JPH0559282A - Resin composition - Google Patents

Abstract

PURPOSE:To obtain a resin composition excellent in blend compatibility, impact resistance, adhesion, etc., by mixing a polyarylene sulfide resin with a specified polyarylene sulfide resin and a thermoplastic resin. CONSTITUTION:The title composition is prepared by mixing a polyarylene sulfide resin (e.g. polyphenylene sulfide) with an amino-containing polyarylene sulfide resin (e.g. a resin prepared from sodium sulfide, p-dichlorobenzene and 2,5-dichloroaniline) and at least another thermoplastic resin (e.g. nylon 66).

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 polyarylene sulfide having an improved compatibility and another thermoplastic resin, which has heat resistance, chemical resistance, dimensional stability and flame retardancy. As a molding material excellent in mechanical properties such as resistance and impact resistance and adhesiveness, it is used in a wide range of fields such as electric, electronic parts, precision equipment parts, automobile parts, sports materials, and miscellaneous goods.

[0002]

2. Description of the Related Art Polyphenylene sulfide (hereinafter referred to as PP
Polyarylene sulfide-based resin (hereinafter abbreviated as S) (hereinafter abbreviated as PAS-based resin) is excellent in heat resistance, high rigidity, moldability, and flame retardancy, chemical resistance, and size. It has attracted attention as a high-performance, high-performance engineering plastic because of its outstanding stability. However, some drawbacks of the PAS resin have been pointed out. For example, mechanical and mechanical properties such as impact resistance, adhesiveness, weather resistance and burr characteristics of molded products, or P
With PS and the like, the glass transition temperature is relatively low at 80 to 90 ° C., and the elastic modulus sharply decreases above the glass transition temperature.

Attempts have been made to improve the drawbacks of PAS resins or to impart the excellent properties of PAS resins to other resins by blending the PAS resins with other thermoplastic resins. Many have been done so far.

However, in any case, the compatibility with the PAS-based resin and the thermoplastic resin to be blended is insufficient, so that the intended effect is not sufficiently exhibited, or in some cases, the characteristics are rather deteriorated. There was a problem such as doing, or the occurrence of other problems. These problems differ depending on the type of thermoplastic resin blended with the PAS resin. For example, Japanese Patent No. 1005081 discloses a composition of a PAS-based resin and a polyamide, a phenoxy resin, a thermoplastic polyester, polyethylene or the like for the purpose of flame retardation. In this case, the purpose of flame retardation is Although achieved, there was a problem that mechanical properties such as impact resistance were not improved or rather decreased due to insufficient compatibility. In addition, JP-A-56
No. 34032 discloses the case of PPS and polyphenylene oxide, and US Pat. No. 4,021,596 discloses PPS.
And polysulfone, polycarbonate, and polyphenylene oxide, and JP-A-63-304046 discloses PPS and ABS resin in JP-A-53-572.
In JP-A-55, the cases of PPS and polyarylate are disclosed respectively, but in each case, there is a problem that properties such as impact resistance cannot be improved because the compatibility is insufficient. In addition, polyethylene and polyphenylene oxide have problems such as insufficient adhesion, and polyamide does not sufficiently improve water absorption.

On the other hand, JP-A-59-58052 and 59
-155461, 59-155462, 59-
164360, 59-207921, 59-2
In each of the 13758 and 59-64657 publications, PP
A method of adding an epoxy resin for the purpose of improving the compatibility of the blend of S with various thermoplastic resins is disclosed. However, even in this method, the effect of improving the compatibility is not sufficient, and the epoxy resin is added. This causes a problem that the moldability is deteriorated due to the effect of thermal decomposition and gelation.

[0006]

DISCLOSURE OF THE INVENTION The present invention has not been sufficiently improved in the prior art or improved in some cases by improving the blending compatibility with other thermoplastic resins blended with the PAS resin. It is an object of the present invention to provide a resin composition that imparts the excellent properties of both resins to be blended to each other, such as improving the physical properties that have been achieved, for example, mechanical properties such as impact resistance. Another object of the present invention is to improve the adhesiveness and the surface affinity for coating, which were not improved depending on the resin to be blended.

[0007]

Means for Solving the Problems The inventors of the present invention have made extensive studies on the above-mentioned problems, and found that a blend of a PAS resin and another thermoplastic resin further contains an amino group in a polyarylene sulfide type. It has been found that these defects are eliminated when a resin is contained, and the present invention has been completed.

That is, the present invention comprises a polyarylene sulfide resin, an amino group-containing polyaryl sulfide resin (hereinafter abbreviated as A-PAS resin), and at least one other thermoplastic resin. The present invention relates to a resin composition characterized in that

The PAS resins used in the present invention are PAS resins represented by the structural formula (-Ar-S-) n (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 (-φ-O-φ-), (-φ
-CO-φ-), (-φ-CH ₂ -φ-), (-φ-S
O ₂ -φ-), (-φ-C (CH ₃ ) ₂ -φ-) (however,-
φ-represents a p-phenylene group, and the same applies hereinafter. )
A divalent aromatic residue containing at least two C6 aromatic rings such as F, Cl and B.
Substituents such as r and CH ₃ may be introduced. This may be a homopolymer, a random copolymer or a block copolymer, and linear, branched, or crosslinked types and mixtures thereof are used.

As for the melt viscosity of the above PAS resin, the crystalline one has a dynamic viscosity [η '] at 10 rad / sec of 10 to 10 ⁵ poise, preferably 50 at a melting point plus 20 ° C. 〜50000 poise, but amorphous one is 10 rad / s in glass transition temperature plus 100 ℃
dynamic viscosity at ec of 50 to 10 ⁶ poise, preferably 1
Those having a poise of 00 to ⁵ × 10 ⁵ are used. 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 (hereinafter abbreviated as PPSS), polyphenylene sulfide ketone (hereinafter PPS).
(Abbreviated as K), a PPS moiety and a PPSS moiety, and a PPS moiety and a PPSK moiety.

PPS is a polymer containing a structural unit represented by (-φ-S-) in an amount of 70 mol%, particularly preferably 90 mol% or more. The other constituent part contained in PPS is mainly the above-mentioned arylene group.

Such PPS is, for example, (1) a reaction between a halogen-substituted aromatic compound and an alkali sulfide (US Pat.
513188, JP-B-44-27671 and JP-B-45-3368), (2) Condensation reaction of thiophenols in the presence of an alkali catalyst or a copper salt (US Pat. No. 3,274,165, British Patent No. 116
No. 0660), (3) Condensation reaction of an aromatic compound with sulfur chloride in the presence of a Lewis acid catalyst (Japanese Patent Publication No. 46-2).
7255, Belgian Patent No. 29437), etc., and can be arbitrarily selected according to the purpose.

PPSS is mainly composed of (-φ-SO ₂ -φ-
It is a polymer having S-) as a repeating unit. PPSS
Examples of the polymerization method include the method of reacting a dihaloaromatic sulfone such as 4,4'-dichlorodiphenyl sulfone with an alkali metal sulfide such as sodium sulfide in an organic amide solvent.

PPSK is mainly composed of (-φ-CO-φ-S
-) Is a polymer having a repeating unit. Examples of the polymerization method of PPSK include a method of reacting 4,4′-dichlorobenzophenone and an alkali metal sulfide in an organic amide solvent.

On the other hand, the A-PAS resin used in the present invention has, for example, an amino group-containing polyarylene sulfide (hereinafter referred to as a repeating unit) represented by the following general structural formula (1), (2) or (3). , A-PAS) and the repeating unit is the above-mentioned general formula (-Ar-S-).
Examples thereof include a copolymer with a polyarylene sulfide (hereinafter, abbreviated as PAS) represented by (Ar: arylene group).

[0017]

[Chemical 1]

(Where Y is --O--, --SO _2- , --C
_{H 2 -, -C (CH 3} ) 2 -, - CO -, - C (CF 3)
₂ -or simply indicates a bond. )

The content of the amino group-containing arylene sulfide structural unit represented by the above general formulas (1) to (3) cannot be unconditionally specified because it varies depending on the purpose of use and the like, but it is 0 in the A-PAS resin. 0.05 to 30 mol%, preferably 0.1 to 20 mol%. In this range, the desired effect is particularly exerted.

Such an A-PAS resin may be a random type or a block type.

The viscosity of the A-PAS resin is usually a melting point plus 20 ° C. when it is crystalline, or a glass transition temperature plus 100 ° C. when it is amorphous, when it is not heat treated. The dynamic viscosity [η '] at 10 rad / sec is 5 to 10 ⁵ poise, preferably 10 to 10 ⁴
It's a poise. However, since the A-PAS resin is rich in crosslinkability by heat treatment, it is possible to use it by heat treatment so that the viscosity is in the above range or more.

Preferred as the A-PAS resin is the PAS portion having PPS, PPSS, PPSK, PPS.
Of the amino group-containing polyphenylene sulfide (hereinafter, referred to as A-P) in which the A-PAS portion is a copolymer of PEG and PPSS or a copolymer of PPS and PPSK.
There is a combination of various copolymers, which is abbreviated as PS). Most typically, the PAS part is PPS
There is a copolymer with A-PPS in which the -PAS portion is represented by the general formula (1).

As the method for producing the A-PAS resin, the method for producing polyphenylene sulfide disclosed in JP-B-45-3368, that is, dihalo fragrance in a polar aprotic solvent such as N-methyl-2-pyrrolidone. A method of copolymerizing 2,5-dichloroaniline, 2-chloroaniline or the like when a group compound is reacted with an alkali metal sulfide such as sodium sulfide, or JP-A-2-296829.
When an alkali metal sulfide and dihalobenzene are reacted in an organic amide solvent as described in Japanese Patent Publication No.

[0024]

[Chemical 2]

An amino group-containing aromatic group represented by (X is halogen, Y is hydrogen, --NH ₂ group or halogen, R is a hydrocarbon group having 1 to 12 carbon atoms, and n is an integer of 0 to 3) Examples thereof include a method of polymerizing coexistence of an aromatic halide.

As the thermoplastic resin used in the present invention, any thermoplastic resin other than the PAS resin described in the publicly known literature concerning PAS resin can be used, but polyamide, thermoplastic polyester, polycarbonate,
Polyarylate, polysulfone, polyphenylene oxide, polyether ketone, polyetherimide, phenoxy resin, α-olefin copolymer, styrene copolymer, ABS resin and fluorine resin are particularly preferably used. The thermoplastic resin used for blending with the PAS resin may be used alone or in combination of two or more kinds. It is also possible to use copolymers and modified products of these thermoplastic resins.

As the polyamide, various known ones can be mentioned. For example, oxalic acid, adipic acid, speric acid,
Dicarboxylic acids such as sebacic acid, terephthalic acid, isophthalic acid, 1,4-cyclohexyldicarboxylic acid and ethylenediamine, pentamethylenediamine, hexamethylenediamine, decamethylenediamine, 1,4-cyclohexyldiamine, m-xylenediamine Polyamides obtained by polycondensation with diamines; polyamides obtained by polymerizing cyclic lactams such as caprolactam and laurinlactam; or polyamides obtained by copolymerizing cyclic lactams with salts of dicarboxylic acids and diamines. Can be mentioned. Of these polyamides, preferably 6 nylon, 66 nylon, 46 nylon, MXD6 nylon (copolymer of m-xylenediamine and adipic acid), 6/10 nylon, 66 / 6.1
Examples thereof include 0 nylon, 6/66 nylon, 12 nylon, 11 nylon, 6 / 6T nylon (a copolymer of caprolactam, a salt of terephthalic acid and hexamethylenediamine) and the like. These polyamides are used in combination of two or more kinds. I don't mind. Particularly preferred are 6 nylon, 66 nylon, 46 nylon, and MXD6 nylon.

As the polyester resin, terephthalic acid, isophthalic acid, orthophthalic acid, naphthalenedicarboxylic acid, 4,4'-diphenyldicarboxylic acid, diphenyletherdicarboxylic acid, α, β-bis (4-carboxyphenoxy) ethane, adipic acid, Sebacic acid, azelaic acid, decanedicarboxylic acid, dodecanedicarboxylic acid, cyclohexanedicarboxylic acid, dicarboxylic acids such as dimer acid or ester-forming derivatives thereof and ethylene glycol, propylene glycol, butanediol,
Pentanediol, neopentyl glycol, hexanediol, octanediol, decanediol, cyclohexanedimethanol, hydrquinone, bisphenol A, 2,2-bis (4-hydroxyethoxyphenyl) propane, xylene glycol, polyethylene ether glycol, polytetramethylene ether Polyester obtained from glycols and glycols such as aliphatic polyester oligomers having hydroxyl groups at both ends, usually measured at 30 ° C in a mixed solvent of phenol and ethane tetrachloride in a weight ratio of 6 to 4. Those having an intrinsic viscosity {η} of 0.3 to 1.5 dl / g are used.

As a comonomer component, a hydroxycarboxylic acid such as glycolic acid, hydroxybutyric acid, hydroxybenzoic acid, hydroxyphenylacetic acid or naphthylglycolic acid, a lactone compound such as propiolactone, butyrolactone, valerolactone or caprolactone, or a heat To the extent that plasticity can be maintained, trimethylolpropane, trimethylolethane, glycerin, pentaerythritol, trimellitic acid, trimesic acid,
It may contain a polyfunctional ester-forming component such as pyromellitic acid.

Further, dibromoterephthalic acid, tetrabromoterephthalic acid, tetrabromophthalic acid, tetrachloroterephthalic acid, 1,4-dimethyloltetrabromobenzene, tetrapromobisphenol A, tetrabromobisphenol A, such as ethylene oxide adducts. Also included are thermoplastic polyester resins obtained by copolymerizing a halogen compound having a halogen compound such as chlorine or bromine as a substituent with an aromatic group and having an ester-forming group.

Particularly preferred polyester resins include polyethylene terephthalate (PET), polybutylene terephthalate (PBT), pohexamethylene terephthalate, poly (ethylene / butylene terephthalate), poly (cyclohexane dimethylene terephthalate), poly (butylene / tetraene). Methylene terephthalate), 2,2-bis (β-hydroxyethoxytetrabromophenyl) propane copolymerized polybutylene terephthalate, and the like.

Polycarbonate (hereinafter abbreviated as PC) may be a homogeneous PC or a PC copolymer based on, for example, one or more of the following bisphenols. Hydroquinone, resorcin, 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) -diisopropylbenzene and compounds in which the nucleus is substituted with alkyl or halogen.

Of these, preferred specific examples of bisphenol include 4,4-dihydroxydiphenyl,
2,2-bis- (4-hydroxyphenyl) -propane, 2,4-bis- (4-hydroxyphenyl) -2-
Methyl butane, 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, 2,2-bis- (3,5-dibromo-4-hydroxyphenyl) -propane and the like can be mentioned, preferably. Is 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 is mentioned.

The preferred PCs are based on the preferred bisphenols mentioned above. A particularly preferred PC copolymer is a copolymer of 2,2-bis- (4-hydroxyphenyl) -propane with one of the above-mentioned particularly preferred other bisphenols.

Another particularly suitable PC is 2,2-bis- (4
-Hydroxyphenyl) -propane or 2,2-bis- (3,5-dimethyl-4-hydroxyphenyl) -propane only.

The PC can be produced by a known method such as a melt transesterification reaction of bisphenol and diphenicarbonate or a two-phase interfacial polymerization method of bisphenol and phosgene.

Polyarylate (hereinafter abbreviated as PAr)
Is a polyester synthesized from bisphenol or its derivative and dibasic acid or its derivative. 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) -Propane and the like can be mentioned, but particularly preferred is 2,2-bis- (4-
Hydroxyphenyl) -propane or bisphenol A.

Examples of dibasic acids are 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, succinic acid, malonic acid, sebacic acid , Glutaric acid, azelaic acid, speric acid, etc., but is preferably a mixture of isophthalic acid and terephthalic acid or derivatives thereof.

Polysulfone (hereinafter abbreviated as PSF) is
Arylene units together with ether and sulfone bonds,
It is defined as a polyarylene compound which is located randomly or in an orderly manner. For example, the following structural formulas (a) to (r) (in the formula, -φ- represents a p-phenylene group and -Bf- represents 3,
6-benzofuranylene group, -Np- represents a 2,7-naphthylene group, -Ph represents a phenyl group, and n represents an integer of 10 or more), and preferably (a) or ( Those having the structure of f) are desirable. These may be a simple substance or a block copolymer. Examples of the block copolymer include the block copolymers of (a) and (b), the block copolymer of (f) and polycarbonate, and the block copolymer of (f) and arylate.

(A) (-φ-O-φ-SO _2- ) _n (b) (-φ-φ-SO _2- ) _n (c) (-SO ₂ -Bf-SO ₂ -φ-O- φ-) _n (d) (-Np-SO ₂ -φ-O-φ-) _n (e) (-SO ₂ -φ-O-φ-SO ₂ -φ-CH ₂ -φ-) _n (f ) (-Φ-C (CH ₃ ) ₂ -φ-O-φ-SO ₂ -φ-O-) _n (h) (-O-φ-CH ₂ -φ-O-φ-SO ₂ -φ-) _n (i) (-O-φ-O-φ-SO ₂ -φ-) _n (j) (- O-φ-CO-φ-O-φ-SO ₂ -φ-) _n (k) (-O-φ-C (Ph) ₂ -φ-O-φ-SO ₂ -φ-) _n (L) (-O-φ-O-φ-O-φ-SO ₂ -φ-) _n (m) (-O-φ-SO ₂ -φ-O-φ-CF ₂ -φ-) _n (n) ( -O-SO ₂ -φ-φ-SO ₂ -φ-O-φ-O-φ-C (CH ₃ ) ₂ -φ-O-) _n (o) (-φ-SO ₂ -φ-O- φ-SO ₂ -φ-O-φ-C (CH ₃ ) ₂ -φ-O-) _n (p) (-φ-SO ₂ -φ-O-φ-SO ₂ -φ-) _n (q) (-Φ-φ-O-φ-SO ₂ -φ-O-) _n (r) (-φ-O-φ-SO ₂ -φ-φ-SO _2- ) _n

The polyphenylene oxide (hereinafter abbreviated as PPO) used in the present invention is also referred to as polyphenylene ether (abbreviated as PPE) and contains one or more monocyclic phenols represented by the following general formula (5). It can be obtained by polycondensation.

[0042]

[Chemical 3]

(However, R ₁ is a lower alkyl group having 1 to 3 carbon atoms, R ₂ and R ₃ are hydrogen or a lower alkyl group having 1 to 3 carbon atoms, and at least one ortho position of the hydroxyl group must be lower. Alkyl substituents must be present.)

The PPO may be a homopolymer or a copolymer. Examples of the monocyclic phenol represented by the formula (5) include 2,6-dimethylphenol, 2,6-diethylphenol, 2,6-dipropylphenol, 2-methyl-6-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-
Examples include 3-propylphenol and the like.

Examples of PPO thus obtained 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 Polymer, 2,6
-Diethylphenol / 2,3,6-trimethylphenol copolymer, 2,6-dipropylphenol / 2,
Styrene, such as 3,6-trimethylphenol copolymer, poly (2,6-dimethyl-1,4-phenylene) ether, 2,6-dimethylphenol / 2,3,6, -trimethylphenol copolymer, etc. And a copolymer obtained by graft-polymerizing

Particularly preferred PPO for use in the present invention
Is a poly (2,6-dimethyl-1,4-phenylene) ether, a 2,6-dimethylphenol / 2,3,6-trimethylphenol copolymer.

The polyether ketone is a repeating unit of the following formula (6) -φ-CO-φ-O- (6) and / or a repeating unit of the following formula (7) -φ-O-φ-CO. A tough crystalline thermoplastic aromatic polyether ketone containing -φ- (7) alone or together with other repeating units and having an intrinsic viscosity (IV) of 0.7 or more.

Other repeating units other than the above formula (6) and / or formula (7) include formula (8) -φ-A-φ-O-φ-CO-φ- (8) (wherein , A is a direct bond, oxygen, sulfur, -SO _2- , -CO-
Alternatively, it is a divalent hydrocarbon group. ) And the formula (9) -φ-CO-φ-O-φ-CO-φ-O- (9), and as the copolymerization unit, the formula (10) -φ-O- φ-SO ₂ -φ-O- (10) and equation (11)

[0049]

[Chemical 4]

The repeating unit represented by is included.

Polyetherimide (PEI) has the following formula.

[0052]

[Chemical 5]

In the above formula, -O-Q ₁ -O- is bonded to the positions 3 or 4 and 3'or 4 ', and Q ₁ is
It is selected from a substituted or unsubstituted aromatic group represented by the following formula (13) or (14), or a divalent substituted or unsubstituted aromatic derivative group represented by (15).

[0054]

[Chemical 6]

Where Q'is independently C ₁ -C ₆ alkyl, aryl or halogen. Q ₃ is, -O
-, - S -, - CO -, - SO 2 -, - SO-, cycloalkylene of 1-6 carbon atoms, selected from cycloalkylidene having 4 to 8 alkylidene carbon atoms or 1 to 6 carbon atoms, Q ₂ Is an aromatic hydrocarbon group having 6 to 20 carbon atoms and a halogenated derivative thereof (wherein the alkyl group includes 1 to 6 carbon atoms), an alkylene having 2 to 20 carbon atoms and It is a polydiorganosiloxane having a cycloalkylene group and a C ₂ -C ₈ alkylene as a terminal group, or the above formula (15).

Examples of the α-olefin of the α-olefin copolymer include ethylene, propylene, butene-1, isobutene, pentene-1, 4-methylpentene-1, and hexene-1. These are used as one type or two or more types of copolymers. Further, other monomers copolymerizable with these α-olefins, for example, vinyl acetate, vinyl propionate, methyl acrylate, methyl methacrylate, acrylonitrile, styrene, vinyl ether, acrylic acid, methacrylic acid, maleic acid, etc. It is also possible to copolymerize a saturated dicarboxylic acid or the like. In addition, it is possible to add Na ⁺ or Z to a copolymer having a carboxylic acid.
An ionomer containing a metal ion such as n ⁺⁺ may be used. Among the above α-olefin-based copolymers, an ethylene-based copolymer is particularly preferably used.

As the styrene-based copolymer, a homopolymer of styrene and a copolymer of a styrene monomer and another monomer copolymerizable with, for example, α-methylstyrene,
Styrene derivative monomers such as dimethylstyrene and chlorostyrene, acrylic acid, methacrylic acid, maleic acid,
Unsaturated carboxylic acid such as maleic anhydride, acrylic acid ester such as methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, or vinyl monomer such as vinyl acetate or vinyl ether, or two or more kinds thereof It is a copolymer with the monomer.

The phenoxy resin used in the present invention is a dihydric phenol, or a bisphenol such as bisphenol A, bisphenol F or tetrachlorobisphenol, a diphenol acid, a diol compound such as a bisphenol / p-xylene dichloride condensation product and epichlorohydrin. It is a thermoplastic polyether having no epoxy groups at both ends, which is synthesized by reaction with epoxy compounds such as butadiene oxide and glycidyl compound. Among them, those synthesized from bisphenol A and epichlorohydrin as main raw materials are preferably used.

The fluororesin used in the present invention is a general term for synthetic polymers containing a fluorine atom in the repeating unit of the polymer and their copolymers, such as polytetrafluoroethylene, polychlorotrifluoroethylene and tetrafluoroethylene.・ So-called fluororesins such as hexafluoropropylene copolymer, tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer, polyvinylidene fluoride, polyvinyl fluoride, tetrafluoroethylene / ethylene copolymer and vinylidene fluoride / hexafluoropropylene The main ones are fluororubbers centering on a system copolymer.

The mixing ratio of the PAS resin and these thermoplastic resins varies depending on the purpose of use, the type of resin, etc., and therefore cannot be specified unconditionally, but usually PA
Thermoplastic resins 1 to 9 relative to 99 to 5 parts by weight of S-based resin
5 parts by weight, particularly preferably, PAS-based resin is 98 to 10 parts by weight, and thermoplastic resin is 2 to 90 parts by weight. (However, the total is 100 parts by weight)

On the other hand, the proportion of the A-PAS-based resin added cannot be unconditionally specified because it varies depending on the purpose of use, the type of resin, etc., but normally, the total amount of the PAS-based resin and the thermoplastic resin is 100 parts by weight. Then, the effect aimed at by the present invention is exhibited by using it in the range of 0.1 to 100 parts by weight, preferably 0.5 to 80 parts by weight, and more preferably 0.8 to 60 parts by weight.

In the resin composition of the present invention, if necessary,
It is possible to add a fibrous or granular reinforcing agent, and further improve strength, rigidity, heat resistance, and dimensional stability by adding the fibrous or granular reinforcing agent in the range of usually 3 to 300 parts by weight with respect to the resin composition. be able to. Examples of the fibrous reinforcing agent include glass fiber, carbon fiber, silane glass fiber, boron fiber, whiskers, 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 which is usually used as a treating agent for the filler.

In the composition of the present invention, a small amount of a release agent, a colorant, a heat stabilizer, and a stabilizer within a range not departing from the object of the present invention.
An ultraviolet stabilizer, a foaming agent, a flame retardant, a flame retardant aid, a rust preventive, or a thermosetting resin such as an epoxy resin, a phenol resin, or 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 with a mixer such as a tumbler or a Henschel mixer, then fed to a uniaxial or biaxial extruder, melt-kneaded at 230 to 400 ° C., and then adjusted as pellets.

[0065]

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

[Reference Example 1] A 2-liter autoclave was charged with 600 g of N-methylpyrrolidone (hereinafter abbreviated as NMP) and 336.3 g (2.0 mol) of sodium sulfide pentahydrate (2.0 mol), and heated to 200 ° C. under a nitrogen atmosphere. The water-NMP mixture was then distilled off. Then, 279.3 g (1.9 mol) of p-dichlorobenzene and 2,5-
Dichloroaniline 16.2 g (0.1 mol) NMP
A solution dissolved in 230 g was added, and the mixture was reacted at 220 ° C for 5 hours and further at 240 ° C for 2 hours under a nitrogen atmosphere. After cooling the reaction vessel, the contents were taken out, a part thereof was sampled, and unreacted 2,5-dichloroaniline was quantified by gas chromatography. The remaining slurry was washed with hot water several times, and the polymer cake was filtered off. This cake at 80 ℃
After drying under reduced pressure, powdery amino group-containing polyphenylene sulfide (A-PPS-1) was obtained.

When the infrared absorption spectrum was measured, it was 3
An absorption spectrum which is considered to be that of an amino group was observed near 380 cm ^-1 . 3380 cm ^-1 measured by FT-IR
The ratio of the amino group-containing phenylene sulfide structural unit to the total phenylene sulfide structural unit estimated from the absorbance ratio in the vicinity of 1900 cm ^-1 is about 3.5 mol%, and the conversion of 2,5-dichloroaniline is 82%. Met. Further, the melting point measured by a differential scanning calorimeter (DSC) was 274 ° C., and the dynamic viscosity at 300 ° C. and 10 rad / sec was 150 poise.

Reference Example 2 The procedure of Reference Example 1 was repeated except that 3,5-dichloroaniline was used instead of 2,5-dichloroaniline. Obtained polymer (A-PPS-2)
When the infrared absorption spectrum was measured in the same manner as for A-PPS-1, the absorption spectrum that was considered to be that of an amino group was observed at around 3380 cm ^-1 . The proportion of the amino group-containing phenylene sulfide structural units to the total phenylene sulfide structural units was estimated from the absorbance ratios of around 3380 cm ^-1 and near 1900 cm ^-1 in the FT-IR measurement was about 4.2 mol%, 3,5-di The conversion of chloraniline was 93%. The melting point of this polymer is 27.
The temperature was 9 ° C., and the dynamic viscosity at 300 ° C. and 10 rad / sec was 20 poise.

Reference Example 3 29 p-dichlorobenzene was used.
Using 2.53 g (1.99 mol) and 1.62 g (0.01 mol) of 2,5-dichloroaniline, Reference Example 1
It carried out similarly to. The obtained polymer (A-PPS-
In 3), when an infrared absorption spectrum was measured in the same manner as A-PPS-1, an absorption spectrum which was considered to be that of an amino group was observed in the vicinity of 3380 cm ^-1 . 3 of FT-IR measurement
The ratio of the amino group-containing phenylene sulfide structural unit to the total phenylene sulfide structural unit estimated from the absorbance ratio around 380 cm ^{-1 and} around 1900 cm ^-1 was about 0.
It was 4 mol% and the conversion of 2,5-dichloroaniline was 92%. The melting point of this polymer is 280 ° C.
And the dynamic viscosity at 300 ° C. and 10 rad / sec was 350 poise.

Reference Example 4 p-dichlorobenzene was added to 23
The same procedure as in Reference Example 1 was conducted using 5.2 g (1.6 mol) and 64.8 g (0.4 mol) of 2,5-dichloroaniline. The obtained polymer (A-PPS-4) is A
When the infrared absorption spectrum was measured in the same manner as in -PPS-1, an absorption spectrum that was considered to be that of an amino group was observed near 3380 cm ^-1 . 3380 for FT-IR measurement
cm ^-1 ratio near the 1900 cm ^-1 vicinity amino group-containing phenylene sulfide structural units to the total phenylene sulfide structural units was estimated from the absorbance ratio of about 12 mol%
And the conversion of 2,5-dichloroaniline was 72%. The melting point of this polymer is 268 ° C.,
The dynamic viscosity at 300 ° C. and 10 rad / sec was 80 poise.

[Reference Example 5] 9.65 kg of sodium hydrofluoride (NaSH.2H ₂ O), 4.05 kg of sodium hydroxide and 50 kg of N-methyl were placed in an autoclave equipped with a distillation outlet, a monomer solution inlet and a nitrogen gas inlet. While stirring the pyrrolidone with nitrogen gas flowing, about 190
Dehydration operation was performed at ℃ for 1 hour. Then, the autoclave was closed, and a solution of 14.7 kg of p-dichlorobenzene and 10 kg of N-methylpyrrolidone was pressed into the system obtained by the dehydration operation heated to 200 ° C. for 40 minutes, and the pressure was increased to 220 After the temperature was raised to ℃, 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. Then, the polymer was separated and warmed with water and acetone. It was washed and dried to obtain PPS.

PPS has a melting point of 285 ° C. determined by DSC.
And the dynamic viscosity [η '] at 305 ° C and 10 rad / sec
Was 800 poise.

[Examples 1 to 8 and Comparative Examples 1 to 3] Reference Example 5
The PPS and nylon 66 obtained in 1. and A-PPS-1 and A-PPS-2 obtained in Reference Examples 1 and 2 were mixed, melt-kneaded at about 300 ° C. using an extruder, and pelletized. After that, a sample piece was prepared with an injection molding machine. An Izod impact test and a bending test were conducted. The results are shown in Tables 1 to 3.
It can be seen that the characteristics are significantly improved by adding A-PPS.

Further, regarding the Example 1 and the Comparative Example 1, the fracture surface of the sample used for the Izod test was observed by a scanning electron microscope (SEM), and in Example 1, fine particles of 1 micron or less were observed. However, in Comparative Example 1, it was observed that spherical particles of about 1 to 10 microns were dispersed.

Further, the sample piece was placed in warm water at 70 ° C. for about 2 minutes.
After being immersed in water for 4 hours, the water absorption rate and the bending strength after water absorption were measured. The results are shown in Tables 1 to 3. Nylon 6
6 used Vydyne 22H by Monsanto.

[0076]

[Table 1]

[0077]

[Table 2]

[0078]

[Table 3]

[Examples 9 to 16 and Comparative Examples 4 to 6] Nylon 6 was used instead of nylon 66 to mix, and Example 1
A sample piece was prepared by the same method as above, and the same examination was performed. The results are shown in Tables 4 to 6. However, Examples 11 and 12
Then, A-PPS-3 and A-PP obtained in Reference Examples 3 and 4
S-4 was used. Similar to nylon 66, A-PP
It can be seen that the characteristics are significantly improved by adding S.

When the fracture surface of each of the samples of Example 9 and Comparative Example 4 was observed by SEM, the dispersed particles of Example 9 were not observed. On the other hand, in Comparative Example 4, 1 to
It was observed that spherical particles of about 10 microns were dispersed.

Nylon 6 is MC-made by Kanebo.
112L was used.

[0082]

[Table 4]

[0083]

[Table 5]

[0084]

[Table 6]

[Examples 17 to 22, Comparative Examples 7 to 9] Instead of nylon 66, polybutylene terephthalate (PB) was used.
T) was mixed, a sample piece was prepared in the same manner as in Example 1, and the same examination was performed. The results are shown in Tables 7-9. It can be seen that the characteristics are improved by adding A-PPS.

Further, regarding Example 17 and Comparative Example 7,
The fracture surface of the sample was observed by SEM. No dispersed particles were observed in Example 17. On the other hand, in Comparative Example 7,
It was observed that coarse particles of about 10 microns were non-uniformly dispersed.

As PBT, PLANAC BT-128 manufactured by Dainippon Ink and Chemicals, Inc. was used.

[0088]

[Table 7]

[0089]

[Table 8]

[0090]

[Table 9]

[Examples 23 to 28, Comparative Examples 10 to 12]
Polyethylene terephthalate (PET) was used instead of nylon 66, mixed, and a sample piece was prepared in the same manner as in Example 1, and the same examination was performed. The results are shown in Table 1.
0 to Table 12 show. It can be seen that the characteristics are improved by adding A-PPS.

Further, regarding Example 23 and Comparative Example 10, the fracture surface of the sample was observed by SEM. Example 23
No dispersed particles were observed in. On the other hand, in Comparative Example 7, it was observed that coarse particles of about 2 to 5 microns were dispersed nonuniformly.

PET is Mitsui PE manufactured by Mitsui Pet Co., Ltd.
TJ-125 was used.

[0094]

[Table 10]

[0095]

[Table 11]

[0096]

[Table 12]

[Examples 29 to 36, Comparative Examples 13 to 16]
PPS and polycarbonate (PC), polyarylate (PAr), polysulfone (PSF), polyetherimide (PEI) and A-PPS-1 or A-PP
S-2 was used and blended as shown in Tables 13 to 16, a sample was prepared in the same manner as in Example 1, and the same examination was performed. Melt-kneading temperature is 300 ° C for PC and 340 for PEI
The temperature was 330C and the other temperatures were 330C. The results are shown in Table 13 to Table 1.
6 shows. The characteristics are significantly improved by adding A-PPS.

In the observation of the fracture surface by SEM, dispersed particles were not observed in PC and PAr in the example, and P
Particles of 5 microns or less were observed in SF, and particles of 2 microns or less were observed in PEI. The adhesion between the dispersed particles and the matrix polymer was good. On the other hand, in the comparative example, a fibrous dispersion of about 5 microns was observed for PC, spherical dispersion particles of about 1 to 20 microns for PAr and PSF, and about 10 microns for PEI were observed. The adhesiveness 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 adhesiveness was poor.

PC is Iupilon S-2000 made by Mitsubishi Gas Chemical Co., PAr is U polymer U-100 made by Unitika, PSF is UDEL P-3 made by Amoco.
703, PEI used Ultem-1000 manufactured by General Electric Company.

[0100]

[Table 13]

[0101]

[Table 14]

[0102]

[Table 15]

[0103]

[Table 16]

[Examples 37 to 42, Comparative Examples 17 to 19]
PPS and ethylene / ethyl acrylate copolymer (EE
A), phenoxy resin, ionomer and A-PPS-
1 or A-PPS-2 was mixed, 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 Tables 17 to 19.
Shown in. The properties were improved by adding A-PPS, and the sample was not broken in the bending test.

Further, in the observation of the fracture surface by SEM, dispersed particles were not found in the examples, but in the comparative examples, spherical particles of 5 to 10 microns were observed. The adhesion between the dispersed particles and the matrix polymer was poor, and the dispersed particles were in a state where they were completely hollow.

EEA is NUC manufactured by Nippon Unicar Co., Ltd.
Copolymer EEA DPDJ-9169, phenoxy resin used was UCAR phenoxy resin manufactured by Union Carbide, grade PKHH, and ionomer used was Himilan 1706 manufactured by Mitsui DuPont Polychemical.

[0107]

[Table 17]

[0108]

[Table 18]

[0109]

[Table 19]

[Examples 43 to 50, Comparative Examples 20 to 22]
PPS and polyphenylene oxide (PPO), ABS
A resin, polyethylene (PE) and A-PPS-1 or A-PPS-2 were blended, a sample was prepared in the same manner as in Example 1, and the Izod impact test and the adhesive strength were measured. The results are shown in Tables 20-22. It can be seen that the characteristics are significantly improved by adding A-PPS.

In the adhesion test, an epoxy adhesive was applied to 1 cm ² , sample pieces were overlapped, and the tensile strength was measured. In addition, when writing characters on the sample surface with magic ink, when A-PPS was not added, the ink repelling phenomenon occurred with PPO and polyethylene.
No repulsion phenomenon was observed in the case of adding PPS.

As the PPO, Noryl 534J-801 manufactured by General Electric Co., Kaneace MUHM-3000 manufactured by Kanegafuchi Chemical Co., Ltd. was used as the ABS resin, and Shorex F-5010 manufactured by Showa Denko KK was used as the polyethylene.

[0113]

[Table 20]

[0114]

[Table 21]

[0115]

[Table 22]

[Examples 51 to 56, Comparative Examples 23 to 25]
PPS and Nylon 66 and A-PPS-1 or A-P
Glass fiber (03-JA404, manufactured by Asahi Fiber Glass Co., Ltd.) 4 per 100 parts by weight of PS-2 and resin content
After mixing 0 parts by weight, melt-kneading with an extruder and pelletizing, sample pieces were prepared using an injection molding machine. An Izod test and a bending test were performed. The results are shown in Tables 23 to 25.
Shown in. It can be seen that the characteristics are significantly improved by adding A-PPS.

Also, soak in warm water at 70 ° C. for about 24 hours,
The rate of weight increase due to water absorption and bending strength were measured. The Izod test and the bending test were based on ASTM.

[0118]

[Table 23]

[0119]

[Table 24]

[0120]

[Table 25]

[0121]

EFFECT OF THE INVENTION The composition of the present invention has remarkably improved blending compatibility, and remarkably improves mechanical properties such as impact resistance and various properties such as adhesiveness. Therefore, the resin composition of the present invention can be used, for example, in electrical / electronic parts such as connectors / printed boards / encapsulation molded articles, automobile parts such as lamp reflectors / various electrical equipment parts, interiors of various buildings and aircraft / automobiles. Materials, leisure and sports equipment such as tennis rackets, skis, golf clubs and fishing rods, acoustic materials such as enclosures such as speakers and back decks of stringed instruments, precision parts such as OA equipment parts, camera parts, clock parts, etc. Injection molding, compression molding, or extrusion molding of composite sheets, pipes, etc.
Molding materials or fibers with excellent mechanical properties such as heat resistance and impact resistance in various molding processing fields such as pultrusion
Used as a film.

Claims (4)

[Claims] 1. A resin composition comprising a polyarylene sulfide resin, a polyarylene sulfide resin containing an amino group, and at least one other thermoplastic resin. 2. The resin composition according to claim 1, wherein the content of the amino group-containing arylene sulfide structural unit in the amino group-containing polyarylene sulfide-based resin is 0.05 to 30 mol%. 3. A polyarylene sulfide-based resin and at least one other thermoplastic resin are used in an amount of 99 to 5 parts by weight and 1 to 95 parts by weight (however, the total is 1
The amount of the polyarylene sulfide-based resin containing an amino group is in the range of 0.1 to 100 parts by weight based on 100 parts by weight). The resin composition described. 4. As other thermoplastic resin, polyamide, thermoplastic polyester, polycarbonate, polyarylate, polysulfone, polyphenylene oxide,
Polyetherketone, polyetherimide, phenoxy resin, α-olefin copolymer, styrene copolymer,
At least 1 selected from ABS resin and fluorine resin
The resin composition according to claim 1, wherein one kind of thermoplastic resin is used.