minutes with no load and then for 10 seconds with a load of 0.98 MPa.
The laminated sheet was taken out of the press machine and allowed to cool in air. A peeling test of the laminated sheet thus obtained was performed using Tensilon. The peeling test was performed using Tensilon with a sample size of 20 mm in width and a length of a part to be peeled off of 40 mm. The measurement conditions of Tensilon were a load cell of 5 kg, a peeling speed of 50 mm / min, and a distance between chucks of 10 mm. In addition, 2-3mm in width
Peeling was performed from the place where the degree was peeled by hand. This peel strength is determined by the adhesive strength (N /
20 mm). (4) Flexural modulus The flexural modulus was measured according to ASTM D-790. (5) Residual stress A pipe (tubular molded product) obtained by extrusion molding is cut into a length of 50 mm in the extrusion direction, and its outer diameter (D ₀ ;
cm) and wall thickness (t; cm). Next, a part of the circumferential portion of the cut pipe was cut in a width 40 parallel to the extrusion direction.
The cylinder was cut at an interval of mm to obtain a shape in which a cylinder was vertically divided, and its outer diameter (D ₁ ; cm) was measured. The residual stress of the pipe was determined by the following equation. S = E × t × [(1 / D ₁ ) − (1 / D ₀ )] S: residual stress [MPa], E: flexural modulus [MPa], t: pipe wall thickness [cm], D ₀ : pipe outer diameter before cutting [cm], D _1: pipe outer diameter after the cutting [cm].

[Preparation Example 1] In a stainless steel autoclave having a capacity of 5 liters and containing epoxy group-containing α-olefin copolymer (c-1) , 2,500 g of pure water was put, and 2.5 g of polyvinyl alcohol was further added as a suspending agent. Dissolved. 700 g of an ethylene / glycidyl methacrylate copolymer (glycidyl methacrylate content: 15% by mass: Nisseki Lexpearl J3700 manufactured by Nippon Petrochemical Co., Ltd.) was added thereto as an epoxy group-containing α-olefin copolymer. Under atmosphere,
Dispersed. Separately, 1.5 g of benzoyl peroxide as a radical polymerization initiator and 6 g of t-butylperoxymethacryloyloxyethyl carbonate as a radical polymerizable organic peroxide were dissolved in 300 g of styrene. This styrene solution was charged into the autoclave and stirred. The temperature of the autoclave was raised to 60 to 65 ° C., and the mixture was stirred for 2 hours to impregnate a styrene solution containing a radical polymerization initiator and a radically polymerizable organic peroxide into an ethylene / glycidyl methacrylate copolymer. Then raise the temperature to 80
After raising the temperature to ８５85 ° C. and maintaining it for 7 hours to complete the polymerization, it was washed with water and dried to obtain a grafted precursor. Then
The grafted precursor was extruded at 200 ° C. with a single screw extruder and chemically reacted to obtain an epoxy group-containing α-olefin-based copolymer (c-1).

Production Example 2 Epoxy Group-Containing α-Olefin Copolymer (c-2) In Production Example 1, ethylene / glycidyl methacrylate copolymer (glycidyl methacrylate content 15% by mass)
An epoxy group-containing α-olefin copolymer (c-2) was obtained in the same manner as in Production Example 1, except that 700 g was changed to 600 g and 300 g of styrene was changed to 400 g.

Example 1 After the components having the mixing ratios shown in Table 1 were previously mixed in a tumbler, the mixture was melt-kneaded at a barrel temperature of 280 to 320 ° C. by a twin-screw extruder, extruded into strands, and cooled. , Cut and pelletized. Using the obtained pellets, cylinder temperature 2 by injection molding machine
A test piece was prepared by injection molding at 80 to 320 ° C., and used for measuring the properties of the resin composition. Table 1 shows the results.

[Examples 2 to 19 and Comparative Examples 1 to 7] Test pieces and pipes were prepared in the same manner as in Example 1 except that the components and their mixing ratios were changed as shown in Table 1. Created. Table 1 shows the results. <Each Polymer Component> Each polymer component used in these Examples and Comparative Examples is as follows. (1) PPS manufactured by Kureha Chemical Industry Co., Ltd., trade name "Fortron KPS"
(Polyphenylene sulfide; 310 ° C., shear rate 12)
(Melt viscosity 380 Pa · s measured at 00 / sec) (2) LL1 Mitsubishi Chemical Corporation, trade name “Mitsubishi Polyethylene-LL UF”
240 "(linear low density polyethylene; density 0.920g
/ Cm ³ ) (3) LL2 manufactured by Mitsui Chemicals, Inc., trade name "Ultzex 1520"
L "(linear low-density polyethylene; density 0.915 g / c
m ³ ) (4) LL3 manufactured by Dow Chemical Company, trade name “Affinity PF1
140 "(linear low density polyethylene; density 0.895g
/ Cm ³ ) (5) LL4 Exxon Corporation, trade name “Exact 3027” (linear low-density polyethylene; density 0.900 g / cm ³ ) (6) VL Nippon Petrochemical Co., Ltd. trade name “Nisseki Soft rex
D9010 "(ultra low density polyethylene; density 0.900
g / cm ³ ) (7) L Nippon Petrochemical Co., Ltd., trade name “Nisseki Lexron J4
0 "(low density polyethylene; density 0.920 g / c
m ³ ) (8) c-1 Epoxy group-containing α-olefin copolymer produced in Production Example 1 (9) c-2 Epoxy group-containing α-olefin copolymer produced in Production Example 2

[0047]

[Table 1]

<Physical Properties of Tubular Molded Product> A representative one was selected from the above Examples and Comparative Examples, and the pellets obtained above were used for single-screw extrusion at a cylinder and die temperature of 280 to 320 ° C. Table 2 according to the outer diameter sizing method
The pipe (tubular molded article) having an outer diameter (D ₀ ) and a wall thickness shown in Table 2 was molded, and the bending elastic modulus, the outer diameter (D ₁ ) after cutting the pipe, and the residual stress were measured. Table 2 shows the results.

[0049]

[Table 2]

Comparative Examples 8 to 10 Polyolefin (b)
A test piece and a pipe were prepared in the same manner as in Example 1 except that an elastomer was used instead of and each component having the compounding ratio shown in Table 3 was used. As the elastomer (E), trade name “Toughmer A-40” manufactured by Mitsui Petrochemical Co., Ltd.
85 "(ethylene / butene copolymer; density 0.880 g
/ Cm ³ ). Table 3 shows the results. Table 3 also shows the results of Examples 12, 17, and 19 corresponding to these Comparative Examples 8 to 10. <Moldability> The moldability of the resin composition was determined according to the following criteria. A: Pelletization and pipe extrusion could be performed stably. B: Pelletization and pipe extrusion were slightly unstable. C: Swell was too large during compounding to stably melt the strand. Extrusion was not possible, pelletization was difficult, and extrusion of the pipe was not possible.

[0051]

[Table 3]

[0052]

According to the present invention, PAS retains high properties such as heat resistance, chemical resistance, flame retardancy, electrical properties, dimensional stability, etc., and has a high impact resistance and moldability. A significantly improved resin composition is provided. When the resin composition of the present invention is formed into a tubular molded article such as a pipe or other extruded molded article, a molded article having extremely small residual stress can be given. The resin composition of the present invention can be suitably used in a wide range of fields such as electric parts and automobile parts by utilizing its excellent properties.

──────────────────────────────────────────────────の Continuation of the front page (51) Int.Cl. ⁶ Identification code Agency reference number FI Technical display location C08L 63:00) B29L 23:00 C08L 33:14 (72) Inventor Satoshi Usui Nishikicho, Iwaki-shi, Fukushima Prefecture Ochiai 16 Kureha Chemical Industry Nishiki Research Laboratory

Claims (11)

[Claims] 1. A resin composition containing a polyarylene sulfide (a), a polyolefin (b), and an epoxy group-containing α-olefin copolymer (c), wherein the compounding ratio of each component is polyarylene sulfide (a). a) 98 to 50% by mass, polyolefin (b) 1 to 2
5 mass%, and 1 to 25 mass% of an epoxy group-containing α-olefin copolymer (c), wherein the polyolefin (b) is at least one selected from the group consisting of linear low-density polyethylene and ultra-low-density polyethylene Wherein the mass ratio (b: c) of the polyolefin (b) and the epoxy group-containing α-olefin copolymer (c) is 1: 5 to 1: 5.
5: 1, and the polyolefin (b) and the epoxy group-containing α-olefin-based copolymer (c) contained in the polyarylene sulfide (a) had an average particle diameter of 0.10 to 3.00 μm, respectively.
m. A resin composition characterized by being dispersed as fine particles of m. 2. The polyolefin (b) has a density of 0.88.
Linear low density polyethylene in which claim 1 resin composition according to 5~0.950g / cm ^3. 3. The epoxy group-containing α-olefin-based copolymer (c) comprises 50.0 to 99.5% by mass of α-olefin unit and 0.5 units of α, β-unsaturated glycidyl ester unit.
The resin composition according to claim 1, which is an α-olefin / α, β-unsaturated acid glycidyl ester copolymer containing from 5 to 50.0% by mass. 4. The adhesive strength between the polyolefin (b) and the epoxy group-containing α-olefin copolymer (c) is as follows:
The resin composition according to claim 1, which is 30 N / 20 mm or more. 5. An epoxy group-containing α-olefin-based copolymer (c) comprising at least one ethylenically unsaturated monomer in the presence of an α-olefin / α, β-unsaturated glycidyl ester copolymer. The resin composition according to claim 1, which is a grafting precursor obtained by polymerizing a polymer and at least one radical (co) polymerizable organic peroxide. 6. An epoxy group-containing α-olefin-based copolymer (c) is added to at least one vinyl monomer in the presence of an α-olefin / α, β-unsaturated glycidyl ester copolymer. The resin composition according to claim 1, wherein a grafting precursor obtained by polymerizing a radical (co) polymerizable organic peroxide is grafted under melting conditions. 7. A mass ratio (b: c) of the polyolefin (b) and the epoxy group-containing α-olefin copolymer (c).
The resin composition according to claim 1, wherein the ratio is 1: 2 to 3: 1. 8. The polyarylene sulfide (a) contains an average particle diameter of 0.13 to 2.0 in the polyarylene sulfide (a).
The resin composition according to claim 1, wherein the resin composition is dispersed as fine particles of 0 µm. 9. The polyarylene sulfide (a) in which the epoxy group-containing α-olefin copolymer (c) is dispersed as fine particles having an average particle diameter of 0.13 to 2.00 μm. Resin composition. 10. An extruded product obtained by extruding the resin composition according to any one of claims 1 to 9. 11. The extruded product according to claim 10, which is a tubular molded product.