JPS63205358A - Thermoplastic composition - Google Patents

Abstract

PURPOSE:To improve the compatibility of a polyphenylene resin with other thermoplastic resin and to enable the formation of molded products having excellent appearance and high mechanical strengths, by blending a mixture of a polyphenylene sulfide resin and other thermoplastic resin with a maleimide compd. CONSTITUTION:This thermoplastic composition contains three components A to C. (A): 99-1pts.wt. polyphenylene sulfide resin and/or block copolymer composed of a polyphenylene sulfide moiety and a polyphenylene sulfide sulfone moiety, (B): 1-99pts.wt. other thermoplastic resin, and (C): 0.1-20pts.wt. (per 100pts.wt. of the total of the components A and B) moleimide compd. Examples of the component B are polyesters, polyarylates, polycarbonates, polyphenylene oxides, polyamides, polyimides, polysulfones, polyether ketones, polyamide elastomers, polyester elastomers, alpha-olefin (co)polymers and a modified products thereof.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to polyphenylene sulfide (hereinafter abbreviated as PPS) and/or a block copolymer (hereinafter referred to as block copolymer) consisting of a PPS moiety and a polyphenylene sulfide sulfone moiety. This relates to thermoplastic resin compositions made by using a maleimide compound in combination with other thermoplastic resins to improve their compatibility with other thermoplastic resins, and to produce molded products with excellent appearance and improved mechanical properties. It can be used for injection molding, extrusion molding materials, etc. in various fields.

(Prior Art and Problems to be Solved by the Invention) PPS is known as a high-performance engineering plastic with excellent heat resistance, chemical resistance, and flame retardancy. However, PPS has little elongation, is brittle, and has a glass transition point of about 90° C., so it has major drawbacks such as a sudden decrease in elastic modulus above the glass transition point. In an attempt to improve these drawbacks, many methods of blending with various thermoplastic resins are known.

In addition, other thermoplastic resins have heat resistance, chemical resistance, flame retardancy,
Many studies have been made on blending pps as an attempt to improve moldability and the like.

However, such blends have poor compatibility and have problems such as deterioration of the surface condition of molded products and deterioration of mechanical properties.

(Means and effects for solving the problem) As a result of intensive studies, the present inventors discovered a maleimide compound as a component that improves the compatibility of pps and/or monoblock copolymers with other thermoplastic resins. We have now been able to provide a highly practical molding material that exhibits the characteristics of each polymer component.

That is, the present invention provides a block copolymer consisting of (g)yW+)-yenylene sulfide and/or a polyphenylene sulfide moiety and a polyphenylene sulfide sulfone moiety.
99 to 1 part by weight (B) 1 to 99 parts by weight of another thermoplastic resin (based on a total of 100 parts by weight of Q maleimide compound 0.1 to 20 parts by weight (body) and (B)) A thermoplastic resin composition is provided.

PPS in the present invention can be obtained by various known methods. For example, methods for producing it include polymerizing p-dichlorobenzene in the presence of sulfur and sodium carbonate, sodium sulfide, sodium bisulfide and sodium hydroxide, or hydrogen sulfide and sodium hydroxide in a polar solvent. Alternatively, methods include polymerization in the presence of sodium aminoalkanoate, self-condensation of p-chlorothiophenol, etc., but sodium sulfide A common method involves reacting p-dichlorobenzene with p-dichlorobenzene. At this time, to adjust the degree of polymerization, use cal? An alkali metal salt of phosphoric acid or sulfonic acid may be added, or an alkali hydroxide may be added. As copolymerization components, 30 tro groups, phenyl groups, alkoxy groups,
Force/I/Bic acid group or Cal? (indicates the metal base of phosphoric acid)
, as long as it does not significantly affect the crystallinity of the trifunctional mer. When phenyl, biphenyl, naphthyl sulfide bonds, etc. with trifunctionality or more are selected for copolymerization, the copolymerization is 3 molar or less, more preferably 1 molar or less. Specific methods for producing such pps include, for example, (1)
Reaction of a halodane-substituted aromatic compound with an alkali sulfide (see U.S. Patent No. 2,513,188, Japanese Patent Publication No. 44-27671 and Japanese Patent Publication No. 45-3368), (2) in the coexistence of an alkali catalyst or copper salt of thiophenols, etc. (3) condensation reaction of an aromatic compound with sulfur chloride in the presence of a Lewis acid catalyst (see Japanese Patent Publication No. 46-27255 and Belgian Patent No. 1160660) 29437), (A) Process for producing high molecular weight pps (% Kosho 52
-12240, Special Publication No. 54-8719, Special Publication No. 53-2
5588. Special Publication No. 57-334, Special Publication No. 55-4313
9, USP 4350810, USP 4324886
) etc.

Further, the block copolymer in the present invention is a block copolymer having mainly polyphenylene sulfide sulfone (hereinafter abbreviated as ppss) moieties, and is used as an uncrosslinked product, a crosslinked product, or a mixture thereof.

As disclosed in Japanese Patent Application No. 60-252857, the block copolymer can be produced by, for example, reacting the end groups of ppss with the end groups of PPS. It is necessary to use a reactive group such as a sulfide group (structural formula: Na5-). As a method of obtaining such pps, the amount of sodium sulfide component of the monomer is adjusted in advance during the polymerization reaction.
- A method in which the reaction is carried out in a 1 to 20 molar excess relative to the dichlorobenzene component can be mentioned.

On the other hand, it is defined as a polymer constituting the block copolymer of the present invention. The molecular weight of this polymer is the logarithmic viscosity η
1nh (where ηinh is phenol/1,1,2.
3 in 2-tetrachloroethane (3:2 weight ratio) mixed solvent
The value was measured at 0°C and calculated according to the following formula: ηinh = tn (relative viscosity)/polymer concentration. ) is 0.0
A value in the range of 5 to 1.0 is preferred. An example of a method for polymerizing this tellimer is a method in which dihaloaromatic sulfo/ and an alkali metal sulfide are reacted in an organic amide solvent (see US Pat. No. 4,102,875).

pps used when synthesizing the block copolymer of the present invention
For example, s can be added to the end of the polymer, for example, by reacting the dihaloaromatic sulfone in a 5 molar excess with respect to the amount of the alkali metal sulfide during the polymer synthesis reaction (US Pat. No. 43012).
74).

When carrying out the copolymerization reaction of ppss and pps in the method of the present invention, it is also possible to use a method of adding a binder such as dihaloaromatic sulfone or sulfurized IJium as a third component. In addition, PPS and ppss, which are block copolymers, may be used without departing from the purpose of the present invention.
It is also possible to use a method in which the other heptamer component is polymerized in the presence of one of the polymers to finally obtain a copolymer.

Furthermore, when carrying out the copolymerization reaction, it is most preferable to make the number of terminal reactive groups of pps and ppss the same, since a block copolymer can be obtained in good yield. On the other hand, when the number of terminal groups of either component is excessive, only the block copolymer can be recovered by fractionating or extracting only the unreacted homopolymer component after the reaction is completed.

The maleimide compound in the present invention is usually a compound represented by the following general formula (1).

The maleimide compound represented by the above formula can be produced by a known method of preparing maleamic acid by reacting maleic anhydride with a monoamine or polyamine, and then cyclodehydrating the maleamic acid. As for the amines used, aromatic amines are preferred from the viewpoint of heat resistance of the final composition, but if flexibility etc. are desired, alicyclic amines and aliphatic amines may be used.

Examples of preferred maleimide compounds include phenylmaleimide, N,N'-(methylene di-p-phenylene)
simaleimide, N, N'-(oxydi-p-)unilene) simaleimide, N, N'-m-phenylene dimaleimide, N, N'-p-phenylene dimaleimide, N, N
' -m-Kyzylene dimaleimide, N, N' -1)-
These include pheasantine dimaleimide, N,N'-hexamethylene dimaleimide, and a compound represented by the following general formula (2).

(n=0.1-10) Polyamino bismaleimide, which is an addition reaction product of t, N, 1 (-(methylenedi-p-phenylene) simaleimide and diaminodiphenylmethane), can also be used.

Other thermoplastic resins include polyester, polyarylate,
The polycarbonate is at least one selected from ester, polyphenylene oxide, polyamide, polyimide, polysulfone, polyetherketone, polyamide type elastomer, IJ ester type elastomer, α-olefin (co)polymer, or a modified product thereof.

For example, in order to improve the elastic modulus above the glass transition point, which is a drawback of PPS and block copolymers of PPS and ppss, combinations of polyarylate, polyphenylene oxide, polyimide, polysulfone, polyether ketone, etc. are selected. , and to improve the toughness, α
- Combinations of olefin (co)polymers or modified products thereof, polyamide elastomers, polyester elastomers, polycarnates, polyesters, polyamides, etc. are selected.

Blending PPS with other thermoplastic resins other than polyetherketone improves chemical resistance, etc., and PPS can be blended with polyarylate, polyphenylene oxide, polyimide, polyamideimide, polyetherimide, polysulfone, polyethersulfone, and polyetherketone. Blending them has the effect of improving fluidity and moldability.

Even if pps and other thermoplastic resins are blended, their compatibility is poor, resulting in problems such as deterioration of the surface condition of molded products and deterioration of mechanical properties.

Adding a maleimide compound as a third component to pps and other thermoplastic resins surprisingly improves their compatibility,
The appearance of the molded product also becomes good, and the problem of deterioration of mechanical properties is also eliminated. Although the reason for this is not clear, it is thought that the unsaturated group of the maleimide compound improves compatibility with both pps and other thermoplastic resins since no reaction occurs and thickening occurs.

Polyester is a polymer or copolymer obtained by a condensation reaction containing dicarboxylic acid and diol as main components.

The polyester used in the present invention includes terephthalic acid,
Isophthalic acid, orthophthalic acid, naphthalenedicarboxylic acid, 4,4'-diphenyldicarboxylic acid, diphenyl etherdicarboxylic acid, α,β-bis(A-carboxyphenoxy)ethane, adipic acid, sepatic acid, azelaic acid, decane Dicarboxylic acids such as dicarboxylic acid, dodecane dicarboxylic acid, dicarboxylic acid, cyclohexanedicarboxylic acid, dimer acid, etc. or their ester-forming derivatives, and ethylene glycol, propylene glycol, butanediol, intanediol, neopentyl glycol, hexanediol, octanediol , decanediol, cyclohexane dimetatool, hydroquinone, bisphenol A, 2.2-
, bis(A'-hydroxyethoxyphenyl)furonoyane, xylene glycol, polyethylene ether glycol, polytetramethylene ether glycol, and aliphatic polyester oligomers having hydroxyl groups at both ends. ,
Normally, the intrinsic viscosity [η] measured at 30°C in a mixed solvent of phenol and tetrachloroethane in a weight ratio of 6:4 is 0.
A range of 3 to 1.5 de/IP is used.

It may contain polyfunctional ester-forming components such as trimethylolethane, trimethylolethane, glycerin, pentaerythritol, trimellitic acid, trimesic acid, and pyromellitic acid within a range that can maintain thermoplasticity. .

Particularly preferred polyesters include polyethylene terephthalate, polybutylene terephthalate, polyhexamethylene terephthalate, poly(ethylene butylene terephthalate), poly(cyclohexane dimethylene terephthalate), 2,2-bis(β-hydroxyethoxytetrabromophene A/ ) Flopane copolymerized polybutylene terephthalate and the like.

A liquid crystalline polyester may be used as the polyester used in the present invention. What is liquid crystalline polyester?
It is an aromatic polyester capable of forming an anisotropic melt phase at a temperature of 0° C. or lower, and includes, for example, those consisting of the following repeating portions I and (2) as essential components.

Acid component. (However, R is methyl, chloro, bromo, or a mixture thereof, and is a group substituted with hydrogen present at the aromatic apex.) The anisotropic melt phase formation temperature of the aromatic polyester is about 4
00℃ or less, preferably 260 to 350℃, especially 28
0 to 330°C is preferred.

Polyarylate is a polyester synthesized from bisphenol or its derivative and dibasic acid or its derivative. Examples of bisphenols: triteha, 2.2-bis-(A-hydroxyphenyl)-gulonoyan, 4.4
'-dihydroxy-diphenyl ether, 4,47-dihydroxy-3,3'-dimethyldiphenyl ether,
4.4'-dihydroxy-3,3'-dichlorodiphenyl ether, 4.4'-dihydroxy-diphenyl sulfide, 4.4'-dihydroxy-diphenyl sulfone, 4.4'-dihydroxy-diphenyl ketone, bis-
(A-hydroxyphenyl)-methane, 1-bis-
(A-hydroxyphenyl)-ethane, 1,1-bis-
(A-hydroxyphenyl)-n-butane, no(A-
hydroxyphenyl)-cyclohexyl-methane, 1.
1-bis-(A-hydroxyphenyl) -2,2,2
-Trichloroethane, 2,2-bis-(A-hydroxy-3,5-dibromophenyA/)-, propane, 2.2
-bis-(A-hydroxy-3,5-dichlorophenyl)-propane, etc., but particularly preferred is 2,2-bis-(A-hydroxyphenyl)-propane, also known as bisphenol A. It is.

Examples of dibasic acids include aromatic dicardic acids such as phthalic acid, isophthalic acid, terephthalic acid, bis-(A-cargoxy)-diphenyl, bis-(A-cargoxyphenyl)-ether, bis-( A-Cal is xyphenyl)-
Sulfone, bis-(A-carboxyphenyl)-rudenyl, bis-(A-carboxyphenyl)-methane, bis-(A-carboxyphenyl)-dichloromethane, 1
．． 2- and 1,1-bis-(A-carboxyphenyl)-ethane, 1,2- and 2,2-bis-(A-carboxyphenyl)-propane, 1,2- and 2,2-
Bis-(3-carboxyphenyl)-furopane, 2,2
-bis-(A-carxyphenyl)-1,1-dimethylpropane, 1,1- and 2,2-bis-(A-carboxyphenyl)-butane, 1,1- and 2,2-bis-( A-carboquinphenyl)-pentane, 3,3-
Bis-(A-ka/I/goxyphenyl)-hebutane, 2
, 2-bis-(A-carboxyphenyA/)-hebutane and aliphatic acids such as oxalic acid, arginic acid, succinic acid, malonic acid, cepatenic acid, geltaric acid, azelaic acid, phosphoric acid, etc. However, isophthalic acid and terephthalic acid or mixtures of these derivatives are preferred.

The polycarbonate (hereinafter abbreviated as PC) of the present invention is a homogeneous P
C or PC copolymers based on, for example, one or more of the bisphenols listed below can be used. hydroquinone,
Resorcinol, dihydroxydiphenyl, bis-(hydroxyphenyl)-alkane, bis-(hydroxyphenyl)-cycloalkane, bis-(hydroxyphenyl)
-sulfide, bis-(hydroxyphenyl)-ketone, bis-(hydroxyphenyl)-ether, bis-
(Hydroxyphenyl)-sulfoxide, bis-(hydroxyphenyl)-sulfone and α, α′-bis-
(Hydroxyphenyl)-diisozolobylbenzene and their compounds substituted with alkyl or halodane in the nucleus.

Among these, specific examples of preferable bisphenols include 4,4-dihydroxydiphenyl, 2,2-bis-(A-hydroxyphenyl)-propane, and 2,4-bis-(A-hydroxyphenyl)-2. - methylbutane,
1,1-bis-(A-hydroxyphenyl)-cyclohexane, α,α′-his-(A-hydroxyphenyl)
-p-diisopropylbenzene, 2,2-bis-(3-
Methyl-4-hydroxyphenyl)-furonone, 2,
2-bis-(3-chloro-4-hydroxyphenyl)-
Pronogun, bis-(3,5-dimethyl-4-hydroxyphenyl)-methane, 2,2-bis-(3,5-dimethyl-4-hydroxyphenyl)-gulonoman, bis-
(3,5-dimethyl-4-hydroxyphenyl)-sulfone, 2,4-bis-(3,5-dimethyl-4-hydroxyphenyl)-2-mercaptan, 1,1-bis-
(3,5-dimethyl-4-hydroxyphenyl)-cyclohexane, α,α′-his-(3,5-dimethy/l/
+4-hydroxyphenyl)-p-diisopropylbenzene, 2,2-bis-(3,5-dichloro-4-hydroxypheny/I/)-7'lonoya/and 2,2-bis-(3,5 -dibromo-4-hydroxyphenyl)-
Examples include propane, preferably ij: 2.2-bis-(A-hydroxyphenyl)-furopane, 2.2-bis-(3,5-dimethyl-4-hydroxyphenyl)-
solomono, 2,2-bis-(3,5-cyclo4-
hydroxyphenyl)-propane, 2,2-bis-(3
, 5-dibromo-4-hydroxyphenyl)-pronocentine and 1,1-bis-(A-hydroxyphenyl)-cyclohexane.

Preferred PCs are those based on the preferred bisphenols described above. Particularly suitable PC copolymer i 2.2-
It is a copolymer of his-(A-hydroxyphenyl)-pronothine and one of the other particularly preferred bisphenols mentioned above.

Other particularly suitable PCs are 2,2-bis-(A-hydroxypheny/I/)-f-ropane or 2,2-bis-(3,5
'-Dimethyl-4-hydroxyphenyl)-zolone is the only pace.

In addition, pc is determined by a known method, for example, bisphenol and diphenyl carbon. It can be produced by a method such as a melt transesterification reaction with phosphate, or a two-phase interfacial polymerization method with bisphenol and phosdan.

Polyphenylene oxide is also called polyphenylene ether, and for example, the general formula CD (wherein R1 and R
2 represents hydrogen, halodane, alkyl having 4 or less carbon atoms, haloalkyl, alkoxy, allyl derivative having 9 or less carbon atoms, or aralkyl group, and n represents the number of repeating units and is an integer of 10 or more. ) 2,6-disubstituted phenol polymer, 2.6
- A polymer of a disubstituted phenol and a polyhydric phenol (see Japanese Patent Application No. 49-24265), etc., and usually has a molecular weight of 2,000 or more, preferably 10,000 to 35,000.

Such resins generally contain phenols such as phenol, 2,6-dimethylphenol, 2,6-dinitylphenol, 2,6-diitupropylphenol 7-/l/, 2
-Methyl-6-medoxyphenol etc. as metal/amine,
It is obtained by a dehydration reaction with oxygen in the presence of a co-catalyst such as a metal chelate/basic organic compound, but any production method can be used as long as the resin satisfies the conditions described above. It's okay to have one. Specific examples include 2,6-dimethylphenylene oxide polymer, 2,6-nomethylphenol A//bisphenol A (former/latter-9515 molar ratio) copolymer, 2
．． Examples include 6-noethylphenylene oxide polymer. Furthermore, ppo grafted with styrene may be used.

In the present invention, the polyamide resin used as one of the raw materials includes various well-known polyamide resins. For example, terephthalic acid, isophthalic acid, oxalic acid, adipic acid, sepacic acid, dicarboxylic acids such as 1,4-cyclohexyldicarboxylic acid, ethylene diamine, pentamethylene diamine, hexamethylene diamine, decamethylene diamine, 1,4-cyclohexyl diamine, m-
Polymerization condensation of diamines such as xylylene diamine; Polymerization of cyclic lactams such as caprolactam and laurolactam:
Can be obtained by polycondensation of aminocarb/acids such as aminononanoic acid, aminoundeca/acid, or copolymerization of the above-mentioned cyclic lactams, dicarboxylic acids, and diamines, 6 nylon, 66 nylon, 610
Examples include nylon, 612 nylon, 11 nylon, 12 nylon, 66/610 copolymer nylon, 6/66 copolymer nylon, and the like, and particularly preferred are 6 nylon, 66 nylon, and 12 nylon.

Furthermore, cyclic lactams such as laurolactam, aromatic dicarboxylic acids such as terephthalic acid and isophthalic acid, and 4,4
'-Diamino-3,3'-dimethylcyclohexylmethane and other cycloaliphatic diamines; polycondensation of asymmetric diamines such as trimethylhexamethylene diamine and aromatic diamines. High quality polyamide resins are also suitable. The polyimide has the general formula [Formula, R is a tetravalent aromatic group or alicyclic group containing at least one carbon 6 member, R1 is a benzenoid group of the formula, R2 is the formula -〇-1H3, R5 and R4 are selected from the group consisting of alkyl and aryl groups, and n is a divalent group selected from the group consisting of an alkyl group and an aryl group; is an integer. ] Polyimide having a repeating unit represented by the general formula [wherein Ra represents the 10th to 90th position of the repeating unit, and represents the remainder of the repeating unit, n is an integer greater than or equal to 2 such that the polymer is thermally stable at at least about 200°C. ] Polyimide having a repeating unit represented by the general formula In the residue, R' represents hydrogen, a methyl group or a phenyl group, respectively, and n is an integer of 2 or more. ] Polyamide-imide having a repeating unit represented by the general formula [where Ar is a trivalent aromatic group containing at least one 6-carbon member, R is a divalent aromatic and/or aliphatic group] is the residue of ] Includes polyetherimide having a repeating unit represented by the following.

? Lysulfone is defined as a polyarylene compound in which arylene units are located in a disordered or orderly manner together with ether and sulfone bonds, such as the following
Examples include those having the structural formula (in the formula, n represents an integer of 10 or more), but preferably those having the structure of ■ or ■.

CH3 polyetherketone contains a repeating unit of formula [1] and/or a repeating unit of formula [2] alone or together with other repeating units, and has an intrinsic viscosity (1, V,) of 0.7 or more. It is a tough crystalline thermoplastic aromatic polyetherketone. Other repeating units other than formula [1] and/or formula [2] include formula [3] [wherein A is a direct bond, oxygen, sulfur, -5o2-1-C
O is a mono- or divalent hydrocarbon group. ] and formula [4].
5] and formula [6] are in the ortho position or noJ with respect to Q'? Q and Q' are the same or different, -co- or -5o2-
, Ar' is a divalent aromatic group, and n is 0
, 1.2 or 3. ] Contains repeating units indicated by.

The polyamide elastomer is a block copolymer elastomer having hard segments of nylon 11 and 12 and soft segments of polyether or polyester components. Specific examples of the polyether component include (-OR+n (R is a C2-C12 alkylene group), and specific examples of the terester component include polycabrolactone or) 10-R-OH (R is a C2-C12 alkylene group).
12 fullkylene groups) and (g, TANCOOH) 2 to 3 as starting components. A typical product name is provided by EMSCHEMIE under the name "Grillamide." Random copolymers of nylon 6, nylon 66, nylon 610, nylon 11 and nylon 12 can also be used.

A polyester elastomer is a block copolymer of a high melting point hard segment mainly consisting of alkylene terephthalate units and a low melting point soft segment consisting of an aliphatic polyester or polyether. Segments mainly composed of alkylene terephthalate units that constitute high melting point segments include terephthalic acid and ethylene glycol, propylene glycol, tetramethylene glycol, pentamethylene glycol, 2,2-dimethyl-trimethylene glycol, hexamethylene glycol, and decamethylene. Mainly units consisting of alkylene glycol such as glycol, and in some cases dicarboxylic acids such as isophthalic acid, 1,5-naphthalene dicarboxylic acid, 2,6-naphthalene dicarboxylic acid, dibenzoic acid, bis(p-cal is xyphenyl) Methane, aromatic dicarboxylic acids such as 4,4'-sulfonyl dibenzoic acid, aliphatic dicarboxylic acids described later, diols such as p-xylylene glycol and cyclohexane dimetatool as glycols,
There is no problem even if a small amount of oxyacid such as p-oxybenzoic acid or p-(β-hydroxyethoxy)benzoic acid is contained as a component.

In addition, low melting point soft segments made of aliphatic polyester or polyether include polyether glycols such as poly(ethylene oxide) glycol, poly(propylene oxide) glycol, and poly(tetramethylene oxide) glycol; Mixture or copolymer, carbon number 2~
Polyesters produced from 12 aliphatic dicarboxylic acids and aliphatic glycols having 2 to 10 carbon atoms, such as polyethylene adipate, polytetramethylene azelate,
Polyethylene se9ate, polyneotylene sepacate, polytetramethylene dodecanate, polytetramethylene azelate, polyhexamethylene azelate, poly-ε-caprolactone, etc., and the above aliphatic polyesters and aliphatic polyethers Examples include polyester polyether copolymers that are a combination of the following.

In the polyester type block copolymer of the present invention, the molecular weight of the low melting point soft segment is 400 to 600.
The content of the soft segment is preferably 0, and the proportion of the soft segment in the copolymer is preferably 5 to 80% by weight.

The α-olefin (co)polymer is at least 50 mo/l
/%, α-olefins, such as ethylene, propylene, butene-1, isobutyne, pentene-1, hexene-1, decene-1,4-methylbutene-1,4-methylbutene-1,4,4-dimethylintene -1, vinylcyclohexane, styrene, alpha-methylstyrene, styrene substituted with lower alkyl substituents, or the like. It is also possible to use mixtures of the abovementioned olefins. Modified products obtained by grafting an unsaturated caldic acid or an unsaturated epoxy compound onto the α-olefin (co)polymer can also be suitably used.

As acid components, citraconic anhydride, 3-methyl-4-
Cyclohexene-1,2-cyclonic acid anhydride (hereinafter referred to as
PMMA), maleic anhydride, (methyl)nadic anhydride, itaconic anhydride, and epoxy components include glycidyl acrylate, glycidyl methacrylate, etc. α-olefin (co)polymer The graft polymerization amount is usually 0.1 to 2.0 parts by weight, preferably 0.2 to 1.5 parts by weight, per 100 parts by weight.

The ratio of pps to other thermoplastic resins is 99/1 to 1/99 (
If the weight ratio deviates from the range, the respective modification effects will be lost, and if the maleimide compound is less than 0.1 part by weight per 100 parts by weight of PP8 and other thermoplastic resins, the effect of improving compatibility will be ineffective. If the amount exceeds 20 parts by weight, molding becomes extremely difficult due to thickening.

The composition of the present invention includes fibrous reinforcing agents such as glass fibers, carbon fibers, potassium titanate, asbestos, silicon carbide, ceramic fibers, metal fibers, and silicon nitride; barium sulfate, calcium sulfate, kaolin, clay, and noerophyllants. , bentonite, sericite, zeolite, mica, mica, nephelinsinite, talc, atalpulgite, wollastonite, PMF, ferrite, calcium silicate, calcium carbonate, magnesium carbonate, dolomite, antimony trioxide, zinc oxide, Inorganic fillers such as titanium oxide, magnesium oxide, iron oxide, molybdenum dioxide, graphite, gypsum, glass beads, glass balloons, and quartz powder; organic reinforcing agents such as aramid fiber, etc.
It can be contained up to 80% by weight in the composition. When adding these reinforcing agents or fillers, known silane coupling agents can be used.

In addition, the composition of the present invention may contain small amounts of epoxy resin, mold release agent, coloring agent, heat stabilizer, ultraviolet stabilizer, blowing agent, flame retardant, flame retardant aid, and preventive agent without departing from the purpose of the present invention. It can contain a rusting agent and the like.

The composition of the invention can be prepared in various known ways. For example, the raw materials are mixed uniformly in advance using a mixer such as a tumbler or Henschel mixer, and then fed to a single-screw or twin-screw extruder where they are melt-kneaded at 230 to 400°C.
A method of pelletizing can be used.

(Effect of the invention) The present invention provides pps and/or PPS, l! : PP5
This composition has excellent compatibility between the block copolymer with S and other thermoplastic resins, and can provide a molded article with improved mechanical properties.

(Examples) Next, the present invention will be specifically explained with reference to Examples, but the present invention is not limited to these Examples.

Reference example 1 Sodium sulfide (60% purity) 984? and 47% of sodium hydroxide to 3080% of N-methylpyrrolidone. After heating to 205℃ while dehydrating, add paranochlorobenzene i i i 3? and N-methylpyrrolidone 5
10iI- was added and heated at 262° C. for 5 hours under pressure, then cooled, washed with water, and dried. The obtained polymer (pp
s) was thermally crosslinked in air at a temperature of 260 °C for 5 hours.

This will be referred to as Polymer (A).

The melt flow rate of polymer (A) is 316°C, 5k
The g load was 250.

Reference Example 2 Sodium sulfide (60% purity) 984/-1 Sodium hydroxide 471-1 Lithium acetate dihydrate 765? was added to 3080y of N-methylpyrrolidone, heated to 205°C while dehydrating, and p-dichlorobenzene 1113y
y-,N-methylpyrrolidone 510? 23 under pressure
The mixture was heated at 0°C for 2 hours and at 260°C for 3 hours, cooled, washed with water, and dried. The obtained pps is referred to as polymer (B).

The melt flow rate of polymer (B) is 316°C, 5k
The g load was 130.

Reference Example 3 A reaction was carried out in the same manner as in Reference Example 1 to obtain terminal chlorophenyl group-type pps (logarithmic viscosity ηinh O-22).

(ηLnh is a solution of 0.5 f/100 rnl)y
T? 'Jmer concentration te, phenol/1,1,2.2-
3 in a mixed solvent of tetrachloroethane (3:2 weight ratio)
Measured at 0°C, formula ηlnh = tn (logarithmic viscosity)/
Calculated based on polymer concentration. ) Also, 3100y of N-methylpyrrolidone, 2.7y of sodium sulfide, 1009yy of water, and 3.7yy of sodium hydroxide.
5? The temperature was raised to 200°C under a nitrogen atmosphere, and then p-dichlorobenzene 1029? , N-methylpyrrolidone 7001? was added and reacted at 260°C to obtain a terminal chlorphenyl group-type ppss with a logarithmic viscosity of 0.14.

Then, the above PPS 2370? , the above PP5S30
Add 0 and N-methylpyrrolidone 1200/-;
The reaction was carried out at 220° C. under a nitrogen atmosphere to obtain a block copolymer 486y-. Such block copolymers are ppss
It contains 46% by weight of
+j? 20 in α-chlornaphthalene at a polymer concentration of
(measured at 6°C) was 0.19.

Examples 1 to 3, Comparative Examples 1 to 5 70 parts by weight of Polymer A (PPS) obtained in Reference Example 1, 30 parts by weight of I resulfone, and 2 parts by weight of bismaleimide were uniformly premixed and then heated to 330°C. With vent 4
The mixture was kneaded using a 00 extruder and pelletized.

A test piece was made using this inlet using an injection molding machine. The appearance of the test piece was light brown and uniform with excellent compatibility.

Test pieces of other examples were prepared in the same manner as in Example 1 using the formulations shown in Table 1. Its characteristics are shown in Table-1.

Examples 4 to 12, Comparative Examples 6 to 14 The formulations shown in Table 2 were extrusion kneaded and pelletized at 330°C. A test piece was made using this Nilet. The characteristics of each are shown in Table-2.

Examples 13-30. Comparative Examples 15 to 32 The formulations shown in Tables 3, 4, 5, and 6 were extrusion-kneaded and pelletized at 290°C to create test pieces. Each characteristic is shown in Tables 3, 4, 5, and 6.

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Claims (1)

[Claims] 1. (A) Polyphenylene sulfide and/or block copolymer 99-1 consisting of a polyphenylene sulfide moiety and a polyphenylene sulfide sulfone moiety
Parts by weight (B) 1 to 99 parts by weight of other thermoplastic resins (C) 0.1 to 20 parts by weight of a maleimide compound (based on a total of 100 parts by weight of (A) and (B)). Plastic resin composition. 2. The other thermoplastic resin is polyester, polyarylate, polycarbonate, polyphenylene oxide, polyamide, polyimide, polysulfone, polyether ketone, polyamide type elastomer, polyester type elastomer, α-olefin (co)polymer or a modified product thereof, The composition according to claim 1, which is at least one thermoplastic resin selected from the following.