JPH04277555A - Resin composition - Google Patents

Abstract

PURPOSE:To provide a resin compsn. remarkably improved in heat resistance, compatibility in blending, mechanical properties such as flexibility and impact strength, water resistance, chemical resistance, etc., as compared with a polyarylene sulfide resin formerly known or a blend thereof. CONSTITUTION:A resin compsn. which comprises a block copolymer consisting of polyphenylene sulfide sulfone parts and polyphenylene sulfide ketone parts, another resin therewith (e.g. a polyamide, thermoplastic polyester, polsulfone, polyphenylene oxide, polyetheretherketone, polyetherimide, polyarylate, polycarbonate, phenoxy resin, epoxy resin, or SBR), and a filler if necessary.

Description

[Detailed description of the invention]

0001

[Field of Industrial Application] The present invention relates to a resin composition with improved heat resistance, chemical resistance, flexibility, water absorption, weather resistance, flame retardancy, etc. parts,
It is used as a molding material in various fields such as automobile parts, interior materials, and sports equipment.

0002

[Prior Art] Polyarylene sulfide resins (hereinafter abbreviated as PAS resins) have excellent properties such as heat resistance, chemical resistance, electrical insulation, flame retardance, and dimensional stability.
It has poor weather resistance and adhesion, is extremely brittle, and has poor impact resistance and flexibility, and this has been pointed out to be the biggest reason why its field of use is restricted. Many attempts have been made to improve the shortcomings of PAS resins or to impart the excellent properties of PAS resins to other resins by blending PAS resins with other polymers. .

However, all currently known PAS resins have problems such as poor affinity between resins and reduced heat resistance, and cannot fully satisfy the original purpose of blending. The current situation is that we are not getting what we should be getting. For example, polyphenylene sulfide (hereinafter referred to as
Regarding the composition of PPS), Japanese Patent No. 100
5081, U.S. Patent No. 4021596, Special Publication No. 56-3
4032, 60-11063, JP-A-53-5725
5, No. 59-213758, No. 59-155461, etc., but due to poor compatibility between resins, the impact resistance and flexibility of PPS may not be sufficiently improved, and in some cases There was a problem that it actually decreased. In addition, regarding the case of polyphenylene sulfide sulfone (hereinafter abbreviated as PPSS),
Although it is disclosed in Publication No. 880 etc., in the case of this resin,
Although the affinity between the resins was improved, there was a problem in that the heat resistance was poor. In addition, regarding the case of polyphenylene sulfide ketone (hereinafter abbreviated as PPSK), JP-A-64
Although it is disclosed in Japanese Patent No. 79259 and the like, it has not yet been put to practical use because it tends to gel during melt-kneading and has poor molding stability. Also, JP-A-63-13
PPS part and PPS disclosed in Publication No. 066 etc.
In the case of a block copolymer for the S portion, although the affinity between the resins is improved, the heat resistance is not satisfactory, and is disclosed in JP-A-2-229857 and JP-A-2-133428. In the case of a block copolymer of a PPS portion and a PPSK portion, flexibility and impact resistance were not sufficiently satisfactory due to poor affinity between the resins.

0004

[Problems to be Solved by the Invention] In view of the above problems, the present inventors have improved the heat resistance, chemical resistance, etc., which are the characteristics of PAS resins, by improving the affinity and compatibility between resins. The aim is to obtain a highly functional resin composition that has excellent properties and has improved impact resistance, flexibility, weather resistance, etc., which are disadvantages of PAS resins. .

[0005]

[Means for Solving the Problems] The present invention provides a block copolymer (hereinafter referred to as PP) consisting of a polyphenylene sulfide sulfone moiety and a polyphenylene sulfide ketone moiety.
The present invention relates to a resin composition comprising at least one polymer miscible with SS/PPSK) and, if necessary, a filler.

[0006] PPSS/ which is a component of the composition of the present invention
PPSK mainly consists of (-φ-SO2-φ-S-)
It is a block copolymer consisting of a part whose repeating unit is (PPSS part) and a part whose repeating unit is (-φ-CO-φ-S-) (PPSK part).
However, -φ- is a p-phenylene group, and will be expressed similarly hereinafter). PPSS/PPSK, like other PAS resins, has excellent chemical resistance, dimensional stability, flame retardancy, moldability, etc., and has a very high melting point of over 300°C, which is a problem with electronics and PPS. It is an ultra-highly functional polymer that satisfies the solder resistance properties of electrical parts.

[0007] The PPSS/PPSK can be obtained by the following manufacturing method and various other manufacturing methods. As a method for manufacturing PPSS/PPSK, for example, Japanese Patent Application Laid-open No. 63-113020 and No. 64-540
A dihalobenzophenone and an alkali metal sulfide are reacted in an organic amide solvent to synthesize terminal chlorphenylene group (or sodium sulfide group) type PPSK using the method disclosed in Publication No. 31, etc. Fourth
102875 and 4301274, a dihaloaromatic sulfone and an alkali metal sulfide are reacted in an organic amide solvent to form terminal sodium sulfide group (or chlorphenylene group) type PPSS.
Examples include a method in which a block copolymer is produced by synthesizing and reacting both in an organic amide solvent. In order to make PPSK or PPSS used in the synthesis of a block copolymer into a polymer having a predetermined terminal group structure, dihaloaromatic sulfone (
Alternatively, it can be obtained by blending either dihalobenzophenone) or an alkali metal sulfide in a somewhat excessive amount. For example, when obtaining a terminal chlorophenylene group type PPSS, it is possible to obtain the dihaloaromatic sulfone in excess of the alkali metal sulfide by about 5 mol %.

Dihaloaromatic sulfones used in the polymerization of PPSS include bis(4-bromophenyl)sulfone,
Bis(4-chlorophenyl)sulfone, bis(4-fluorophenyl)sulfone, etc. are suitable, and as the dihalobenzophenone used for polymerization of PPSK, 4,4'-
Dichlorobenzophenone, 4,4'-difluorobenzophenone, 4,4'-dibromobenzophenone and the like are preferred. Further, as the alkali metal sulfide, lithium sulfide, sodium sulfide, etc. are preferable, and those obtained by the reaction of alkali metal hydrosulfide and alkali metal hydroxide may also be used. In addition, as organic amide solvents, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone,
-Pyrrolidone and the like are preferably used.

[0009] The ratio of the PPSS part and the PPSK part in the block copolymer cannot be unconditionally defined because it varies depending on the type of resin to be blended and the purpose of use.
The SS portion ranges from 20 to 80 mol%, preferably from 25 to 75 mol%. A content within this range is particularly preferable for compatibility between resins, thermal stability, and heat resistance.

[0010] The PPSS/PPSK may contain a PPSS homopolymer or a PPSK homopolymer that may be included during production, as long as it does not impair the effects of the present invention. In addition, the PPSS/PPSK contains 30 mol% or less, preferably 10 mol% or less of polyarylene sulfide as shown below as another copolymer component.
It may contain the following. The polyarylene sulfide component that may be included includes divalent aromatic residues such as p-phenylene, m-phenylene, o-phenylene, 2,6-naphthalene, 4,4'-biphenylene, etc., or (- φ-O-φ-), (-φ-CH2-φ-)
, (-φ-C(CH3)2-φ-), etc., each aromatic ring contains F, Cl, Br. , CH3, etc. are introduced.

The melt viscosity of the PPSS/PPSK is the dynamic viscosity at 10 rad/sec at 20° C. above the melting point [
η'] is 50 to 105 poise, preferably 100 to 5
0000 poise is used.

[0012] As the other resin that is miscible with the PPSS/PPSK, which is the other component of the composition of the present invention, it is possible to use known resins related to conventionally known PAS resin compositions. Among them, polyamide, thermoplastic polyester, polysulfone, polyphenylene oxide, polyetherimide, polyether ketone, polyarylate, polycarbonate, phenoxy resin, α-olefin copolymer, styrene copolymer, conjugated diene copolymer, etc. Hydrogenated polymers, ABS resins, fluorine resins, and epoxy resins are preferably used.

[0013] As the polyamide (hereinafter abbreviated as PA), various well-known polyamides can be mentioned. Dicarboxylic acids such as oxalic acid, adipic acid, superic acid, sebacic acid, terephthalic acid, isophthalic acid, 1,4-cyclohexyldicarboxylic acid and ethylenediamine, pentamethylenediamine, hexamethylenediamine, decamethylenediamine, 1,4-cyclohexyl Polyamides obtained by polycondensing diamines such as diamines and diamines such as m-xylene diamine; polyamides obtained by polymerizing cyclic lactams such as caprolactam and laurinlactam; or salts of cyclic lactams, dicarboxylic acids, and diamines. Examples include polyamides obtained by copolymerization. Among these polyamides, preferably nylon 6, nylon 66, nylon 46, nylon MXD6 (copolymer of m-xylene diamine and adipic acid), nylon 6/10, nylon 66/6/10, nylon 6/66
, nylon 12, nylon 11, nylon 6/6T (a copolymer of caprolactam, terephthalic acid, and hexamethylene diamine), and two or more types of these polyamides may be used in combination. Particularly preferred are nylon 6, nylon 66, nylon 46, and nylon MXD6. PA has excellent heat resistance, flexibility, impact resistance, etc., but has problems such as flame retardancy and a decrease in strength due to water absorption. The composition of the present invention improves these problems.

Examples of thermoplastic polyesters include terephthalic acid, isophthalic acid, orthophthalic acid, naphthalene dicarboxylic acid, 4,4'-diphenyldicarboxylic acid, diphenylene ether dicarboxylic acid, α,β-bis(4-carboxyphenoxy)ethane, Adipic acid, sebacic acid,
Dicarboxylic acids such as azelaic acid, decanedicarboxylic acid, dodecanedicarboxylic acid, cyclohexanedicarboxylic acid, and dimer acid or their ester-forming derivatives 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, aliphatic polyester oligomers with hydroxyl groups at both ends, etc. It is a polyester obtained from glycols, and it usually has an intrinsic viscosity of {η
} is used in a range of 0.3 to 1.5 dl/g.

[0015] As a comonomer component, hydroxycarboxylic acids such as glycolic acid, hydroxybutyric acid, hydroxybenzoic acid, hydroxyphenylacetic acid, and naphthylglycolic acid, lactone compounds such as propiolactone, butyrolactone, valerolactone, and caprolactone, or thermal Within the range that can maintain plasticity, trimethylolpropane, trimethylolethane, glycerin, pentaerythritol, trimellitic acid, trimesic acid,
It may also contain a polyfunctional ester-forming component such as pyromellitic acid.

[0016] In addition, dibromoterephthalic acid, tetrabromoterephthalic acid, tetrabromophthalic acid, tetrachloroterephthalic acid, 1,4-dimethyloltetrabromobenzene, tetrabromobisphenol A, ethylene oxide adduct of tetrabromobisphenol A, etc. Also included are thermoplastic polyester resins in which an aromatic group has a halogen compound such as chlorine or bromine as a substituent, and a halogen compound having an ester-forming group is copolymerized.

Particularly preferred polyester resins include polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyhexamethylene terephthalate, poly(ethylene butylene terephthalate), and poly(cyclohexane dimethylene terephthalate).
, poly(butylene tetramethylene terephthalate),
Examples include 2,2-bis(β-hydroxyethoxytetrabromophenyl)propane copolymerized polybutylene terephthalate. Thermoplastic polyester is a polymer that has relatively well-balanced properties such as sliding properties, heat resistance, impact resistance, and weather resistance, but it does have some problems with heat resistance. In addition, there is a problem that mechanical properties such as impact resistance are significantly reduced in a blend system with PPS. The composition of the present invention improves these problems.

[0018] Polysulfone (hereinafter abbreviated as PSF) is
Arylene units together with ether and sulfone bonds,
It is defined as a polyarylene compound positioned in a disordered or orderly manner, for example, the following structural formulas (a) to (r) (wherein -Df- represents a 3,6-benzofuranylene group, and -Np- represents a 2-benzofuranylene group). , 7-naphthylene group, -Ph represents a phenyl group, and n represents an integer of 10 or more), but those having the structure (a) or (f) are preferred. These may be a single substance or a block copolymer. As a block copolymer, (
These include block copolymers of a) and (b), block copolymers of (f) and polyarylate, and block copolymers of (f) and polycarbonate.

(a) (-φ-O-φ-SO2-)n(b) (
-φ-φ-SO2-)n (c) (-SO2-Df-SO2-φ-O-φ-)
n(d) (-Np-SO2-φ-O-φ-)n(e
) (-SO2-φ-O-φ-SO2-φ-CH2-
φ-)n(f) (-φ-C(CH3)2-φ-O-
φ-SO2-φ-O-)n(h) (-O-φ-CH
2-φ-O-φ-SO2-φ-)n(i) (-O-
φ−O−φ−SO2−φ−)n(j) (−O−φ−
CO-φ-O-φ-SO2-φ-)n(k) (-O
-φ-C(Ph)2-φ-O-φ-SO2-φ-)n(
l) (-O-φ-O-φ-O-φ-SO2-φ-)
n(m) (-O-φ-SO2-φ-O-φ-CF2
-φ-)n(n) (-O-SO2-φ-φ-SO2
-φ-O-φ-O-φ-C(CH3)2-φ-O-)n (o) (-φ-SO2-φ-O-φ-SO2-φ-
O-φ-C(CH3)2-φ-O-)n (p) (-φ-SO2-φ-O-φ-SO2-φ-
)n(q) (−φ−φ−O−φ−SO2−φ−O−
)n(r) (-φ-O-φ-SO2-φ-φ-SO
2-)n

Polyphenylene oxide (hereinafter abbreviated as PPO) is polyphenylene ether (PPE).
It can be obtained by polycondensing one or more types of monocyclic phenols represented by the following general formula [1].

[0021]

[Chemical formula 1]

(However, R1 is a lower alkyl group having 1 to 3 carbon atoms, R2 and R3 are hydrogen or a lower alkyl group having 1 to 3 carbon atoms, and there is always a lower alkyl substituent at the ortho position of at least one of the hydroxyl groups. ) The above PPO may be a homopolymer or a copolymer.

Examples of the monocyclic phenol represented by the formula [1] include 2,6-dimethylphenol and 2,6-dimethylphenol.
, 6-diethylphenol, 2,6-dipropylphenol, 2-methyl-6-ethylphenol, 2-methyl-6-propylphenol, 2-ethyl-6-propylphenol, m-cresol, 2,3-dimethyl Phenol, 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 from this 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, 2,6-dipropylphenol/2,3,6
-trimethylphenol copolymer, poly(2,6
-dimethyl-1,4-phenylene) ether and 2,6-
Examples include copolymers obtained by graft polymerizing styrene onto dimethylphenol/2,3,6,-trimethylphenol copolymers.

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

Polyetherimide (hereinafter abbreviated as PEI) has the following formula [2].

[0027]

[Case 2]

In the above formula, -O-Q1-O- is bonded to the 3 or 4 and 3' or 4' positions, and Q1 is a substituent such as [3] or [4] shown below. or an unsubstituted aromatic group, or a divalent substituted or unsubstituted aromatic derivative group of [5]

[0029].

[Chemical formula 3]

Here, Q' is independently C1-C6 alkyl, aryl or halogen. Q3 is
selected from -O-, -S-, -CO-, -SO2-, -SO-, cycloalkylene having 1 to 6 carbon atoms, alkylidene having 1 to 6 carbon atoms, or cycloalkylidene having 4 to 8 carbon atoms, Q2 are aromatic hydrocarbon groups having 6 to 20 carbon atoms and their halogenated derivatives (wherein the alkyl group contains 1 to 6 carbon atoms), alkylene having 2 to 20 carbon atoms and It is a polydiorganosiloxane having a cycloalkylene group and a C2 to C8 alkylene as a terminal group, or the above formula [5].

Polyetherketone (hereinafter abbreviated as PEK) is a repeating unit (-φ-CO-φ-O-) of the following formula [6].
[6] and/or a repeating unit of the following formula [7] (-φ-O-φ-CO-φ-)
It is a tough crystalline thermoplastic aromatic polyetherketone containing [7] alone or together with other repeating units and having an intrinsic viscosity (I.V.) 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, -SO2-,
-CO- or a divalent hydrocarbon group. ] and formula [9] (-φ-CO-φ-O-φ-CO-φ-O-)
[9], and further, as a copolymerization unit, formula [10] (-φ-O-φ-S02-φ-O-)
[10] and formula [11]

[0032]

[C4]

It includes a repeating unit represented by:

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
'-Dimethyl diphenyl 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-
Examples thereof include 3,5-dichlorophenyl)-propane, and a particularly preferred one is 2,2-bis-(4-hydroxyphenyl)-propane, which is called 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, succinic acid, malonic acid, sebacic acid, glutaric acid, azelaic acid, and speric acid, preferably isophthalic acid and terephthalic acid or mixtures of these derivatives. .

As the polycarbonate (hereinafter abbreviated as PC), homogeneous PC or PC copolymers based on one or more of the following bisphenols 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)-diisopropylbenzene and their compounds substituted with alkyl or halogen in the nucleus.

Among these, preferred bisphenols 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)-
Examples include propane, and 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 is mentioned.

Preferred PCs are those based on the preferred bisphenols described above. Particularly suitable PC copolymers are 2
, 2bis-(4-hydroxyphenyl)-propane and one of the other particularly preferred bisphenols mentioned above.

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

[0040] The PC may be processed using a known method, for example, Bispha.
It can be produced by a method such as a melt transesterification reaction between alcohol and diphenica carbonate, or a two-phase interfacial polymerization method between bisphenol and phosgene.

[0041] Above, PSF, PPO, PEI, PEK,
PAr and PC both have high glass transition temperatures (Tg)
Although it has excellent mechanical properties such as impact resistance, it has been problematic that it has poor moldability and chemical resistance. Also, P
There has been a problem that when PO and PEI are blended with PPS, mechanical properties such as impact resistance are significantly reduced. According to the composition of the present invention, these problems can be improved.

ABS resin is produced by polymerizing two or more compounds selected from vinyl cyanide monomers, aromatic vinyl monomers, and acrylic monomers in the presence of conjugated diene rubber. This is a graft copolymer obtained by 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. Can be done. Examples of the conjugated diene rubber in the graft copolymer include polybutadiene, butadiene-styrene copolymer, butadiene-acrylonitrile copolymer, etc., and examples of the vinyl cyanide monomer include acrylonitrile, methacrylonitrile, etc. Examples of the vinyl monomer include styrene, vinyltoluene, dimethylstyrene, chlorostyrene, and particularly preferably α-methylstyrene. In addition, acrylic monomers include acrylic acid, methacrylic acid, methyl acrylate,
Examples include ethyl acrylate, butyl acrylate, methyl methacrylate, and hydroxyl acrylate.

The α-olefin of the α-olefin copolymer includes ethylene, propylene, butene-1, isobutene, pentene-1, 4-methylpentene-1, hexene-1, and the like. These may be used alone or as a copolymer of two or more. Furthermore, other monomers copolymerizable with these α-olefins, such as butadiene,
Vinyl acetate, vinyl propionate, methyl acrylate,
It is also possible to copolymerize methyl methacrylate, acrylonitrile, styrene, vinyl ether, acrylic acid, methacrylic acid, and unsaturated dicarboxylic acids such as maleic acid. In addition, N
Ionomers containing metal ions such as a+ and Zn++ may also be used. Among the above α-olefin copolymers, ethylene copolymers are particularly preferably used.

Examples of the styrenic copolymer include styrene homopolymers and copolymers with other monomers copolymerizable with styrene, such as α-methylstyrene,
Styrene derivative monomers such as dimethylstyrene and chlorstyrene; acrylic acid, methacrylic acid, maleic acid,
Unsaturated carboxylic acids such as maleic anhydride; acrylic acid esters such as methyl acrylate, methyl methacrylate, ethyl acrylate, and ethyl methacrylate; or one or more vinyl monomers such as vinyl acetate and vinyl ether. It is a copolymer with the monomer of

Hydrogenated conjugated diene copolymers include homopolymers of diene monomers such as butadiene and pentadiene, and hydrogenated copolymers of diene monomers and other monomers copolymerizable. For example, copolymers of the above-mentioned styrene-based copolymers with styrene derivative monomers, unsaturated carboxylic acids, acrylic esters, vinyl monomers, etc. may be mentioned.

[0046] Phenoxy resin is a high molecular weight thermoplastic polyether resin that does not have epoxy groups at either end and is synthesized using bisphenol A and epichlorohydrin as main raw materials. Further, dihydric phenol, bisphenol such as bisphenol F, tetrachlorobisphenol, diphenolic acid, bisphenol and p-
It includes thermoplastic polyethers that do not have epoxy groups at both ends and are synthesized by the reaction of a diol compound such as a xylene dichloride condensate with an epoxy compound such as epichlorohydrin, butadiene oxide, or a glycidyl compound.

[0047] Fluororesin is a general term for synthetic polymers containing fluorine atoms in their repeating units and their copolymers, including polytetrafluoroethylene, polychlorotrifluoroethylene, and tetrafluoroethylene/hexafluoropropylene. So-called fluororesins such as copolymers, tetrafluoroethylene/perfluoroalkyl vinyl ether copolymers, polyvinylidene fluoride, polyvinyl fluoride, tetrafluoroethylene/ethylene copolymers, and vinylidene fluoride/hexafluoropropylene copolymers The main one is fluororubber, mainly .

The epoxy resin contains (1) bisphenol A,
The combination of epichlorohydrin and an active hydrogen compound having a phenolic hydroxyl group such as dihydric phenol or novolac resin, a carboxyl group such as terephthalic acid or methacrylic acid, or an amino group or amide group such as aniline, p-phenylenediamine or sulfonamide, etc. Epoxy resins obtained by reaction, such as reaction products of bisphenol A and epichlorohydrin, glycidyl ethers of phenol or cresol novolak resins, glycidyl esters of organic acids such as phthalic acid and methacrylic acid, etc. (2) double bonds Compounds such as epoxy resins obtained by liquid phase oxidation with hydrogen peroxide, peracetic acid, etc., such as olefin compounds, butadiene, or oxidation products with peracids such as soybean oil, oleic acid or its esters, etc. (3) Epoxy resin obtained by air oxidation of double bond compounds,
Examples include styrene oxide. Among them,
Bisphenol type or novolak type epoxy resins are preferably used.

[0049] The proportion of each resin in the composition of the present invention varies depending on the type of resin and purpose of use, so it cannot be unconditionally defined, but usually when using an epoxy resin,
0.1 to 1 per 100 parts by weight of PPSS/PPSK
0 parts by weight, preferably 0.2 to 5 parts by weight, α-
When using an olefin copolymer, styrene copolymer, hydrogenated conjugated diene copolymer, or phenoxy resin, P
For 100 parts by weight of PSS/PPSK, it is 1 to 100 parts by weight, preferably 2 to 80 parts by weight, and for other resins, 95 to 5 parts by weight of PPSS/PPSK and 5 to 95 parts by weight of other resins. Parts by weight, preferably PPSS/
90 to 10 parts by weight of PPSK and 10 to 90 parts by weight of other resins.

[0050] The resin composition of the present invention may contain, if necessary,
By incorporating fibrous or granular fillers, it is possible to improve heat resistance, mechanical properties, and dimensional stability. Examples of fibrous fillers include glass fiber, carbon fiber,
Examples include silane glass fibers, boron fibers, whiskers, potassium titanate, asbestos, silicon carbide, aramid fibers, ceramic fibers, and metal fibers. Further, examples of the granular filler 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 fillers can also be treated with a silane-based or titanium-based coupling agent that is commonly used as a processing agent for fillers. The proportion of filler added varies depending on the type of filler and purpose of use, but usually 10 to 300 parts by weight, preferably 30 to 200 parts by weight of fibrous filler is added to 100 parts by weight of resin.
In the case of granular fillers, it is usually 2 to 10 parts by weight.
0 parts by weight, preferably 5 to 80 parts by weight.

The composition of the present invention may also contain small amounts of a mold release agent such as polyethylene wax, colorants such as various pigments, heat stabilizers, antioxidants, ultraviolet stabilizers, A blowing agent, a flame retardant, a flame retardant aid, a rust preventive, a silane coupling agent such as aminosilane or epoxysilane, or a titanate coupling agent can be contained. In addition, as heat-resistant stabilizers, hydroxides, oxides, and aromatic carboxylates of Group IIa metals of the Periodic Table, excluding magnesium, and aromatic carboxylates, carbonates, and hydroxides of Group Ia metals of the Periodic Table. As antioxidants, basic compounds such as phosphates, borates, etc., especially hydroxides and oxides of calcium and barium, and hindered phenol compounds, hindered amine compounds, and phosphorus compounds, especially 3 As a rust preventive agent, a phosphorus compound having a valence of and zinc carbonate are preferably used.

The composition of the present invention can be prepared by various known methods. For example, after mixing the raw materials in a mixer such as a dumbler or Henschel mixer, the raw materials are fed to a single or twin screw extruder, melt-kneaded at 290 to 420°C, and pelletized, or the raw materials are mixed in a solvent. After the mixing treatment, the obtained resinous material is melt-kneaded in an extruder and pelletized, or the resinous material and PPSS/PPSK are mixed.
There are cases where a thermoplastic resin and a thermoplastic resin are melt-blended.

[0053]

[Examples] Examples will be shown below, but the present invention is not limited thereto.

[Reference Example 1] (Synthesis example of PPSS/PPSK) In a 10 L autoclave, 1980 g of N-methylpyrrolidone (NMP) and sodium sulfide 2.7 hydrate (N
a2S) 656g, sodium hydroxide (NaOH) 2
g, and bis(p-chlorophenyl)sulfone 1436
g was charged and reacted at 200° C. for 6 hours under a nitrogen atmosphere. Furthermore, 72 g of bis(p-chlorophenyl)sulfone
and 200g of NMP were added and reacted at 210°C for 1 hour.
A slurry of a PPSS reactant having a terminal chlorine group was obtained.

Next, add NMP 2 to a 10L autoclave.
940g, Na2S 964g, and NaOH 3.6
g, put into a nitrogen atmosphere, heated to 190°C over about 2 hours while draining water, and cooled to 100°C.
1750g of 4,4'-dichlorobenzophenone and NM
700 g of P was added and the mixture was further reacted at 240° C. for 3 hours to obtain a slurry of the PPSK reactant having terminal sodium sulfide groups.

[0056] The above PPSK reactant slurry, PPSS reactant slurry and NMP were charged into an autoclave, and 21
React at 0°C for 3 hours, purify by a known method, and obtain PPSK.
block copolymer (PPSS/PP
SK) was obtained. P determined by scanning differential calorimeter (DSC)
The melting point of PSS/PPSK is 340°C, 360°C,
The dynamic viscosity at 10 rad/sec was 700 poise.

[Example 1, Comparative Example 1] PPSS/PPS
K and modified PPO were blended in a 1:1 ratio, melted and kneaded at 350°C to form pellets, and then sample pieces were created using an injection molding machine. Both moldability and appearance of the molded product were good. Izod impact test (no notch), bending test, and penetration test were conducted. In addition, as a comparative example, PPS and modified PP
In case of O, as a reference example, PPSS/PPSK
A similar study was conducted for PPS and PPS alone. Although the comparative example had good moldability, the appearance of the molded product was uneven and poor. The results are shown in Table-1. Incidentally, an attempt was made to melt blend PPSK and modified PPO, but gelation occurred and molding was not possible. When the fractured surface of the sample piece subjected to the Izod test was observed with a scanning electron microscope (SEM), it was found that
In the examples, it was observed that dispersed particles of about 1 to 10 microns were uniformly dispersed. In addition, in the comparative example, 10 to 5
It was observed that 0 micron spherical dispersed particles were non-uniformly dispersed.

The modified PPO used was Noryl 534J-801 manufactured by General Electric Co., and the PPS used was B-600 manufactured by Dainippon Ink Chemical Co., Ltd. In addition, for the Izod test, a bar-shaped specimen with a cross-sectional area of 3.2 x 3.2 mm2 was used, and for the bending test, a bar specimen with a width of 10 mm, a thickness of 2 mm, and a span length of 3 was used.
A 0 mm sample piece was used, and TMA-SS120C manufactured by Seiko Electronics Industries, Ltd. was used for the penetration test. In addition, all blending ratios are expressed as weight ratios, and the same applies hereinafter.

[Examples 2 and 3] The mixing ratio of PPSS/PPSK and modified PPO was 7:3 (Example 2) and 3:7.
(Example 3) A sample piece was prepared in the same manner as in Example 1, and a bending test and an Izod impact test (without a notch) were conducted. Both moldability and appearance of the molded product were good. The results are shown in Table-1.

[Example 4, Comparative Example 2] PPSS/PPS
K, modified PPO, and glass fiber were blended as shown in Table 1, samples were prepared in the same manner as in Example 1, and the same studies were conducted. However, the total resin amount and glass fiber amount are 6
The score was 4 vs. Heat deformation test (HDT) instead of penetration test
I did it. Further, as a comparative example, a similar study was conducted using PPS. The results are shown in Table-1.

As the glass fiber, chopped strand CS06MA404 manufactured by Asahi Fiberglass Co., Ltd. was used.

[0062]

[Table 1]

[Examples 5-7, Comparative Examples 3-5] PPSS
/PPSK and polyethersulfone (PES), PEI
, using polyetheretherketone (PEEK),
The same study as in Example 1 was conducted. In all cases, moldability and appearance of the molded products were both good. Note that the melt-kneading temperature was 350 to 360°C. The results are shown in Table-2. Further, as a comparative example, a similar study was conducted on a blend system of PPS and each resin. Although the moldability was good, the appearance of the molded product was poor and the compatibility was poor.

[0064] For PES and PEEK, VICTREX PES-4100 and PEEK-380 manufactured by ICI Corporation were used, respectively, and for PEI, Ultem 1000 manufactured by General Electric Company was used.

[Examples 8 to 11] Similar studies as in Examples 2 and 3 were conducted regarding the cases of PPSS/PPSK, PES, and PEI. Both moldability and appearance of the molded product were good. The results are shown in Table-2.

[0066]

[Table 2]

[Examples 12 to 17, Comparative Examples 6 and 7] PP
In the case of SS/PPSK, PAr and PC, table-
3, and the same study as in Example 1 was conducted. In all cases, the moldability and appearance of the molded products were good. The results are shown in Table-3. Note that the penetration test was conducted only in the case of a 1:1 ratio. Furthermore, similar studies were conducted using PPS as a comparative example. The results are shown in Table-3.

[0068] PAr is U polymer manufactured by Unitika Co., Ltd.
U-100 was used, and Iupilon S-2000 manufactured by Mitsubishi Gas Chemical Co., Ltd. was used as the PC.

[0069]

[Table 3]

[0070] In addition, PAr was immersed in 20% sodium hydroxide and PC was immersed in acetone for about 50 hours to examine their solvent resistance. When the block copolymer and PAr are 4:6, the bending strength is 90 MPa, and when PPS and PAr are 4:6, the bending strength is 90 MPa.
In the case of pair 6, the bending strength was 46 MPa. When the block copolymer and PC are 1:1 and 3:7, the weight increase rate is 1.05% and 1.07%, respectively, and the bending strength is 70 MPa and 75 MPa, respectively.Similarly, PPS and PC
When the ratio is 1:1 and 3:7, the weight increase rate is 1.
13% and 1.18%, and the bending strengths were 35 MPa and 25 MPa, respectively. Note that when the ratio of PPS and PC was 3 to 7, cracks were generated in the sample piece due to immersion.

[Examples 18 to 21, Comparative Examples 8 and 9] PP
Table of SS/PPSK, nylon 66 and nylon 46
The same study as in Example 1 and Comparative Example 1 was carried out using the mixture as shown in 4. In all Examples, moldability and appearance of the molded products were both good. Although the moldability of the comparative example was good, the appearance of the molded product was pearl-like and inferior. The results are shown in Table-4. Note that the penetration test was conducted only in the case of a 1:1 ratio.

Regarding Example 18 and Comparative Example 8, S
The fracture surface was observed by EM, and in the examples, dispersed particles of 1 micron or more were not observed, but in the comparative examples, spherical particles of 3 to 20 microns were observed to be non-uniformly dispersed. Ta.

In addition, regarding the case of Example 20 (block copolymer/nylon 66: 3:7), the sample piece was
It was immersed in warm water at 0°C for 50 hours, and its water absorption and bending strength were measured. The weight increase rate due to water absorption was 2.2%, and the bending strength was 88 MPa. In addition, when PPS and nylon 66 were used in a ratio of 3:7, the water absorption rate was 3.8% and the bending strength was 54 MPa.

[0074] Nylon 66 is UBE manufactured by Ube Industries, Ltd.
Nylon 2026D was used, and nylon 46 was JSR nylon 46 manufactured by DMS.

[Example 22, Comparative Example 10] PPSS/P
PSK, nylon 66, and glass fiber were mixed as shown in Table 4, samples were prepared in the same manner as in Example 4, and the same studies were conducted. However, the total amount of resin and the amount of glass fiber were 6:4. Further, as a comparative example, a similar study was conducted using PPS. The results are shown in Table-4.

[0076]

[Table 4]

[Examples 23 to 26, Comparative Examples 11 and 12]
PPSS/PPSK, PBT, and PET were mixed as shown in Table 5, and the same study as in Example 1 was conducted. In all Examples, moldability and appearance of the molded products were both good. Although the moldability of the comparative example was good, the appearance of the molded product was pearl-like and inferior. The results are in the table-
5. Note that the penetration test was conducted only in the case of a 1:1 ratio.

Note that Planac BT-128 manufactured by Dainippon Ink and Chemicals Co., Ltd. was used as PBT, and Mitsui PET J-125 manufactured by Mitsui PET Co., Ltd. was used as PET.

[Example 27, Comparative Example 13] PPSS/P
PSK, PBT, and glass fiber were blended as shown in Table 5, samples were prepared in the same manner as in Example 4, and the same studies were conducted. However, the total resin amount and glass fiber amount are 6
The score was 4 vs. Further, as a comparative example, a similar study was conducted using PPS. The results are shown in Table-5.

[0080]

[Table 5]

[Examples 28-32, Comparative Examples 14-18]
PPSS/PPSK and polyethylene, ionomer, phenoxy resin, hydrogenated styrene/butadiene rubber (SBR
), polyvinylidene fluoride (PVdF), and glass fiber were mixed as shown in Table 6, and the same study as in Example 1 or Example 4 (when glass fiber was added) was conducted. In all Examples, moldability and appearance of the molded products were both good. Although the comparative example had good moldability,
The appearance of the molded product was uneven and poor. The results are shown in Table-6. Note that a needle penetration test was not conducted.

[0082] The polyethylene was Shorex F-5010 manufactured by Showa Denko, and the ionomer was Himilan 1707 manufactured by DuPont Mitsui Polychemicals.
The phenoxy resin is UCAR manufactured by Union Carbide.
Phenoxy PKHH was used, hydrogenated SBR was Tuftix M193G manufactured by Asahi Kasei Corporation, and PVdF was used Neoflon PVDF VP-810 manufactured by Daikin Industries.

[0083]

[Table 6]

[Example 33] PPSS/PPSK100
2 parts by weight of the epoxy resin was added to each part by weight, a sample was prepared in the same manner as in Example 1, and the same study as in Example 1 was conducted. Izod impact strength is 25Kg・cm/cm
2. The bending deflection was 5.2% and the bending strength was 130 MPa.

The epoxy resin used was Epicron N-965 manufactured by Dainippon Ink Chemical Co., Ltd.

[0086]

[Effects of the Invention] The resin composition of the present invention has significantly improved blend compatibility and heat resistance, and various properties such as mechanical properties such as impact resistance and chemical resistance. Therefore, the resin composition of the present invention can be used, for example, in electrical and electronic parts such as connectors, printed circuit boards, and sealed molded products, and in automobile parts such as lamp reflectors and various electrical components.
Interior materials for various buildings, aircraft, and automobiles, leisure and sports equipment such as tennis rackets, skis, golf clubs, and fishing rods, audio materials such as enclosures for speakers, back decks for stringed instruments, and OA equipment parts and cameras. Injection molding of precision parts such as parts and watch parts
It is used as a molding material with excellent mechanical properties such as heat resistance and impact resistance in various molding fields such as compression molding, extrusion molding, and pultrusion molding of composite sheets and pipes.

Claims (3)

[Claims] 1. A resin composition comprising (A) a block copolymer comprising a polyphenylene sulfide sulfone moiety and a polyphenylene sulfide ketone moiety; and (B) at least one miscible resin. 2. A block copolymer comprising (A) a polyphenylene sulfide sulfone moiety and a polyphenylene sulfide ketone moiety; (B) at least one miscible resin; and (C) a filler. Resin composition. 3. (B) polyamide as the miscible resin;
Thermoplastic polyester, polysulfone, polyphenylene oxide, polyetherketone, polyetherimide, polyarylate, polycarbonate, phenoxy resin, α-olefin copolymer, styrene copolymer, hydrogenated conjugated diene copolymer, ABS type 3. The resin composition according to claim 1, wherein at least one resin selected from resins, fluororesins, and epoxy resins is used.