JPH08302148A - Polyphenylene sulfide resin composition - Google Patents

Abstract

PURPOSE: To obtain a polyphenylene sulfide resin compsn. in which ingredients are mixed with each other with good compatibilities and which is lightweight and excellent in heat resistance, mechanical strengths, and impact resistance by compounding a polyphenylene sulfide resin with a graft polyolefin resin. CONSTITUTION: This compsn. comprises 100 pts.wt. polyphenylene sulfide resin and 1-100 pts.wt. graft polyolefin resin. The graft resin is obtd. by preparing a water-base suspension contg. 0.1-30 pts.wt. epoxy monomer component comprising a glycidyl compd. represented by formula I (wherein Ar is a 6-23C arom. hydrocarbon group having at least one glycidyl group; and R is H or methyl) (pref. the compd. represented by formula II) and/or an unsatd. glycidyl ester, 0.1-500 pts.wt. vinyl monomer, and a free-radical polymn. initiator in an amt. of 0.001-10wt.% of the sum of the monomers and impregnating 100 pts.wt. polyolefin resin with the suspension to cause graft polymn.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin composition comprising a polyphenylene sulfide resin and a graft-modified polyolefin resin, which is lightweight, has excellent heat resistance and mechanical strength, and is also excellent in impact resistance. .

[0002]

2. Description of the Related Art Since polyphenylene sulfide resin has extremely high heat resistance, excellent chemical resistance and rigidity, molding materials reinforced with reinforcing materials such as glass fiber are used for electric / electronic parts, automobile parts, It is expected as a metal substitute material in a wide range of fields such as office equipment parts and aerospace equipment parts. However, the polyphenylene sulfide resin itself has drawbacks that it has extremely low impact strength and elongation and is extremely brittle, and it is difficult to use it alone as a molding material. In particular, in the field of injection molding, use as a non-reinforcing molding material is limited, and a material using a reinforcing material is the mainstream. Further, when a large amount of the reinforcing material is added, there is a problem that the molding workability deteriorates and the appearance of the molded product is impaired.

As a method for improving the toughness of a polyphenylene sulfide resin, a method of blending a polyphenylene sulfide resin with a polyolefin resin such as polypropylene has been attempted. However, since the polyphenylene sulfide resin and the polyolefin resin are originally poor in compatibility, they cannot be uniformly dispersed even if they are simply mixed, and only those having poor mechanical strength can be obtained.

Therefore, as a method for improving the compatibility between the polyphenylene sulfide resin and the polyolefin resin, JP-A-6-9850 and JP-A-6-88024 disclose olefin resins graft-modified with a polyphenylene sulfide resin and a compound having a glycidyl group. As a method of blending with an elastomer, JP-A-6-128483 proposes a method of blending a polyphenylene sulfide resin with a polypropylene modified with an epoxy group-containing vinyl monomer and an aromatic vinyl monomer. However, although the compatibility is improved by these methods, the effect of improving the mechanical properties is not always sufficient.

[0005]

DISCLOSURE OF THE INVENTION The present invention solves the problems of the conventional compositions, improves the compatibility of the polyphenylene sulfide resin and the polyolefin resin, and is lightweight, and has excellent heat resistance and mechanical properties. Provided is a resin composition having strength and excellent impact resistance.

[0006]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors impregnated a polyolefin resin with a modifier having a specific glycidyl group and a vinyl monomer to perform graft polymerization. The inventors have found that the above object can be achieved by blending a modified polyolefin resin and a polyphenylene sulfide resin, and have reached the present invention.

That is, the present invention comprises the following components (A) and (B): (A) is 100 parts by weight, and (B) is
Is 1 to 100 parts by weight. (A) Polyphenylene sulfide resin, (B) (a)
100 parts by weight of polyolefin resin, (b) the following general formula (I)

[0008]

Embedded image

(Wherein Ar represents a C _{6 to} C ₂₃ aromatic hydrocarbon group bonded to at least one glycidyloxy group, and R represents a hydrogen atom or a methyl group). And / or unsaturated glycidyl ester of 0.1 to 30 parts by weight, (c) vinylic monomer of 0.1 to 500 parts by weight, and (d) of a radical polymerization initiator as component (b) and ( c) Total amount of 10 ingredients
An aqueous suspension containing 0.001 to 10 parts by weight relative to 0 parts by weight was prepared, and (b) the general formula (I) in the aqueous suspension was prepared.
A compound having a glycidyl group represented by and / or an unsaturated glycidyl ester and (c) a vinyl-based monomer are impregnated into the (a) polyolefin-based resin, and the (b) is represented by the general formula (I). A graft-modified polyolefin resin obtained by polymerizing a compound having a glycidyl group and / or an unsaturated glycidyl ester and (c) a vinyl monomer with the (a) polyolefin resin.

The polyphenylene sulfide resin (A) used in the present invention is represented by the following general formula (III)

[0011]

[Chemical 4]

Those containing 70 mol% or more of the structural unit represented by the formula (1) are preferable because they give a composition having excellent characteristics. Further, the other copolymerization structural unit is not limited as long as it is a copolymerizable unit, for example, orthophenylene sulfide unit, metaphenylene sulfide unit, diphenyl sulfide ether unit, diphenyl sulfide sulfone unit, diphenyl sulfide ketone unit , A diphenyl sulfide ether unit, a biphenyl sulfide unit, a naphthalene sulfide unit, a substituted phenylene sulfide unit, a trifunctional phenylene sulfide unit, and the like, and these may be used alone or in combination of two or more. The copolymerization component is preferably less than 30 mol% and more preferably 10 mol% or less. When the amount is more than the above range, sufficient strength, which is a characteristic of crystalline polymer, cannot be obtained, and the balance of toughness, chemical resistance, etc. tends to be deteriorated. In particular, when a phenyl, biphenyl or naphthyl sulfide unit having a functionality of 3 or more is selected as a copolymerization component, the content is preferably 3 mol% or less, more preferably 1 mol% or less from the viewpoint of not impairing crystallinity. These copolymers may be block copolymerized or random copolymerized. The polyphenylene sulfide resin is generally known by its production method to have a substantially linear molecular structure having no branched or crosslinked structure and one having a branched or crosslinked structure, but in the present invention, any of them is known. It is also effective for types.

The (B) graft-modified polyolefin resin of the present invention comprises (a) a polyolefin resin, (b) a compound having a glycidyl group represented by the general formula (I) and / or an unsaturated glycidyl ester, and ( It is produced by polymerizing c) a vinyl monomer in an aqueous suspension in the presence of (d) a radical polymerization initiator. The component (c) vinyl-based monomer realizes uniform impregnation and polymerization of (a) a polyolefin-based resin with (b) a compound having a glycidyl group represented by the general formula (I) and / or an unsaturated glycidyl ester. Is an essential ingredient for
By using the vinyl monomer (c), a resin composition having an excellent balance of physical properties such as mechanical strength can be obtained.

As the polyolefin resin (a) to be graft-modified, ethylene, propylene, 1-butene,
1-pentene, isobutene, butadiene, isoprene,
Chloroprene, phenylpropadiene, cyclopentadiene, 1,3-cyclohexadiene, 1,4-hexadiene, 1,3-octadiene, 1,5-cyclooctadiene, methylenenorbornene, 1,5-norbornadiene, ethylidenenorbornene, α, Homopolymers or copolymers selected from the group of ω-non-conjugated dienes by one kind or a combination of two or more kinds can be mentioned. These may be used alone or in combination of two or more.

As the compound having a glycidyl group, which is one of the components (b) for modifying the polyolefin resin (a), the following general formula (I) is used.

[0016]

Embedded image

(Wherein Ar represents a C _{6 to} C ₂₃ aromatic hydrocarbon group bonded to at least one glycidyloxy group, and R represents a hydrogen atom or a methyl group). It is preferably used. The modifier having a glycidyl group is an important component of the present invention and is derived from a compound having at least one acrylamide group and one glycidyl group in the molecule. The acrylamide group includes a methacrylamide group in addition to the acrylamide group.

Such a compound is disclosed, for example, in JP-A-60 / 1985.
It can be manufactured by the method described in No. 130580. That is, the target compound is obtained by condensing an aromatic hydrocarbon having at least one phenolic hydroxyl group and N-methylolacrylamide or N-methylolmethacrylamide in the presence of an acidic catalyst, and then glycidylating the hydroxyl group with epihalohydrin. Is obtained. As the aromatic hydrocarbon having at least one phenolic hydroxyl group, a phenol compound having 6 to 23 carbon atoms is used. Specific examples of the phenol compound include phenol, cresol, xylenol, carvacrol, thymol, naphthol, resorcin, hydroquinone, pyrogallol, phenanthrol and the like. Among them, monohydric phenol having an alkyl substituent is preferable. For example, when 2,6-xylenol and N-methylolacrylamide are used as starting materials, the following structural formula (II)

[0019]

[Chemical 6]

The compound represented by can be obtained. When orthocresol and N-methylolacrylamide are used as starting materials, the following structural formula (IV)

[0021]

[Chemical 7]

A compound represented by can be obtained. Among these, the compound represented by the structural formula (II) is particularly preferably used.

The unsaturated glycidyl ester, which is another component (b) used in the present invention, includes glycidyl acrylate, glycidyl methacrylate, mono- and diglycidyl esters of itaconic acid, mono-, di- and butenetricarboxylic acid. Triglycidyl esters, mono and diglycidyl esters of citraconic acid, endo-cis-bicyclo (2,2,1) hept-5-ene-2,3
-Mono- and diglycidyl esters of dicarboxylic acids, mono- and diglycidyl esters of endo-cis-bicyclo (2,2,1) hept-5-ene-2-methyl-2,3-dicarboxylic acid, mono- and allyl-succinic acids and Examples thereof include diglycidyl ester and glycidyl ester of p-styrenecarboxylic acid, which may be used alone or in combination of two or more kinds. Among these, glycidyl methacrylate is preferable from the viewpoints of cost and impregnability with a polyolefin resin.

(B) The compound having a glycidyl group represented by the general formula (I) and / or the unsaturated glycidyl ester is used in an amount of 0.1 to 30 parts by weight based on 100 parts by weight of the polyolefin resin (a). Part, preferably 0.5-
20 parts by weight. When it is more than the above range, the mechanical properties and fluidity of the resin composition are deteriorated, and when it is less than the above range, the compatibilizing effect is poor. When a mixture of the compound having a glycidyl group represented by the general formula (I) and the unsaturated glycidyl ester is used as the component (b), the mixing ratio of the unsaturated glycidyl ester is represented by the general formula (I). 0.01 to 100 parts by weight of the compound having a glycidyl group
~ 500 parts by weight, preferably 0.05 to 300 parts by weight,
More preferably, it is 0.1 to 100 parts by weight. When the amount is more than the above range, the fluidity of the resin composition is lowered,
When the amount is small, the physical properties such as mechanical properties are unbalanced.

The vinyl monomer (c) which is one of the constituents of the graft-modified polyolefin resin (B) is, for example, styrene as an aromatic vinyl compound.
O-methyl styrene, p-methyl styrene, m-methyl styrene, υ-methyl styrene, vinyltoluene, divinylbenzene and the like are methyl methacrylate and methacrylic acid as the methacrylic acid alkyl ester having 1 to 22 carbon atoms. Ethyl, -i-propyl methacrylate, -n-butyl methacrylate, -t-butyl methacrylate, 2-ethylhexyl methacrylate, allyl methacrylate, stearyl methacrylate, etc. are acrylics having 1 to 22 carbon atoms. Examples of the acid alkyl ester include methyl acrylate, ethyl acrylate, -i-propyl acrylate, -n-butyl acrylate, -t-butyl acrylate, 2-ethylhexyl acrylate, and stearyl acrylate. Vinyl alkyl ether having a number of 1 to 22 The Le, vinyl methyl ether, vinyl ethyl ether, vinyl -n- propyl ether, vinyl -i- propyl ether, vinyl -i- ether, vinyl -n- amyl ether, vinyl -
i-amyl ether, vinyl-2-ethylhexyl ether, vinyl octadecyl ether and the like, unsaturated nitrile compounds such as acrylonitrile and methacrylonitrile, and unsaturated amino compounds such as
Acrylamide, methacrylamide, and the like include maleic acid di-n as maleic acid di-alkyl ester.
-Amyl ester, maleic acid di-n-butyl ester, maleic acid di-i-amyl ester, maleic acid di-i-butyl ester, maleic acid dimethyl ester,
Maleic acid di-n-propyl ester, maleic acid di-
Octyl esters, maleic acid dinonyl esters and the like, allyl alkyl ethers having 1 to 8 carbon atoms such as allyl ethyl ether and allyl-n-octyl ether, and diene compounds such as dicyclopentadiene, butadiene and isoprene. , Chloroprene, phenylpropadiene, cyclopentadiene, 1,5-norbornadiene, 1,3-cyclohexadiene, 1,4
-Cyclohexadiene, 1,5-cyclohexadiene,
And 1,3-cyclooctadiene and the like, and other vinyl monomers include acrylic acid, methacrylic acid, maleic acid, maleic anhydride, vinyl acetate and the like. These may be used alone or in combination of two or more. Among these, styrene, α-, from the viewpoints of cost, (b) copolymerizability with a compound having a glycidyl group represented by the general formula (I) and an unsaturated glycidyl ester, and impregnability with a polyolefin resin.
Methyl styrene, methyl methacrylate, allyl methacrylate, butyl acrylate, and acrylonitrile are preferable, and these are used alone or in combination of two or more kinds.

The mixing ratio of (c) vinyl monomer is
(A) 0.1% based on 100 parts by weight of the polyolefin resin.
The amount is 1 to 500 parts by weight, preferably 0.1 to 200 parts by weight, and more preferably 0.1 to 100 parts by weight. If more than the above range, because the polymerization of vinyl monomers is the main, excessive aggregation in the aqueous suspension during polymerization,
Fusing, agglomeration, etc. occur. When the amount is less than the above range, it becomes difficult to uniformly impregnate the component (a) polyolefin resin with the component (b) the compound having a glycidyl group represented by the general formula (I) and the unsaturated glycidyl ester, and to perform graft polymerization. .

The radical polymerization initiator (d) used in the production of the above (B) graft-modified polyolefin resin is, for example, methyl ethyl ketone peroxide or di-
t-Butyl peroxide, 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, n-butyl-4,4-bis (t-butylperoxy) valerate, 2,5- Dimethylhexane-2,5-
Dihydroperoxide, α, α′-bis (t-butylperoxy-m-isopropyl) benzene, 2,5-
Organic peroxides such as dimethyl-2,5-di (t-butylperoxy) hexane, 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-3 and benzoyl peroxide, or For example, 1,1′-azobis (cyclohexane-1-carbonitrile), 1-[(1
-Cyano-1-methylethyl) azo] formamide, 2
-Phenylazo-4-methoxy-2,4-dimethyl-valeronitrile, 2,2'-azobis (2-methylbutyronitrile), 2,2'-azobisisobutyronitrile,
Examples of the azo compound include 2,2'-azobis (2,4,4-trimethylpentane), 2,2'-azobis (2-acetoxypropane), and 2,2'-azobis (2-acetoxybutane). , And these are used alone or in combination of two or more kinds. Further, as these radical polymerization initiators, desired ones can be appropriately selected depending on the impregnation and polymerization conditions.

The amount of the radical polymerization initiator (d) used is such that the component (b) a compound having a glycidyl group represented by the general formula (I) and / or an unsaturated glycidyl ester and the component (c) a vinyl-based monomer. The amount is 0.001 to 10 parts by weight, preferably 0.
05 to 3 parts by weight. If the amount is more than the above range, the viscosity will be increased due to excessive crosslinking or the molecular weight will be reduced due to the main chain cleavage, and if it is less than the above range, the polymerization will be insufficient.

When the (B) graft-modified polyolefin resin is produced in the present invention, (b) a compound having a glycidyl group represented by the general formula (I) and / or an unsaturated glycidyl ester, and (c) a vinyl monomer. If necessary, an aqueous suspension containing a monomer and (d) a radical polymerization initiator may be substantially (b) substantially a compound having a glycidyl group represented by the general formula (I) and / or an unsaturated glycidyl ester, or (C) The vinyl-based monomer is heated and brought into contact with each other under the condition that it does not homopolymerize or copolymerize,
(B) The aqueous suspension containing the compound having a glycidyl group represented by the general formula (I) and / or unsaturated glycidyl ester and (c) a polyolefin resin impregnated with a vinyl monomer (a). Is heated to a temperature at which the crystalline portion of the polyolefin resin is substantially melted, and (b) the compound having a glycidyl group represented by the general formula (I) and / or the unsaturated glycidyl ester and the (c). By polymerizing a vinyl-based monomer, (a)
For the polyolefin resin, the (b) general formula (I)
The compound having a glycidyl group represented by and / or the unsaturated glycidyl ester and the vinyl monomer (c) can be uniformly and efficiently grafted, and the compatibilizing effect can be enhanced. In order to obtain the (B) graft-modified polyolefin resin of the present invention, for example, water, a suspending agent, an emulsifying agent, a dispersant, etc. may be appropriately used. There is no limitation as long as the aqueous suspension comprising the reaction mixture of each component is kept in a stable state to the extent that it does not excessively agglomerate or fuse.

In the present invention, the mixing ratio of the two components of (A) polyphenylene sulfide resin and (B) graft-modified polyolefin resin is (B) graft-modified polyolefin-based resin to 100 parts by weight of (A) polyphenylene sulfide-based resin. Resin is 1 to 100 parts by weight, preferably 3 to 50 parts by weight. If the mixing ratio of the above two components is out of the above range, the balance of physical properties such as heat resistance, impact resistance, surface properties, rigidity, moldability, and chemical resistance will be insufficient.

As the filler used in the present invention, silica, talc, mica, glass fiber, neutral clays, carbon fiber, wholly aromatic polyester fiber, aromatic polyamide fiber, silicon carbide fiber, titanate fiber, ceramics. Examples include fibers and metal fibers. The fillers are used alone or in combination of two or more in a proportion of 1 to 100 parts by weight, preferably 5 to 70 parts by weight, based on 100 parts by weight of the resin composition of the present invention. When the amount is more than the above range, the balance of the mechanical properties and molding fluidity of the resin composition is poor, and when the amount is less than the above range, the effect of addition is poor.

In the resin composition of the present invention, if necessary,
Flame retardants, stabilizers, antioxidants, nucleating agents and inorganic fillers can be added. As the flame retardant, tetrabromobisphenol A, 2,2-bis (4-hydroxy-)
3,5-dibromophenyl) propane, hexabromobenzene, tris (2,3-dibromopropyl) isocyanurate, 2,2-bis (4-hydroxyethoxy-)
3,5-dibromophenyl) propane, decabromodiphenyl oxide, brominated polyphosphate, chlorinated polyphosphate, halogenated flame retardants such as chlorinated paraffin; ammonium phosphate, tricresyl phosphate, triethyl phosphate, Phosphorus flame retardants such as trischloroethyl phosphate, tris (β-chloroethyl) phosphate, trisdichloropropylphosphate, cresylphenyl phosphate, xylenyldiphenylphosphate, acidic phosphates, nitrogen-containing phosphorus compounds and the like; Inorganic flame retardants such as red phosphorus, tin oxide, antimony trioxide, zirconium hydroxide, barium metaborate, aluminum hydroxide, magnesium hydroxide, etc.
Brominated polystyrene, brominated poly α-methylstyrene,
Examples include polymer flame retardants such as brominated polycarbonate, brominated polyepoxy resin, chlorinated polyethylene, chlorinated poly α-methylstyrene, chlorinated polycarbonate, and chlorinated polyepoxy resin. The above flame retardants are used alone or in combination of two or more at a ratio of 1 to 50 parts by weight, preferably 3 to 30 parts by weight, based on 100 parts by weight of the resin composition of the present invention.

Examples of the stabilizers include, for example, light stabilizers such as dimethyl-1- (2-hydroxyethyl) -4-hydroxy-2,2,6,6-tetramethylpiperidine polycondensate of succinate and hindered amine. Examples thereof include system compounds, which may be used alone or in combination of two or more. The amount of the stabilizer used is 100% by weight of the resin composition of the present invention.
It is in the range of 0.01 to 20 parts by weight with respect to parts by weight.

As the above antioxidant, 2,4-bis (n-octylthio) -6- (4-hydroxy-3,5) is used.
-Di-t-butylanilino) -1,3,5-triazine, pentaerythrityl-tetrakis [3- (3,5-
Di-t-butyl-4-hydroxyphenyl) propionate], 2,2-thio-diethylenebis [3- (3,5
-Di-t-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 2,
2-thiobis (4-methyl-6-t-butylphenol), 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl)
Phenolic compounds such as benzene, thioether compounds or tetrakis (2,4-di-t-butylphenyl) -4,4'-biphenylene phosphonite, tris (2,4-di-t-butylphenyl) phosphonate Phosphorous compounds such as phonite may be used, and these may be used alone or in combination of two or more. The antioxidant is used in an amount of 0. 0 with respect to 100 parts by weight of the resin composition of the present invention.
It is in the range of 01 to 20 parts by weight.

Examples of the nucleating agent include inorganic substances such as silica, kaolin, talc, hydrotalcite, wollastonite and boron nitride, calcium stearate, aluminum stearate, dipotassium succinate, calcium benzoate, disodium phthalate. , Trisodium trimellitate, metal salts of organic carboxylic acids such as tetrapotassium pyromellitic acid, polymers having a higher melting point than polyphenylene sulfide such as polyphenylene sulfide ketone and nylon 46, and these are used alone or 2
Used in combination of two or more species. The amount of the nucleating agent used is in the range of 0.01 to 20 parts by weight with respect to 100 parts by weight of the resin composition of the present invention.

As the above-mentioned inorganic filler, calcium carbonate, calcium sulfate, barium sulfate, kaolin, clay, pyroferrite, bentonite, sericite,
Zeolite, nepheline sinite, attabalgite,
Wollastonite, PMF, ferrite, calcium silicate, magnesium carbonate, dolomite, antimony trioxide, zinc oxide, titanium oxide, magnesium oxide, iron oxide, molybdenum disulfide, graphite, gypsum, glass beads, glass powder, glass balloon, Examples thereof include quartz and quartz glass, which may be used alone or in combination of two or more kinds. The amount of the inorganic filler used is in the range of 1 to 50 parts by weight with respect to 100 parts by weight of the resin composition of the present invention.

Further, the resin composition of the present invention may optionally contain a plasticizer such as an aromatic hydroxy derivative, a mold release agent, a silane or titanate coupling agent, a lubricant, a dispersant, an organic or inorganic pigment. , Foaming agent, crosslinking agent, rust inhibitor,
An ion trap agent, an antistatic agent, etc. can be added.

The method for producing the resin composition of the present invention includes:
Although not particularly limited, for example, it is preferably manufactured by charging each raw material into a kneading device and melt-kneading. As the kneading device, an extruder, a Banbury mixer, a mill, a kneader, a heating roll, or the like can be used, or a combination thereof can be used.As a method for inexpensively producing, a single-screw or multi-screw extruder is used. preferable.

[0039]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples, and various modifications can be made without departing from the scope of the invention. In the following description,
"Parts" and "%" mean "parts by weight" and "% by weight", respectively, unless otherwise specified.

Reference Example 1: Graft-modified polyolefin resin (MPO1) Propylene-ethylene copolymer particles (ethylene content 3
%, DSC melting point 147 ° C.) 1470 parts, N- [4-
(2,3-Epoxypropoxy) -3,5-dimethylbenzyl] acrylamide 105 parts, styrene 525 parts,
3.78 parts of di-t-butyl peroxide, 31.5 parts of tribasic calcium phosphate, and 0.945 parts of an emulsifier (Latemul PS: registered trademark, manufactured by Kao Corporation) were mixed and mixed with stirring to form an aqueous suspension. Obtained. The aqueous solution was stirred at 100 ° C. for 1 hour and then at 150 ° C. for 2 hours to complete the polymerization. The obtained particles are washed with water to remove residual monomers, tricalcium phosphate, and latemuru PS, and then dried to obtain a graft-modified polyolefin resin (MP
O1) was obtained.

Reference Example 2: Graft-modified polyolefin resin (MPO2) In Reference Example 1, instead of 105 parts of N- [4- (2,3-epoxypropoxy) -3,5-dimethylbenzyl] acrylamide, N- A graft modified polyolefin resin (MPO2) was obtained in the same manner as in Reference Example 1 except that 84 parts of [4- (2,3-epoxypropoxy) -3,5-dimethylbenzyl] acrylamide and 21 parts of glycidyl methacrylate were used.

Reference Example 3: Graft-modified polyolefin resin (MPO3) In Reference Example 1, instead of 105 parts of N- [4- (2,3-epoxypropoxy) -3,5-dimethylbenzyl] acrylamide, N- A graft-modified polyolefin resin (MPO3) was obtained in the same manner as in Reference Example 1 except that 21 parts of [4- (2,3-epoxypropoxy) -3,5-dimethylbenzyl] acrylamide and 84 parts of glycidyl methacrylate were used.

Reference Example 4: Graft modified polyolefin resin (MPO4) In Reference Example 1, glycidyl methacrylate was used instead of 105 parts of N- [4- (2,3-epoxypropoxy) -3,5-dimethylbenzyl] acrylamide. 105
A graft modified polyolefin resin (MPO4) was obtained in the same manner as in Reference Example 1 except that the parts were used.

Reference Example 5: Graft-Modified Polyolefin Resin (MPO5) In a pressure-resistant closed reaction vessel, an ethylene-propylene-non-conjugated diene copolymer (iodine value 12, propylene content 24%, relative to 6000 parts of pure water) was used. Mooney viscosity 26, diene: 5-ethylidene-2-norbornene) 1500
Part, N- [4- (2,3-epoxypropoxy) -3,
5-dimethylbenzyl] acrylamide 96 parts, styrene 281 parts, 1,1-bis (t-butylperoxy)-
4.53 parts of 3,3,5-trimethylcyclohexane, 31.5 parts of tribasic calcium phosphate, and 0.945 parts of an emulsifier (Latemul PS manufactured by Kao Corporation) were mixed and stirred to obtain an aqueous suspension. . The aqueous solution was stirred at 100 ° C. for 1 hour and then at 110 ° C. for 3 hours to complete the polymerization. After washing the obtained particles with water to remove residual monomers, tricalcium phosphate, and latemul PS,
Dry and graft modified polyolefin resin (MPO
5) was obtained.

Reference Example 6: Graft-modified polyolefin resin (MPO6) In Reference Example 5, instead of 96 parts of N- [4- (2,3-epoxypropoxy) -3,5-dimethylbenzyl] acrylamide, N- A graft modified polyolefin resin (MPO6) was obtained in the same manner as in Reference Example 5 except that 72 parts of [4- (2,3-epoxypropoxy) -3,5-dimethylbenzyl] acrylamide and 24 parts of glycidyl methacrylate were used.

Reference Example 7: Graft-modified polyolefin resin (MPO7) In Reference Example 5, an ethylene-propylene copolymer (propylene content 26%) was used instead of the ethylene-propylene-non-conjugated diene copolymer. Except for the above, the graft-modified polyolefin resin (MPO
7) was obtained.

Comparative Reference Example 1: Graft-Modified Polyolefin Resin (MPO8) In Reference Example 1, except that 105 parts of N- [4- (2,3-epoxypropoxy) -3,5-dimethylbenzyl] acrylamide was not used. A graft-modified polyolefin resin (MPO8) was obtained in the same manner as in Reference Example 1.

Comparative Reference Example 2: Graft Modified Polyolefin Resin (MPO9) In Reference Example 5, except that 96 parts of N- [4- (2,3-epoxypropoxy) -3,5-dimethylbenzyl] acrylamide was not used. A graft-modified polyolefin resin (MPO9) was obtained in the same manner as in Reference Example 5.

Examples 1 to 9 and Comparative Examples 1 to 6 Each component of the resin composition of the present invention, (A) polyphenylene sulfide resin, and (B) graft-modified polyolefin resin are shown in Table 1 below. A resin composition was produced with a combination of respective components and a mixing ratio, and test pieces for each characteristic evaluation were prepared. (A) Polyphenylene sulfide resin Polyphenylene sulfide [Ryton R-4 manufactured by Philip Petroleum Co., Ltd .: registered trademark (40% glass fiber reinforced), abbreviated as PPS in the table. (B) Graft-modified polyolefin-based resin Graft-modified polyolefin-based resin produced in Reference Examples 1 to 7 and Comparative Reference Examples 1 and 2 (abbreviated as MPO in the table) MPO1 to MPO9 Ethylene-glycidyl methacrylate copolymer (Sumitomo Chemical Co., Ltd., Bond First 2C: registered trademark, abbreviated as BF in the table.) Unmodified polypropylene resin (Mitsui Petrochemical Co., Ltd.,
Hypol B200: registered trademark, abbreviated as PP in the table. ) Unmodified polyethylene-propylene-non-conjugated diene copolymer (manufactured by Japan Synthetic Rubber Co., Ltd., EP181SP: registered trademark, abbreviated as EPDM in the table).

The resin composition and the test piece were prepared by the following method. A cylinder temperature of 290 was obtained by dry-blending the polyphenylene sulfide resin (A) and the graft-modified polyolefin resin (B) in the proportions shown in Table 1.
It is supplied to a 45 mm twin-screw extruder (TEX44: registered trademark of Japan Steel Works, Ltd.) set at ℃ at a rate of 8 kg / hour,
Melt kneading was performed at a screw rotation speed of 100 rpm. The extrudate was cooled with water and pelletized, and then dried under reduced pressure at 120 ° C. for 15 hours to produce a resin composition. The resin composition was injection-molded with an injection molding machine at a cylinder temperature of 310 ° C. and a mold temperature of 140 ° C. to prepare a test piece.

Evaluation of each characteristic of the resin composition (molded product) of the present invention was carried out by the following methods. (1) Flexural modulus: The flexural modulus at 23 ° C. was evaluated according to the method specified in ASTM D790. (2) Tensile breaking elongation: The tensile breaking elongation at 23 ° C. was evaluated according to the method specified in ASTM D638. (3) Izod impact strength: The Izod impact strength with V-notch at 23 ° C. was evaluated according to the method defined in ASTM D256. (3) Heat resistance: The heat distortion temperature was measured under a load of 18.6 kg according to the method specified in ASTM D648. The characteristic evaluation results are shown in Table 1.

[0052]

[Table 1]

[0053]

As described in detail above, the resin composition of the present invention is lightweight, has excellent heat resistance and mechanical strength,
It also has excellent impact resistance. Such a resin composition of the present invention can be suitably used for various engineering plastics, particularly electric / electronic parts, automobile parts, home electric appliance parts, industrial parts and the like.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display area C08L 81/02 LRG C08L 81/02 LRG

Claims (6)

[Claims] 1. A composition comprising the following components (A) and (B):
A resin composition in which (A) is 100 parts by weight and (B) is 1 to 100 parts by weight. (A) Polyphenylene sulfide resin, (B) (a) 100 parts by weight of polyolefin resin,
(B) The following general formula (I): (In the formula, Ar represents a C _{6 to} C ₂₃ aromatic hydrocarbon group bonded to at least one glycidyloxy group, and R represents a hydrogen atom or a methyl group.) A compound having a glycidyl group And / or 0.1 to 30 parts by weight of unsaturated glycidyl ester, (c) vinyl monomer 0.1
To 500 parts by weight, and 0.001 to 10 parts by weight of the radical polymerization initiator (d) based on 100 parts by weight of the total amount of the components (b) and (c) are prepared. In the aqueous suspension, (b) a compound having a glycidyl group represented by the general formula (I) and / or an unsaturated glycidyl ester and (c) a vinyl monomer are added to the above (a).
And (b) a compound having a glycidyl group represented by the general formula (I), which is impregnated with a polyolefin resin, and /
Alternatively, a graft-modified polyolefin resin obtained by polymerizing an unsaturated glycidyl ester and (c) a vinyl monomer with the (a) polyolefin resin. 2. A compound having a glycidyl group represented by the general formula (1) has the following structural formula (II): The resin composition according to claim 1, which is a compound represented by: 3. The resin composition according to claim 1, wherein the unsaturated glycidyl ester (b) is glycidyl methacrylate. 4. The vinyl monomer (c) is an aromatic vinyl compound, an alkyl acrylate having an alkyl group having 1 to 22 carbon atoms, or a methacrylic acid having an alkyl group having 1 to 22 carbon atoms. Alkyl esters, vinyl alkyl ethers having an alkyl group having 1 to 22 carbon atoms, vinyl alcohol, unsaturated nitrile compounds, unsaturated amino compounds, maleic acid dialkyl esters having an alkyl group having 1 to 9 carbon atoms, and alkyl groups The resin composition according to claims 1 to 3, which is at least one selected from the group consisting of an allyl alkyl ether having 1 to 8 carbon atoms, a diene compound, maleic anhydride, maleic acid, acrylic acid, methacrylic acid, and vinyl acetate. Stuff. 5. The (c) vinylic monomer is styrene or α
The resin composition according to claim 4, which is at least one selected from the group consisting of methylstyrene, methyl methacrylate, allyl methacrylate, butyl acrylate, and acrylonitrile. 6. Silica, talc, mica, glass fiber, with respect to 100 parts by weight of the resin composition according to claim 1.
1 to 100 parts by weight of at least one filler selected from the group consisting of neutral clays, carbon fibers, wholly aromatic polyester fibers, aromatic polyamide fibers, silicon carbide fibers, titanic acid fibers, ceramic fibers and metal fibers. The resin composition obtained from.