JP3173006B2 - Resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial application field> The present invention relates to a resin composition comprising a polyarylene sulfide or other thermoplastic resin having improved compatibility, and has heat resistance, chemical resistance, As a molding material with excellent mechanical properties such as dimensional stability, flame retardancy and impact resistance, and excellent adhesion, it is used in a wide range of fields such as electricity, electronic parts, precision equipment parts, automotive parts, sports materials, sundries, etc. .

<Prior art> Polyarylene sulfide resin (PAS resin) represented by polyphenylene sulfide (PPS) has heat resistance,
High rigidity, excellent moldability, flame retardancy, chemical resistance,
Due to its outstanding performance in dimensional stability, it is attracting attention as a high-performance, high-performance engineering plastic. However, the PAS-based resin has also been pointed out with some disadvantages. For example, mechanical and mechanical adhesion such as impact resistance,
In terms of adhesiveness, weather resistance, burr characteristics of molded articles, and PPS, the glass transition temperature is relatively low at 80 to 90 ° C., and the elastic modulus sharply decreases at a temperature higher than the glass transition temperature.

By blending PAS resin and other thermoplastic resins, the drawbacks of PAS resin can be improved or
Many attempts have been made to impart the excellent properties of AS resins to other resins.

However, in any case, because the compatibility with the thermoplastic resin to be blended with the PAS-based resin is insufficient, the intended effect is not sufficiently exhibited, or in some cases, the properties are rather deteriorated, Or, there have been other problems. These problems differ depending on the type of thermoplastic resin blended with the PAS-based resin. For example, Japanese Patent No. 1005081 discloses a composition of a PAS-based resin and a polyad, a phenoxy resin, a thermoplastic polyester, a polyethylene, etc. for the purpose of flame retardancy. Although achieved, there was a problem that mechanical properties such as impact resistance were not improved or rather lowered due to insufficient compatibility. Also, JP-A-56-34032 discloses PPS
And in the case of polyphenylene oxide, U.S. Pat.
In 506, the case of PPS and polysulfone, polycarbonate, polyphenylene oxide, in the case of PPS and ABS resin in JP-A-63-304046, and in the case of PPS and polyarylate in JP-A-53-57255. However, there is a problem that properties such as impact resistance are not improved due to insufficient compatibility in each case. Polyamide and polyphenylene oxide also have problems such as insufficient adhesiveness, and polyamide has problems such as insufficient improvement in water absorption. On the other hand, JP-A Nos. 59-58052, 59-155461, 59-155462, and 5
9-164360, 59-207921, 59-213758, 59
JP-64657-A discloses a method of adding an epoxy resin for the purpose of improving the blend compatibility between PPS and various thermoplastic resins, but this method also does not have a sufficient compatibility improving effect. At the same time, the addition of an epoxy resin causes a problem that the influence of thermal decomposition and gelation cause the moldability to decrease.

<Problems to be Solved by the Invention> The present invention improves the blend compatibility of other thermoplastic resins to be blended with a PAS-based resin, for example, it has not been sufficiently improved in the past, or in some cases, It provides a resin composition that imparts the excellent properties of both resins to be blended, such as improved mechanical properties such as impact resistance, which have been reduced, and does not improve depending on the resins to be blended. The purpose of this study was to improve the adhesiveness and surface affinity for painting.

<Means for Solving the Problems> That is, the present invention provides a polyarylene sulfide resin,
A polyarylene sulfide-based resin containing a carboxyl group, and at least one other thermoplastic resin, and wherein the polyarylene sulfide-based resin containing a carboxyl group is a dihalogeno aromatic carboxylic acid and / or A block copolymer containing the alkali metal salt as a copolymerization component, and a carboxyl group-containing arylene sulfide structural unit content of 0.5 to 30.
The present invention relates to a resin composition characterized in that the resin composition is mol% resin.

The PAS resin used in the present invention has the structural formula (-Ar-S) n
PAS resins represented by (Ar: arylene group). Here, -Ar- of the arylene group is a divalent aromatic residue such as P-phenylene, m-phenylene, o-phenylene, 2,6-naphthalene, 4,4′-biphenylene, or And the like, and a divalent aromatic residue containing at least two aromatic rings having 6 carbon atoms such as F, Cl, B
Substituents such as r and CH ₃ may be introduced. This may be a homopolymer, a random copolymer, a block copolymer, and a linear, branched, or crosslinked type, or a mixture thereof is used.

The melt viscosity of the PAS resin is of the crystallinity in a temperature range of the melting point plus 20 ° C., a dynamic viscosity at 10rad / sec [η '] is 10 to 10 ⁵ poise, preferably those of 50 to 50,000 poise However, for amorphous materials, the glass transition temperature plus 100
In a temperature range of ° C., a dynamic viscosity at 10 rad / sec is 50-10 ⁶ poise, preferably used are those of 100 to 5 × 10 ⁵ poise. The glass transition temperature is a peak value in the temperature dispersion of the loss elastic modulus [E ″] at 1 Hz.

Preferred PAS resins for use in the present invention are polyphenylene sulfide (PPS), polyphenylene sulfide sulfone (PPSS), polyphenylene sulfide ketone (PP
SK), and the PPS and PPSS parts, and the PPS part
It is a copolymer consisting of PPSK moieties.

PPS is Is a polymer containing 70 mol%, particularly preferably 90 mol% or more, of the structural unit represented by The other constituents contained in the PPS are mainly the above arylene groups.

Such PPS includes, for example, (1) a reaction between a halogen-substituted aromatic compound and an alkali sulfide (see U.S. Pat. No. 2,513,188, JP-B-44-27671 and JP-B-45-3368), and (2) thiophenols Reaction in the presence of an alkali catalyst or a copper salt (US Pat. No. 3,274,165)
(3) Synthesis of aromatic compounds by sulfur condensation with sulfur chloride in the presence of a Lewis acid catalyst (JP-B-46-27255, Belgian Patent No. 29439). And can be arbitrarily selected according to the purpose.

PPSS is mainly Is a polymer having a repeating unit. Examples of the PPSS polymerization method include a method of reacting a dihalo aromatic sulfone such as 4,4'-dichlorodiphenyl sulfone with an alkali metal sulfide such as sodium sulfide in an organic amide solvent.

PPSK is mainly Is a polymer having a repeating unit. PPSK polymerization method is
For example, there is a method of reacting 4,4'-dichlorobenzophenone with an alkali metal sulfide in an organic amide solvent.

On the other hand, the polyarylene sulfide-based resin containing a carboxyl group (CPAS-based resin) used in the present invention is a block copolymer containing a dihalogeno aromatic carboxylic acid and / or an alkali metal salt thereof as a copolymer component, Moreover, it is a resin having a carboxyl group-containing arylene sulfide structural unit content of 0.5 to 30 mol%, for example,
A block composed of a carboxyl group-containing polyarylene sulfide structural unit having a repeating unit represented by the above general structural formula (1), (2) or (3); and a repeating unit having the general formula (-Ar-S -) (Ar: an arylene group) and a block comprising a polyarylene sulfide structural unit.

(Wherein, Y is _{-O -, - SO 2 -,} - CH 2 -, - C (C
_{H 3) 2 -, - CO} -, - C (CF 3) 2 - or an single bond. The content of the carboxyl group-containing arylene sulfide structural unit represented by the above general formulas (1) to (3) is 0.5 to 30 mol%, preferably 0.8 to 20 mol% in the CPAS resin. The intended effect is particularly exhibited in such a range.

 Such a CPAS resin is a block type.

In addition, the viscosity of the CPAS resin is usually the melting point plus 20
℃ or glass transition temperature plus 10 for amorphous
It has a dynamic viscosity [η '] at 0 ° C. and 10 rad / sec of ⁵ to 10 ⁵ poise, preferably 10 to 10 ⁴ poise.

Preferable as a CPAS-based resin, the PAS portion is PPS,
PPSS, PPSK, a copolymer of PPS and PPSS or a copolymer of PPS and PPSK, wherein the CPAS portion is a carboxyl group-containing polyphenylene sulfide (CPPS) represented by the above general formula (1)
There are various copolymers consisting of the following combinations. The most typical example is a copolymer in which the PAS part is PPS and the CPAS part is CPPS represented by the general formula (1).

The method for producing the CPAS resin includes, for example, (1) a dihalogeno aromatic carboxylic acid and / or an alkali metal salt thereof and a sulfidizing agent (alkali sulfide: alkali metal hydrosulfide) in a polar solvent in which a PAS prepolymer is present. (2) reacting a dihalogeno aromatic compound with a sulfidizing agent in a polar solvent in which a CPAS prepolymer is present, and (3) reacting a PAS prepolymer in a polar solvent. There is a method of reacting the polymer with the CPAS prepolymer.

The thermoplastic resin used in the present invention may be any thermoplastic resin other than the PAS-based resin described in the known literature on PAS-based resins, but polyamides, thermoplastic polyesters, polycarbonates, polyarylates , Polysaphon, polyphenylene oxide, polyetherketone, polyetherimide, phenoxy resin, α
-Olefin copolymers, styrene copolymers, ABS resins and fluorine resins are particularly preferably used. The thermoplastic resin used for blending with the PAS-based resin may be used alone or in combination of two or more. It is also possible to use copolymers and modified products of these thermoplastic resins.

Various known polyamides can be used. For example, oxalic acid, adipic acid, speric acid, sebacic acid, terephthalic acid, isophthalic acid, dicarboxylic acids such as 1.4-cyclohexyldicarboxylic acid and ethylenediamine, pentamethylenediamine, mexamethylenediamine, decamethylenediamine, 1.4-cyclohexyldiamine, m A polyamide obtained by polycondensing a diamine such as xylene diamine; a polyamide obtained by polymerizing a tubular lactam such as caprolactam or laurin lactam; or a copolymer of a cyclic lactam and a salt of a dicarboxylic acid and a diamine. And the like. Among these polyamides, 6 nylon, 66 nylon, 46 nylon, MXD6 nylon (copolymer of m-xylene diamine and adipic acid),
6.10 nylon, 66 / 6.10 nylon, 6/66 nylon, 12
Nylon, 11 nylon, 6 / 6T nylon (copolymer of salt of caprolactam, terephthalic acid, and hexamethylenediamine) and the like, and these polyamides may be used in combination of two or more. Particularly preferred are nylon 6, nylon 66, nylon 46, and MXD6 nylon.

As polyester resins, terephthalic acid, isophthalic acid, orthophthalic acid, naphthalenedicarboxylic acid, 4,
4'-diphenyldicarboxylic acid, diphenylether dicarboxylic acid, α, β-bis (4-carboxyphenoxy) ethane, adipic acid, sebacic acid, azelaic acid,
Decanedicarboxylic acid, dodecanedicarboxylic acid, cyclohexanedicarboxylic acid, dicarboxylic acid such as dimer acid or an ester-forming derivative thereof and ethylene glycol,
Propylene glycol, butanediol, pentanediol, neopentyl glycol, hexanediol, octanediol, decanediol, cyclohexanedimethanol, hydroquinone, bisphenol A, 2,2-
Bis (4-hydroxyethoxyphenyl) propane, xylene glycol, polyethylene ether glycol,
Polytetramethylene ether glycol, a polyester obtained from a glycol such as an aliphatic polyester oligomer having a hydroxyl group at both terminals, usually in a mixed solvent of phenol and ethane tetrachloride in a weight ratio of 6: 4, Those having an intrinsic viscosity {η} measured at 30 ° C. of 0.3 to 1.5 dt / g are used.

In addition, as a comonomer component, glycolic acid, hydroxybutyric acid, hydroxybenzoic acid, hydroxyphenylacetic acid, hydroxycarboxylic acid such as naphthyllicholic acid, propiolactone, butyrolactone, valerolactone, lactone compound such as caprolactone or retains thermoplasticity To the extent possible, it may contain polyfunctional ester-forming components such as trimethylolpropane, trimethylolethane, glycerin, pentaerythritol, trimellitic acid, trimesic acid, and pyromellitic acid.

Also, aromatic compounds such as dibromoterephthalic acid, tetrabromoterephthalic acid, tetrabromophthalic acid, tetrachloroterephthalic acid, 1,4-dimethyloltetrabromobenzene, tetrabromobisphenol A, and ethylene oxide adduct of tetrabromobisphenol A And a thermoplastic polyester resin having a halogen compound such as chlorine or bromine as a substituent and copolymerizing a halogen compound having an ester-forming property.

Particularly preferred polyester resins include polyethylene terephthalate, polybutylene terephthalate, pohexamethylene terephthalate, poly (ethylene / butylene terephthalate), poly (cyclohexane dimethylene terephthalate), poly (butylene / tetramethylene terephthalate), and 2,2-bis (Β-hydroxyethoxytetrabromophenyl) propane copolymerized polybutylene terephthalate.

Polycarbonate (hereinafter abbreviated as PC) can be a homogeneous PC or a PC copolymer based on one or more of the following bisphenols. Hydroquinone, resorcin, dihydroxydiphenyl, bis- (hydroxyphenyl) -alkane, bis- (hydroxyphenyl) -cycloalkane, bis- (hydroxyphenyl) -sulfide, bis- (hydroxyphenyl) -ketone, bis- (hydroxyphenyl) Ethers, bis- (hydroxyphenyl) -sulphoxides, bis- (hydroxyphenyl) -sulphones and α, α′-bis- (hydroxyphenyl) -diisopropylbenzene and their compounds in which the nucleus is substituted by alkyl or halogen.

Specific examples of preferred bisphenols among these include 4,4-dihydroxydiphenyl, 2,2-bis-
(4-hydroxyphenyl) -propane, 2,4-bis-
(4-hydroxyphenyl) -2-methylbutane, 1,1
-Bis- (4-hydroxyphenyl) -cyclohexane, α, α'-bis- (4-hydroxyphenyl) -p
-Diisopropylbenzene, 2,2-bis- (3-methyl-4-hydroxyphenyl) -propane, 2,2-bis-
(3-chloro-4-hydroxyphenyl) -propane,
Bis- (3,5-dimethyl-4-hydroxyphenyl)-
Methane, 2,2-bis- (3,5-dimethyl-4-hydroxyphenyl) -propane, 2,2-bis- (3,5-dimethyl-
4-hydroxyphenyl) -sulfone, 2,4-bis-
(3,5-dimethyl-4-hydroxyphenyl) -2-mercaptan, 1,1-bis- (3,5-dimethyl-4-hydroxyphenyl) -cyclohexane, α, α′-bis-
(3,5-dimethyl-4-hydroxyphenyl) -p-diisopropylbenzene, 2,2-bis- (3,5-dichloro-
4-hydroxyphenyl) -propane and 2,2-bis- (3,5-dibromo-4-hydroxyphenyl) -propane, and the like, preferably, 2,2-bis- (4-hydroxyphenyl) propane, 2,2-bis- (3,5-dimethyl-4-hydroxyphenyl) -propane, 2,2-bis- (3,5-dichloro-4-hydroxyphenyl) -propane, 2,2-bis- (3 , 5-dibromo-4-hydroxyphenyl) propane and 1,1-bis- (4-hydroxyphenyl) -cyclohexane.

Preferred PCs are based on the preferred bisphenols described above. Particularly preferred PC copolymers are 2,2 bis- (4-
(Hydroxyphenyl) -propane is a copolymer of one of the above particularly preferred other bisphenols.

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

Incidentally, PC can be produced by a known method, for example, a method of melt transesterification of bisphenol and diphenyl carbonate, a two-phase interfacial polymerization method of bisphenol and phosgene, and the like.

Polyarylates are polyesters synthesized from bisphenols or derivatives thereof and dibasic acids or derivatives thereof. Examples of bisphenols include 2,2-bis- (4-hydroxyphenyl) -propane, 4,4'-
Dihydroxy-diphenyl ether, 4,4'-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- (4-hydroxyphenyl)
-Methane, 1,1-bis- (4-hydroxyphenyl)-
Ethane, 1,1-bis- (4-hydroxyphenyl) -n
-Butane, di- (4-hydroxyphenyl) -cyclohexyl-methane, 1,1-bis- (4-hydroxyphenyl) -2,2,2-trichloroethane, 2,2-bis- (4-hydroxy-3, 5-dibromophenyl) -propane, 2,2-
Bis- (4-hydroxy-3,5-dichlorophenyl)-
Although propane and the like are mentioned, particularly preferred is 2,2.
-Bis- (4-hydroxyphenyl) -propane or bisphenol A.

Examples of dibasic acids include aromatic dicarboxylic acids such as isophthalic acid, terephthalic acid, bis- (4-carboxy) -diphenyl, bis- (4-carboxyphenyl) -ether, bis- (4-carboxyphenyl) −
Sulfone, bis- (4-carboxyphenyl) -carbonyl, bis- (4-carboxyphenyl) -methane, bis- (4-carboxyphenyl) -dichloromethane, 1,
2- and 1,1-bis- (4-carboxyphenyl) -ethane, 1,2- and 2,2-bis (4-carboxyphenyl) -propane, 1,2- and 2,2-bis- (4 -Carboxyphenyl) -1,1-dimethylpropane, 1,1- and
2,2-bis- (4-carboxyphenyl) -butane, 1,1
-And 2,2-bis- (4-carboxyphenyl) -pentane, 3,3-bis- (4-carboxyphenyl) -heptane, 2,2-bis- (4-carboxyphenyl) -heptane; and aliphatic Acids such as oxalic acid, adipic acid,
Examples include succinic acid, malonic acid, sebacic acid, glutaric acid, azelaic acid, speric acid, and the like. Isophthalic acid, terephthalic acid, and a mixture of these derivatives are preferred.

Polysulfone is defined as a polyarylene compound in which an arylene unit is located randomly or orderly together with an ether and a sulfone bond, and includes, for example, the following structural formulas (a) to (r) (where -φ- is p -Phenylene group, -Ph represents a phenyl group, and n represents an integer of 10 or more), and preferably has a structure of (a) or (f). These may be a simple substance or a block copolymer. As the block copolymer, a block copolymer of (a) and (b),
(F) and polycarbonate block copolymer or (f)
And arylate block copolymers.

The PPO used in the present invention is also referred to as polyphenylene ether (abbreviated as PPE), and can be obtained by polycondensing at least one kind of a monocyclic phenol represented by the following general formula (4).

(However, R ₁ is a lower alkyl group having 1 to 3 carbon atoms, R ₂ and
R ₃ is hydrogen or a lower alkyl group having 1 to 3 carbon atoms,
There must be a lower alkyl substituent in at least one ortho position of the hydroxyl group. The PPO may be a homopolymer or a copolymer.

Examples of the monocyclic phenol represented by the formula (4) include 2,6-dimethylphenol, 2,6-diethylphenol, 2,6-dipropylphenol, and 2-methyl-6-phenol.
Ethylphenol, 2-methyl-6-propylphenol, 2-ethyl-6-propylphenol, m-cresol, 2,3-dimethylphenol, 2,3-diethylphenol, 2,3-dipropylphenol, 2-methyl -3-
Ethylphenol, 2-methyl-3-propylphenol, 2-ethyl-3-methylphenol, 2-ethyl-
3-propylphenol, 2-propyl-3-methylphenol, 2-propyl-3-ethylphenol, 2,3,
6-trimethylphenol, 2,3,6-triethylphenol, 2,3,6-tripropylphenol, 2,6-dimethyl-
3-ethyl-phenol, 2,6-dimethyl-3-propylphenol and the like.

Examples of PPO obtained therefrom include poly (2,6-
Dimethyl-1,4-phenylene) ether, poly (2,6-diethyl-1,4-phenylene) ether, poly (2,6-dipropyl-1,4-phenylene) ether, poly (2-methyl-6- Ethyl-1,4-phenylene) ether, poly (2-methyl-6-propyl-1,4-phenylene) ether, poly (2-ethyl-6-propyl-1,4-phenylene) ether, 2,6- Dimethylphenol / 2,3,6-trimethylphenol copolymer, 2,6-dimethylphenol / 2,3,6-triethylphenol copolymer, 2,6-diethylphenol / 2,3,6-trimethylphenol copolymer Polymer, 2,6-dipropylphenol / 2,3,6-trimethylphenol copolymer, and poly (2,6-dimethyl-1,4-
Phenylene) ether and 2,6-dimethylphenol / 2,3,
Copolymers obtained by graft-polymerizing styrene to a 6-trimethylphenol copolymer and the like are included.

In particular, the preferred PPO for use in the present invention is poly (2,6-
Dimethyl-1,4-phenylene) ether and 2,6-dimethylphenol / 2,3,6-trimethylphenol copolymer.

Polyetherketone is a repeating unit of the following formula (5) And / or a repeating unit of the following formula (6) Is a tough, crystalline, thermoplastic, aromatic polyether ketone which contains, alone or together with other repeating units, and has an intrinsic viscosity (IV) of 0.7 or more. Equation (5) and / or
Or, as another repeating unit other than formula (6), formula (7) (In the formula, A is a direct bond, oxygen, sulfur, -SO ₂ -, - CO-
Or a divalent hydrocarbon group. ) And equation (8) And further represented by the formula (9) And equation (10) (Subunit in the formula Is in the ortho or para position with respect to the group Y or Y ', Y and Y' are the same or different, and -CO-
Or —SO ₂ —, and Ar ′ is a divalent aromatic group;
And η is 0, 1, 2 or 3. ) Is included.

Polyetherimide (PEI) has the following formula:

In the above formula, —O—Q ₁ —O— is bonded at the 3 or 4 and 3 ′ or 4 ′ position, and Q ₁ is A substituted or non-substituted aromatic group such as Or a divalent substituted or unsubstituted aromatic derivative group of Here, Q ′ is independently C ₁ -C ₆ alkyl, aryl or halogen. Q ₃ is -O-, -S-, -CO
—, —SO ₂ —, —SO—, cycloalkylene having 1 to 6 carbon atoms, alkylidene having 1 to 6 carbon atoms or cycloalkylidene having 4 to 8 carbon atoms, and Q ₂ has 6 to 20 carbon atoms. (where the alkyl group contains 1 to 6 carbon atoms) aromatic hydrocarbon radicals and halogenated derivatives thereof having an atomic, alkylene and Shirukoakiren groups and C ₂ -C ₈ containing from 2 to 20 carbon atoms An alkylene-terminated polydiorganosiloxane or the above formula (14).

As the α-olefin of the α-olefin copolymer,
Examples include ethylene, propylene, butene-1, isobutene, pentene-1, 4-methylpentene-1, and hexane-1. These are used as one or more copolymers. Further, other monomers copolymerizable with these α-olefins, for example, vinyl acetate, vinyl propionate, methyl acrylate, methyl methacrylate,
It is also possible to copolymerize acrylonitrile, styrene, vinyl ether, acrylic acid, methacrylic acid, and unsaturated dicarboxylic acids such as maleic acid. Also,
An ionomer containing a metal ion such as Na ⁺ or Zn ⁺⁺ may be used as the copolymer having a carboxylic acid. The above α-
Among olefin copolymers, ethylene copolymers are particularly preferably used.

Styrene-based copolymers include styrene homopolymers and copolymers with other monomers copolymerizable with styrene monomers, for example, styrene derivative monomers such as α-methylene styrene, dimethyl styrene, chlorostyrene, and acrylic. Unsaturated carboxylic acids such as acid, methacrylic acid, maleic acid, maleic anhydride, etc., methyl acrylate,
It is a copolymer with one or more monomers such as acrylates such as methyl methacrylate, ethyl acrylate and ethyl methacrylate or vinyl monomers such as vinyl acetate and vinyl ether.

The phenoxy resin is a high-molecular-weight thermoplastic polyether resin synthesized using bisphenol A and epichlorohydrin as main raw materials and having no epoxy groups at both ends. Further, dihydric phenols or bisphenols such as bisphenol F and tetrachlorobisphenol, diol compounds such as diphenolic acid and bisphenol and p-xylene dichloride condensate, and epoxy compounds such as epichlorohydrin, butadiene oxide and glycidyl compounds And thermoplastic polyethers having no epoxy groups at both ends synthesized by the reaction with

ABS resin is obtained by polymerizing two or more compounds selected from vinyl cyanide monomer, aromatic vinyl monomer and acrylic monomer in the presence of conjugated diene rubber. It is a graft copolymer. Also, if necessary,
It may contain a copolymer obtained by polymerizing two or more compounds selected from vinyl cyanide monomers, aromatic vinyl monomers and acrylic monomers. As the conjugated diene rubber in the graft copolymer, polybutadiene, butadiene-styrene copolymer, butadiene-acrylonitrile copolymer and the like, and as the vinyl cyanide monomer, acrylonitrile, methacrylonitrile and the like, As the vinyl monomer, styrene,
Vinyl toluene, dimethyl styrene, chlorostyrene and the like, particularly preferably styrene and α-methyl styrene can be mentioned. In addition, acrylic monomers such as acrylic acid, methacrylic acid, methyl acrylate,
Examples thereof include ethyl acrylate, butyl acrylate, methyl methacrylate, and hydroxy acrylate.

The fluororesin used in the present invention is a general term for a synthetic polymer containing a fluorine atom in a repeating unit of the polymer and a copolymer thereof, and includes polytetrafluoroethylene, polychlorotrifluoroethylene, and tetrafluoroethylene hexafluoro. So-called fluororesins such as propylene copolymer, tetrafluoroethylene / perfluoroalkylvinyl ether copolymer, polyvinylidene fluoride, polyvinyl fluoride, tetrafluoroethylene / ethylene copolymer and vinylidene fluoride / hexafluoropropylene copolymer The main one is fluororubber, mainly of coalescence.

The mixing ratio of the PAS-based resin and these thermoplastic resins differs depending on the purpose of use, the type of the resin, and the like, and cannot be unconditionally specified.
1 to 95 parts by weight of a thermoplastic resin, particularly preferably 98 to 10 parts by weight of a PAS resin, and 2 to 90 parts by weight of a thermoplastic resin.
Parts by weight. (However, the total is 100 parts by weight.) On the other hand, the ratio of the addition of the CPAS resin cannot be unconditionally specified because it differs depending on the purpose of use, the type of the resin, and the like. By using 0.5 to 60 parts by weight, preferably 0.8 to 50 parts by weight with respect to 100 parts by weight in total, the desired effects of the present invention can be obtained.

In the resin composition of the present invention, if necessary, a fibrous or granular reinforcing agent can be compounded, and the resin composition is usually mixed in a range of 3 to 300 parts by weight. Strength, rigidity, heat resistance, and dimensional stability can be further improved. Examples of the fibrous reinforcing agent include glass fiber, carbon fiber, silane glass fiber, boron fiber, whisker, potassium titanate, asbestos, silicon carbide, aramid fiber, ceramic fiber, and metal fiber. Examples of the granular reinforcing material include silicates such as mica and talc, carbonates, sulfates, metal oxides, glass beads, and silica. Two or more of these may be used in combination, and these inorganic fillers may be treated with a silane-based or titanium-based coupling agent that is usually used as a filler treating agent.

In addition, the composition of the present invention contains a small amount of a release agent, a colorant, a heat stabilizer, an ultraviolet stabilizer, a foaming agent, a soft burner, a soft burn assistant, a rust preventive, without departing from the objects of the present invention. Alternatively, a thermosetting resin such as an epoxy resin, a phenol resin, and a polyimide can be contained.

The composition of the present invention can be prepared by various known methods. For example, there is a method in which the raw materials are mixed by a mixer such as a dambler or a Henschel mixer, fed to a single-screw or twin-screw extruder, melt-kneaded at 230 to 400 ° C., and then adjusted as pellets.

The composition of the present invention has a remarkably improved blend compatibility, and has remarkably improved mechanical properties such as impact resistance and various properties such as adhesion. Therefore, the resin composition of the present invention can be used, for example, for electrical and electronic parts such as connectors, printed circuit boards, and encapsulation molded articles, for automotive parts such as lamp reflectors and various electrical components, and for interiors of various buildings and aircraft and automobiles. Materials, leisure and sporting goods such as tennis rackets, skis, golf clubs, fishing rods, etc., acoustic materials such as enclosures for speakers and back decks for stringed instruments, and precision parts such as OA equipment parts, camera parts, clock parts, etc. It is used as a molding material with excellent mechanical properties such as heat resistance and impact resistance in various molding processing fields such as injection molding, compression molding, and extrusion molding and pultrusion molding of composite sheets and pipes.

<Examples> Hereinafter, the present invention will be described specifically with reference to examples, but the present invention is not limited to these examples.

Reference Example 1 A 2 L autoclave was charged with 540 g of NMP, 139.2 g of sodium hydrosulfide (NaSH) having a purity of 73% by weight, and 72 g of sodium hydroxide, and heated to 200 ° C. under a nitrogen atmosphere to obtain a water-NMP mixture. Was distilled off. Further, a solution prepared by dissolving 264.6 g of p-dichlorobenzene in 200 g of NMP was added to the system, and reacted at 220 ° C. for 5 hours and further at 240 ° C. for 1 hour under a nitrogen atmosphere. The reaction solvent A was cooled to 80 ° C.
38.2 g of dichlorobenzoic acid, 15.5 g of NaSH, 16.0 g of sodium hydroxide and 80 g of NMP were added, and reacted at 220 ° C. for 5 hours and 240 ° C. for 1 hour under a nitrogen atmosphere. The reaction product was washed with hot water, methanol and acetone, and dried to obtain a block copolymer type CPPS-3. When the infrared absorption spectrum was measured, an absorption spectrum that was considered to be that of a carboxyl group was observed at 1700 and 3000 Kaiser, and the content of phenylene sulfide having a carboxyl group with respect to all phenylene sulfide units determined by elemental analysis was 6.0 mol%. there were. The melting point measured by DSC is 275
° C, and the dynamic viscosity [η '] at 295 ° C and 10 rad / sec is
It was 300 poise. Further, CPPS-3 was heat-treated at 260 ° C. for about 1 hour to obtain CPPS-4. The dynamic viscosity of CPPS-4 is 10
It was 00 poise.

<Reference Example 2> Aqueous sodium hydroxide (NaSH · 2H ₂ O) was placed in an autoclave having a reservoir outlet, a monomer solution inlet, and a nitrogen gas inlet.
9.65 kg, 4.05 kg of sodium hydroxide and 50 kg of N-methylpyrrolidone were stirred for about 19
A dehydration operation was performed at 0 ° C. for 1 hour. Next, the autoclave was sealed, and a solution of 14.7 kg of p-dichlorobenzene and 10 kg of N-methylpyrrolidone was press-fitted into the system obtained by the dehydration operation heated to 200 ° C. for 40 minutes, and the pressure was increased to 220 ° C. After raising the temperature, the reaction was carried out for 4 hours. Then, 6 kg of water was injected into the reaction system, the temperature was raised to 240 ° C., and the reaction was carried out for 3 hours. The polymer was separated and washed with warm water and acetone. And dried to obtain PPS.

PPS has a melting point of 285 ° C. determined by DSC, 305 ° C., 10 ra
The dynamic viscosity [η '] of d / sec was 800 poise.

Examples 1 and 2, Comparative Examples 1 and 2 PPS obtained in Reference Example 2 and nylon 66 or nylon 6 and C
PPS-4 was mixed at a ratio as shown in Table 1, melt-kneaded at about 300 ° C. using an extruder, pelletized, and then a sample piece was prepared with an injection molding machine. An Izod impact test and a bending test were performed. The results are shown in Table 1. It can be seen that the properties are greatly improved by adding CPPS. Further, with respect to Example 1 and Comparative Examples 1 and 2, when the fracture surface of the sample used for the Izod test was observed by a scanning electron microscope (SEM), no dispersed particles were observed in Example 1.
On the other hand, in Comparative Examples 1 and 2, it was observed that spherical particles of about 1 to 10 microns were dispersed. In addition, nylon 66
In the case of, the sample piece was immersed in warm water at 70 ° C. for about 24 hours, and the water absorption and the bending strength after water absorption were measured. The results are shown in Table
It is shown in FIG.

Incidentally, Vydyne 22H manufactured by Monsanto was used for nylon 66, and MC-112L manufactured by Kanebo was used for nylon 6.

Comparative Examples 3 and 4 PPS obtained in Reference Example 2 and polybutylene terephthalate (P
BT) or polyethylene terephthalate (PET) were mixed at the ratios shown in Table 2, sample pieces were prepared in the same manner as in Example 1, and the same examination was performed. The melting and kneading temperature was 300 ° C. The results are shown in Table 2. In Comparative Examples 3 and 4, the fracture surfaces of the samples were observed by SEM. In Comparative Example 3, spherical coarse particles of about 1 to 10 microns and in Comparative Example 4 of about 2 to 5 microns were observed to be unevenly dispersed.

PBT is Planac BT-128, manufactured by Dainippon Ink and Chemicals, Inc.
As the PET, Mitsui PET J-125 manufactured by Mitsui Pet Co., Ltd. was used.

Comparative Examples 5 to 8 PPS and polycarbonate (PC), polyarylate (P
Ar), polysulfone (PSF), polyetherimide (PE
I) was blended as shown in Table 3, samples were prepared in the same manner as in Example 1, and the same examination was performed. The melt-kneading temperature was 300 ° C for PC, 340 ° C for PEI, and 330 ° C for the others. The results are shown in Table-3. In the observation of the fracture surface by SEM, the fibrous dispersion of about 5 microns was found to be PAr on PC.
In addition, spherical dispersed particles of about 1 to 20 microns in PSF and about 10 microns in PEI were observed. The adhesion between the dispersion and the dispersed particles and the matrix polymer was such that the dispersion was completely removed from the matrix polymer, and the adhesion was poor.

The PC is Iupilon S-2000 manufactured by Mitsubishi Gas Chemical Company,
PAr used Unitika U-polymer U-100, PSF used Amoco UDEL P-3703, and PEI used General Electric's Ultem-1000.

Comparative Examples 9-11 PPS and ethylene / ethyl acrylate copolymer (EEA),
The phenoxy resin and the ionomer were mixed at the ratios shown in Table 4, and a sample was prepared in the same manner as in Example 1, and the same examination was performed. The melt-kneading temperature was 300 ° C. The results are shown in Table-4. In observation of the fracture surface by SEM, spherical particles of 5 to 10 microns were observed in all of the comparative examples. The adhesion between the dispersed particles and the matrix polymer was poor, and the dispersed particles were in a state of being completely removed.

EEA is NUC copolymer EEA D manufactured by Nippon Unicar.
PDJ-9169 and phenoxy resin used were UCAR phenoxy resin manufactured by Union Carbide, grade PKHH, and ionomer used was Himilan 1706 manufactured by DuPont Mitsui Polychemicals.

Comparative Examples 12-14 PPS and polyphenylene oxide (PPO), ABS resin,
Polyethylene was blended as shown in Table 5, samples were prepared in the same manner as in Example 1, and Izod impact test and adhesive strength were measured. The results are shown in Table-5. The adhesion test
An epoxy adhesive was applied to 1 cm ² , the sample pieces were overlapped, and the tensile strength was measured. In addition, when characters were written on the sample surface with magic ink, the ink repelling phenomenon occurred with PPO and polyethylene when CPPS was not added.

PPO is Noryl manufactured by General / Electric.
534J-801, ABS resin is Kaneace MU manufactured by Kaneka Corporation
For HM-3000 and polyethylene, Shorex F-5010 manufactured by Showa Denko KK was used.

Examples 3 to 8 Using PPS and PBT, PC, PAr, PSF, phenoxy resin, ionomer and CPPS-4, compounded as shown in Table 6, and
A similar study was conducted. The results are shown in Table-6.

<Effect of the Invention> The composition of the present invention is one in which the blend compatibility is significantly improved, and various properties such as mechanical properties such as impact resistance and adhesiveness are remarkably improved.

──────────────────────────────────────────────────続 き Continuation of the front page (72) Inventor Ichitaka Murata 76-2 Jonai-cho, Sakura-shi, Chiba (56) References JP-A-2-283763 (JP, A) JP-A-63-305131 (JP, A) JP-A-3-231968 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08L 81/00-81/02 C08L 101/00-101/08

Claims (4)

(57) [Claims] 1. A polyarylene sulfide resin comprising a polyarylene sulfide resin, a polyarylene sulfide resin containing a carboxyl group, and at least one other thermoplastic resin, and containing a carboxyl group. The resin is a block copolymer containing a dihalogeno aromatic carboxylic acid and / or an alkali metal salt thereof as a copolymerization component, and is a resin having a carboxyl group-containing arylene sulfide structural unit content of 0.5 to 30 mol%. A resin composition comprising: 2. A polyarylene sulfide resin having a carboxyl group is represented by the following general formula (1): The composition according to claim 1, which is a carboxyl group-containing polyphenylene sulfide-based resin containing a structural unit represented by the formula: 3. The use ratio of the polyarylene sulfide resin and at least one other thermoplastic resin is as follows:
Use of a polyarylene sulfide-based resin containing a carboxyl group in an amount of 1 to 95 parts by weight (provided that the total is 100 parts by weight) and 99 to 5 parts by weight, and 100 parts by weight of the total. 3. The resin composition according to claim 1, wherein the proportion is in the range of 0.5 to 60 parts by weight. 4. Other thermoplastic resins include polyamide, thermoplastic polyester, polycarbonate, polyarylate, polysulfone, polyphenylene oxide, polyetherketone, polyetherimide, phenoxy resin, α-olefin copolymer, and styrene copolymer. 3. The method according to claim 1, wherein at least one thermoplastic resin selected from the group consisting of a polymer, an ABS resin and a fluorine resin is used.
Or the resin composition according to 3.