JPH03244633A - New resin composition - Google Patents

Abstract

PURPOSE:To improve the elastic modulus of a polyphenylene ether without allowing anisotropy to occur and without deteriorating the heat resistance, flexibility, and mechanical properties inherent in the polyphenylene ether by copolymerizing it with a specific arom. polyamide. CONSTITUTION:A compd. having an arom. diamine residue of formula I {wherein R1 is phenylene, naphthalene, or a group of formula II or III [wherein X is S, SO2, CO, O, C(R3)2 (wherein R3 is H, halogen, or a 1-8C aliph. or arom. hydrocarbon group)]; R2 is a substituent on an arom. ring, e.g. halogen, or a 1-8C aliph. or arom. hydrocarbon group; and (a) is 0-8} is polycondensed with a compd. having a dicarboxylic acid residue of formula IV [wherein R4 is R1 (wherein R6 is R3); R5 is R2; and (b) is (a)] to give an arom. polyamide, which is copolymerized with a polyphenylene ether to give the title compsn.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a novel polyphenylene ether resin composition having excellent elastic modulus, heat resistance, flexibility, and fluidity. This invention relates to a novel resin composition in which part or all of an aromatic polyamide is copolymerized.

[Conventional technology]

Polyphenylene ether has excellent heat resistance, rigidity, electrical properties, etc. It is a resin and a polymeric material useful as an engineering plastic. However, the modulus of elasticity, which indicates the rigidity of a material, is about 20,000 Kt/cd, which is insufficient when considering applications that require rigidity, such as replacement of metals. Therefore, in order to improve the elastic modulus while taking advantage of polyphenylene ether's excellent characteristics such as heat resistance and electrical properties, high elastic modulus fibers such as glass fiber, carbon fiber, and even aramid (wholly aromatic polyamide) fiber are used. Techniques for reinforcing materials to improve the elastic modulus have been developed, and some are in practical use. However, although these techniques certainly improve the elastic modulus of polyphenylene ether, they have the problem that they only provide materials with poor flexibility, such as breaking immediately or before the yield point in a tensile test. have.

Furthermore, when the aforementioned fibers are blended into polyphenylene ether, they tend to become oriented in the machine direction, especially during injection molding. For this reason, there is also the problem that the elastic modulus is strengthened only in the flow direction, that is, only materials with anisotropy in the elastic modulus can be obtained. For this reason, we have already considered a technology for blending fully aromatic polyamides, such as aramid resin, which are polymers with high elastic modulus and excellent heat resistance, with polyphenylene ether, and have previously applied for a patent ( JP-A-6O-15435).

Although the resulting blend had improved modulus of elasticity and heat resistance, it was a brittle material that had lost its flexibility and had anisotropy in modulus of elasticity and strength. Therefore, we investigated copolymerization of polyphenylene ether and aramid resin with the aim of improving this point.

[Problem that the invention seeks to solve]

That is, an object of the present invention is to improve the elastic modulus of polyphenylene ether without impairing its heat resistance, flexibility, and mechanical properties, and without causing anisotropy.

[Means for solving problems]

The problem of the present invention is that (A) is a polyphenylene ether (B) is a compound (Rz)a having an aromatic diamino compound residue represented by the general formula (1) [where R1: is the same or different] Moyoi phenylene, S
1SO2, Co, O, C(R3)2 (R3: hydrogen, halogen, aliphatic or aromatic hydrocarbon group having 1 to 8 carbon atoms, which may be the same or different)) R2: substituent on aromatic ring and represents a halogen, an aliphatic or aromatic hydrocarbon group having 1 to 8 carbon atoms, which may be the same or different, and a: 0 or an integer from 1 to 8. ] and a compound having an aromatic dicarboxy compound residue represented by the general formula (R4) [here, R4: phenylene, s, s, which may be the same or different;
o2, co, o, c 11)2 (Re: hydrogen, halogen, which may be the same or different, carbon number 1 to 8
aliphatic or aromatic hydrocarbon group)) R5: halogen, which is a substituent on the aromatic ring and may be the same or different, an aliphatic or aromatic hydrocarbon group having 1 to 8 carbon atoms, b Indicates double or an integer from 1 to 8. ] When an aromatic polyamide obtained by polycondensation of

(A) polyphenylene nitert, general formula (■), (
Obtained by polycondensing a compound having 11 aromatic diamino compound residues and aromatic dicarboxy compound residues (
The problem was solved by B) a resin composition obtained by copolymerizing one or more selected from the aromatic polyamide group.

The polyphenylene ether which is the AFli component used in the resin composition of the present invention is a one-terminal hydroxy type polyphenylene ether obtained by polycondensing one or more monocyclic phenols represented by the general formula fl[ll, and This includes both polyphenylene ethers with hydroxyl terminals obtained by polycondensing the monocyclic phenol in the presence of an aromatic dihydroxy compound.

1 (Here, R1 is a lower alkyl group having 1 to 3 carbon atoms or a halogenated alkyl group, R2 and R3 are a hydrogen atom, a lower alkyl group having 1 to 3 carbon atoms, or a halogenated alkyl group, and at least one of the hydroxyl groups (There is always a lower alkyl substituent at the ortho position of
, a compound (modifier) that simultaneously has a β-unsaturated double bond and at least one functional group selected from a group of functional groups such as a carboxy group, an acid anhydride group, a hydroxy group, an ester group, an amino group, an epoxy group, etc. Alternatively, it also includes modified polyphenylene ether obtained by reacting a vinyl aromatic compound in the presence or absence of a radical initiator in a solution or under melt-kneading. This polyphenylene ether may be a homopolymer or a copolymer.

Examples of the monocyclic phenol represented by the general formula (ffl) include 2.6-dimethylphenol and 2.6-dimethylphenol.
diethylphenol, 2,6-dipropylphenol,
2-methyl-6-ethylphenol, 2-methyl-6-
propylphenol, 2-ethyl-6-propylphenol, m-fresol, 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-drimethylphenol, 2,3.6-driethylphenol, 2.3.6-
) Dipropylphenol, 2.6-dimethyl-3-ethylphenol, 2.6-dimethyl-3-propylphenol, 2.6-dichlorophenol, 2-chloro-6-
Methylphenol, 2,6-dimethyl-3-chlorophenol, 2,6-dichlorophenol, 2-bromo-6
-Methylphenol, 2.6-dimethyl-6-promophenol, 2.6-cyclomethylphenol, 2-chloromethyl-6-methylphenol, 2.6-dibromomethylphenol, 2-bromomethyl-6-methylphenol , 2,6-diallylphenol, 2-allyl-6
-Methylphenol, 2.6-dicarboxyphenol, 2-carboxyl-6-methylphenol, 2.6-
Examples include dimethyl-3-carboxylphenol. As the one-terminal hydroxy type polyphenylene ether obtained by polycondensation of one or more of these phenols, for example, poly(2#6-cymethyl-1.4-
7enylene)ether, poly(2#6-diethyl-1,
4-phenylene) ether, poly(2,6-diprobyl-1,4-7enylene) ether, poly(2-methyl-
6-ethyl-1,4-phenylene)zf, poly(
2-Methyl-6-broby-1,4-phenylene) ether, poly(2-ethyl-6-broby-1,4-phenylene) ether, 2°6-dimethylphenol/2.
3.6-) diethylphenol copolymer, 2.6-ethylphenol/2.3.6-) diethylphenol copolymer, 2,6-diethylphenol/2.3.6-dolimethylphenol copolymer 2,6-dipropylphenol/2.3.6-) diethylphenol copolymer. Among these, the preferred one is poly (
Examples include 2,6-dimethyl-1,4-phenylene) ether and poly(2,6-diethylphenol/2,3,6-drimethylphenol copolymer).

The aromatic dihydroxy compound represented by the general formula (II+), which is used to coexist during the polycondensation of monocyclic phenols to obtain a polyphenylene ether with hydroxyl terminals, is an aromatic compound having two hydroxy groups. Examples include dihydroxybenzenes, dihydroxynaphthalenes, dihydroxybiphenyls, and bisphenols. Specifically, hydroquinone, resorcinol, 2.6
-1 and 1,5-s7talediol, 4,4'- and 4,3-dihydroxybiphenyl, bisphenol A, bisphenol S, 4,4'- and 4,3-thiobiphenol, 4. 41- and 4,3-dihydroxydiphenyl ketone, 4,4'- and 4,3-dihydroxydiphenyl ether, and at least one hydrogen of these benzene nuclei is CI, Br, halogen such as 1, lower alkyl group, alkoxy Examples include nuclear-substituted derivatives substituted with groups such as phenyl groups, naphthyl groups, and the like. Moreover, these may be used in combination. Preferred among these are hydroquinone, resorcin; methylated, isopropyl, tert-butyl, phenylhydroquinone and resorcin; 2,6- and 1,5-naphthalenediol #4
, 4/- and 4,3-dihydroxybiphenyl, bisphenol A1 bisphenol S, 4.4'- and 4.3-thiobiphenol, 4.4'- and,
4.3-dihydroxydiphenyl ketone, 4.4'- and 4.3-dihydroxydiphenyl ether; 3.
5.3', 5'-tetramethyl-4°4'-dihydroxybiphenyl, 3.5.3'5'-tetramethylbisphenol A, 3.5°3', 5'-tetramethylbisphenol S13°5. 3',5'-tetramethyl4.
4'-thiobiphenol, 3,5.3',5'-tetramethyl 4.4'-dihydroxyphenyl ketone, 3.5
゜3',5'-tetramethyl-4,4'-dihydroxydiphenyl ether, more preferred is 3.
5.3',5'-tetramethyl-4゜42-dihydroxybiphenyl, 3.5.3'5'-tetramethylbisphenol A, 3,5゜3',5'-tetramethylbisphenol S, 3゜5 .3'5'-tetramethyl4.4'
-Thiobiphenol, 3.5.3', 5'-tetramethyl 4°4'-dihydroxyphenyl ketone, 3,5
．． 3'.

5'-tetramethyl-4,4'-dihydroxydiphenyl ether, the most preferred is 3°5.3',
5'-Tetramethylbisphenol A.

Therefore, examples of the polyphenylene ethers include all those obtained by polycondensing one or more of all the phenols exemplified as monocyclic phenols in the presence of one or more of the aromatic dihydroxy compounds exemplified. This is an example. Among these polyphenylene ethers, monocyclic phenols, 3,5,3', 5'
-tetramethyl-4,4'-dihydroxybiphenyl,
3°5.3',5'-tetramethylbisphenol A.

3.5.3',5'-tetramethylbisphenol S,
3,5.3', 5'-tetramethyl 4,4'-thiobiphenol, 3,5.3', 5'-tetramethyl 4,4'-dihydroxyphenyl ketone, 3.5.3'
, 5'-tetramethyl-4,4'-dihydroxydiphenyl ether copolymer, and the more preferred one is 2.
It is a copolymer of 6-diethylphenol alone or a mixture of 2.6-diethylphenol and 2°3.6-)diethylphenol. Most preferred is 2,6-dimethylphenol alone or a mixture of 2,6-dimethylphenol and 2,3,6-dimethylphenol.
．． It is a copolymer of 5.3',5'-tetramethylbisphenols.

This is a modifier for modified polyphenylene ether.The molecule contains a β-unsaturated double bond and a functional group selected from a group of carboxy groups, acid anhydride groups, hydroxy groups, ester groups, amino groups, and epoxy groups. , a compound having at least one type of modifying agent, specifically, for example, α,β-unsaturated dicarboxylic acids exemplified by maleic acid, chloromaleic acid, citraconic acid, itaconic acid, etc.; acrylic acid, puranic acid. , crotonic acid, vinyl acetic acid, methacrylic acid, pentenoic acid, angelic acid, etc.; acid anhydrides of these α,β-unsaturated dicarboxylic acids and unsaturated monocarboxylic acids; glycidyl acrylate; α, β exemplified by glycidyl methacrylate
-Unsaturated carboxylic acid glycidyl ester compounds; methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, hexyl acrylate, hydroxyethyl acrylate, phenyl acrylate,
and α,β-unsaturated carboxylic acid ester compounds such as these esters of methacrylic acid; examples of acrylamide and methacrylamide include β-unsaturated carpondeamide. Among these, preferred are maleic acid, citraconic acid, acrylic acid,
Methacrylic acid, maleic anhydride, citraconic anhydride, glycidyl methacrylate, glycidyl acrylate, methacrylamide, acrylamide, and more preferred are maleic anhydride, citraconic anhydride, glycidyl methacrylate, glycidyl acrylate, and the like. Also, the most preferred one is maleic anhydride.

Further, examples of vinyl aromatic compounds include styrene, α-methylstyrene, chlorostyrene, vinyltoluene, divinylbenzene, etc., and preferred ones include styrene, α-methylstyrene, etc. These modifiers and vinyl aromatic compounds are used in an amount of 0.01 to 20 Wt96 for polyphenylene ether having hydroxy type at one end and both ends. The polyphenylene ether of the present invention is polyphenylene ether with hydroxy type at one end and both ends, and modified products thereof, and all of these can be used in combination. Preferred polyphenylene ethers are polyphenylene ethers with hydroxyl type at both ends, and mixtures of polyphenylene ethers with hydroxyl type on both ends and polyphenylene ether with hydroxyl type on one end, and most preferred polyphenylene ethers are polyphenylene ether with hydroxyl type on both ends and polyphenylene ether with hydroxyl type on one end. It is a mixture of

Next, the compounds having an aromatic diamino compound residue represented by the general formula +I+ constituting the aromatic polyamide of the resin composition of the present invention include diaminobenzenes, diaminonaphthalenes, diaminobiphenyls, etc. etc. Illustrated here. Specifically, p- and m-7 enylene diamine, 2,6- and 1,5-naphthalene diamine, 4,4' and 4,3-diaminobiphenyl, 4,
4'- and 4,3'-diaminodiphenylpropane 4
#4'- and 4.3'-diaminodiphenylsulfone, 4,4'- and 4,3-diaminodiphenylsulfide, 4.4'- and 4゜3-diaminodiphenyl ketone, 4.4' - and 4,3-diaminodiphenyl ether and at least one hydrogen of these benzene nuclei is CI.

Examples include nuclear-substituted derivatives substituted with halogens such as Br, (1), lower alkyl groups, alkoxy groups, phenyl groups, naphthyl groups, and the like.

It also includes these aliphatic aromatic carboxylic acid diamides typified by diacetamide. Among these, preferred are p- and m-phenylenediamine, p-
and m-toluylenediamine, 4,4'- and 4
, 3'-diaminobiphenyl, 4,4'- and 4,3
'-Diaminodiphenylpropane, 4,4'- and 4,3'-diaminodiphenylsulfone, 4°4'- and 4,3'-diaminodiphenylsulfide, 4#
4'- and 4,3I-diaminodiphenyl ketone,
4.4'- and 4.3'-diaminodiphenyl ether, and more preferred are p- and m-phenylenediamine, p- and m-)ylenediamine, and 4.3'-diaminodiphenyl ether. It is. Moreover, these may be used in combination.

Further, the compound having an aromatic dicarboxy compound residue represented by the general formula (seal) as used in the present invention is exemplified by phthalic acids, naphthalene dicarboxylic acids, dicarboxybiphenyls, and the like. Specifically, terephthalic acid, isophthalic acid, 2#6- and 1.5-naphthalene, dicarboxylic acid, 4.4'-button, 4.3'-dicarboxybiphenyl, 4゜4'- and , 4.3'-dicarboxydiphenylpropane, 4.4'- and 4.3'-
dicarboxydiphenyl sulfone, 4.4'-1 and
4.3'-Dicarboxydiphenyl sulfide, 4.4
'- and 4,3'-dicarboxydiphenyl ketone, 4,4'- and 4,3I-dicarboxydiphenyl ether, and at least one water g of these benzene nuclei is Cl, Br%11, etc. o) Nuclear w1-substituted derivatives substituted with groups such as f, lower alkyl, alkoxy, phenyl, naphthyl, etc. can be exemplified. Furthermore, dihalides of these dicarboxylic acids represented by acid dichlorides, aliphatic aromatic alcohols, and diester compounds with phenols are also included. Among these, preferred are terephthalic acid, isophthalic acid, 2.6-1 and 11.5-naphthalene dicarboxylic acids and acid dichlorides thereof. Most preferred are these acid dichlorides. Moreover, these dicarboxylic acids can also be used in combination.

The aromatic polyamide of the present invention can be obtained by polybonding one or more compounds having these aromatic diamino compound residues with one or more compounds having dicarboxy compound residues by a known method described below.

Preferred examples of the aromatic polyamide of the present invention include polyparaphenylene terephthalamide, polyparaphenylene isophthalamide, polymethaphenylene isophthalamide, polymethaphenylene terephthalamide, polymethatolylene terephthalamide, and polymethatolylene isophthalamide 1.4 .4'-diaminodiphenyl ether/isophthalic acid, 4°4'-diaminodiphenyl ether/terephthalic acid, 4.41-diaminodiphenyl ether/2, polyamide consisting of 6-naphthalene dicarboxylic acid, 4°3'-diaminodiphenyl ether/isophthalic acid, 4.3'-diaminodiphenyl ether/tele7kMt, 4,3'-diaminodiphenyl ether/2°6-naphthalene dicarboxylic acid polyamide, polymetaphenylene 2,6-naphthylamide, polyparaphenylene 2,6- Naphthylamide, polymethatoluylene 2,6-naphthylamide, and diamines and dicarboxylic acid components of these polyamides, such as metatolylenediamine/paraphenylenediamine/terephthalic acid and metatolylenediamine obtained by mixing them. /paraphthalate; diamine/isophthalic acid, metatolylene diamine/meta-phenylene diamine/isophthalic acid, meta-tolylene diamine/meta-phenylene diamine/terephthalic acid, meta-tolylene diamine/4,
A polyamide consisting of three components such as 4'-diaminodiphenyl ether/4, 3'-diaminodiphenyl ether/isophthalic acid/2, 6-naphthalene dicarboxylic acid, paraphenylenethiamine/terephthalic acid/2,6-naphthalene dicarboxylic acid, etc. Four-component polyamides similar to can be used. More preferred examples include polyparaphenylene terephthalamide, polyparaphenylene isophthalamide, polymetaphenylene isophthalamide, polymetaphenylene terephthalamide, polymethatoluylene terephthalamide, polymethatolylene isophthalamide, 4.4'-diaminodiphenyl ether/
4, 3'-diaminodiphenyl ether/isophthalic acid, 4,4'-diaminodiphenyl ether/terephthalic acid, 4,4'-diaminodiphenyl ether/2,
Polyamide consisting of 6-naphthalene dicarboxylic acid, polymethaphenylene 72.6-naphthylamide, polyparaphenylene 2.6-su7tylamide, polymethatolylene 2
6-naphthylamide is mentioned, and the most preferred examples include polymethaphenylene isophthalamide, polymethaphenylene terephthalamide, polymethatolylene terephthalamide, and polymethatolylene isophthalamide.

Polycondensation for producing these aromatic polyamides may be carried out by any known method, including interfacial polycondensation, dehydrochlorination reaction in a solid phase or a suitable solvent or heat medium, direct amidation, acid amidation exchange reaction, Examples include, but are not limited to, polycondensation using a synthetic reaction of a dicarboxylic acid and a diisocyanate compound, an ester rod reaction, and the like. A preferred method for producing aromatic polyamide is an interfacial method in which aromatic dicarboxylic acid dichloride is used as the aromatic dicarboxylic component, and polycondensation with aromatic diamine is performed in the presence of aqueous caustic alkali and an organic solvent such as an alkyl halide. This is a dehydrochloric acid reaction by polycondensation.

The resin composition of the present invention obtained by copolymerizing polyphenylene ether as component A and aromatic polyamide as component B of the resin composition includes polyphenylene ether 1 to 1oo96, Preferably, the composition is 5 to 100% copolymerized with polyamide.

In preparing the resin composition of the present invention, the following method is used to copolymerize the constituent components, polyphenylene ether and aromatic polyamide.

0) A method of polycondensing an aromatic diamino compound and an aromatic dicarboxy compound in the presence of polyphenylene ether.

+bl A method of polycondensing an aromatic diamino compound and an aromatic dicarboxy compound in the presence of a terminal-modified polyphenylene ether.

fcl A method of bonding polyphenylene ether and aromatic polyamide through an intermolecular reaction.

Method (a) is not particularly limited, and all applicable methods include polycondensation of polyamide in the presence of the polyphenylene ether of the present invention by any of the above-mentioned known methods. Preferably, polyphenylene ether is dissolved in an appropriate organic solvent such as an alkyl halide such as chloroform or methylene chloride, and this is used as an organic phase to carry out interfacial polycondensation of polyamide to remove the terminal hydroxy groups of polyphenylene ether. Alternatively, derived from a monofunctional phenol of general formula (I), or
This is a method of copolymerizing aromatic polyamide with polyphenylene ether using functional groups derived from a modifier. (in the method) except modifying the end of polyphenylene ether and using it instead of polyphenylene ether (al
is the same as As a method for modifying the terminal end of polyphenylene ether, a compound having both an acid chloride group and an acid anhydride group in the molecule, such as trimellitic acid chloride, is reacted with the terminal hydroxyl group of polyphenylene ether. Examples include a method of forming terminal acid anhydride-containing polyphenylene ether. Method (C
1 is polyphenylene ether and aromatic polyamide, diisocyanate compounds such as diphenylmethane diisocyanate, diphenyl ether diisocyanate, toluylene diisocyanate; jepoxy compounds such as resorcin diglycidyl ether; bisoxazoline compounds such as phenylene bisoxazoline; succinic acid, maleic acid,
Dicarboxylic acids such as phthalic acid; carboxylic anhydrides such as phosuccinic anhydride, maleic anhydride, phthalic anhydride, and trimellitic anhydride; and dicarboxylic anhydride compounds such as pyromellitic anhydride, as appropriate. These methods include a reaction in a solution, or a method of copolymerization by melt-kneading using a roll mill, Pampari mixer, extruder U, etc. Preferred methods include dissolving polyphenylene ether in a suitable organic solvent and performing interfacial polycondensation in the presence of polyphenylene ether using the terminal hydroxyl group to produce aromatic polyamide; (method a) polyphenylene ether; A method of copolymerizing and aromatic polyamide with a binder such as diincyanate or jepoxy in an appropriate solution, or by melt-kneading using a roll mill, Pampari mixer, extruder, etc., in the main chain. Examples include a method of copolymerizing polyphenylene ether having a reactive site with the above-mentioned polyamide by the method described above (Method C), but a more preferable method is to copolymerize polyphenylene ether in an appropriate organic solvent. This is a method (methods a and b) in which the aromatic polyamide is copolymerized by dissolving and copolymerizing the aromatic polyamide by performing interfacial polycondensation in the presence of polyphenylene ether using the terminal hydroxyl groups.

In the resin composition of the present invention, in order to achieve the object of the present invention, the average degree of polymerization of the A component and the Btc component is each about 2 to 1000, preferably 5 to 500.

The ratio of the peripheral components is (A) polyphenylene ether part 5 ~
95 weight ffi%, (B) aromatic polyamide part 95-5
The weight% is desirable, and the more preferable ratio is (A) 25 to 80% by weight of the polyphenylene ether portion, and (B) 75 to 20f of the aromatic polyamide portion! The amount is %. Most preferably (A) polyphenylene ether moiety 25-70
weight tIk%, (B) aromatic polyamide portion 75 to 30 weight ff1%. If the polyphenylene ether portion is less than this, heat resistance will be insufficient, and if it is more than this, moldability will be poor. If the aromatic polyamide portion is less than this, the effect of improving the elastic modulus will be insufficient, and if it is more than this, the mechanical properties and heat resistance will be insufficient.

The resin composition of the present invention may optionally contain other resins; elastomers; flame retardants; flame retardant aids; stabilizers; ultraviolet absorbers:
Plasticizers; various additives such as lubricants, pigments, fillers, and other components are appropriately blended.

Examples of other resins include: polystyrene resins; elastomer-modified high-impact polystyrene resins; phenoxy resins; epoxy resins; hexamethylene diamine, nonamethylene diamine, undecamethylene diamine, dodecamethylene diamine, dodecamethylene diamine, metaxylylene diamine Polymers obtained by polycondensation of diamines such as , and dicarboxylic acids such as terephthalic acid, isophthalic acid, adipic acid, sepathic acid, dodecane dibasic acid, and geltaric acid, or copolymers thereof, such as nylon. 4
,6,7.8.11.12.6.6,MXD,5.6,
9.6, 10.6.11.6°12.6T, 6/6.
6.6/12.6/6T.

Polyamide exemplified by 61/67 etc.: General formula (f
f) Aromatic polycarbonate having a repeating unit represented by f).

1 (-0-A -0-C-) (ff)A:
A divalent aromatic group derived from an aromatic dihydroxy compound (the aromatic dihydroxy compound used here is the one mentioned above, and the most preferable one is bisphenol A
Polymer combinations of phenylhydroquinone and terephthalic acid, homopolycondensates of hydroxybenzoic acid, copolymers of hydroxybenzoic acid and polyalkylene tere(iso)phthalate, especially polyethylene terephthalate, hydroxybenzoic acid and hydroquinone, dihydroxy The above-mentioned aromatic dihydroxy compounds represented by diphenyl and iso,
Polymers with liquid crystallinity, such as polybonded compounds made of aromatic dicarboxylic acids such as terephthalic acid and naphthalene dicarboxylic acid, and polycondensates of these using hydroxynaphthoic acid instead of hydroxybenzoic acid. Fully aromatic polyester; Polyether sulfone represented by the polycondensate obtained from 4,4'-dichlorobiphenylsulfone; Polysulfone represented by the polycondensate obtained from 4,4'-dichlorobiphenylsulfone and bisphenol-A #4 Polyether ether ketone represented by polycondensate obtained from 47-cyfluorobiphenyl ketone and hydroquinone; polyester ether; polyester carbonate: polyimide: polyester imide; polyether imide; polyphenylene sulfide;
Examples include polyoxymethylene, etc., and one or more copolymers containing two or more thereof. Among these, aromatic polycarbonate, liquid crystalline wholly aromatic polyester,
Polyetherimide, polyphenylene sulfide, etc. are preferably used.

Further, the elastomer used in the composition of the present invention is an elastomer in a general sense, such as A, V, To
bolski IF″Proqerties and
5truc-ture of Polymers
(John '1M1y &5ons,
inc ml 1960) on pages 71 to 78, an elastomer is defined as an elastomer having a Young's modulus of 10 to 10 dynes/! (0,
1 to 1020 Kp/m). Specific examples of elastomers include A-B-AZ type elastomeric block copolymers, A-B-A' type elastomeric copolymers in which the double bond in the polybutadiene portion is hydrogenated, polybutadiene, polyisoprene, and diene. Copolymers of compounds and vinyl aromatic compounds, nitrile rubber, ethylene-propylene copolymers, ethylene-propylene-
Diene copolymers (EPDM), thiol rubber, polysulfide rubber, acrylic acid rubber, polyurethane rubber, graft products of butyl rubber and polyethylene, polyester elastomers whose hard segments have a polyester crystal structure and soft segments have a polyether crystal structure,
Examples include polyamide elastomer.

To give examples of the various additives mentioned above, examples of flame retardants include triphenyl phosphate, tricresyl phosphate,
Phosphate obtained from a mixture of isopropylphenol and phenol and phosphorus oxychloride, a difunctional phenol such as benzohydroquinone or bisphenol-A and other alcohols, or phosphates obtained from phenols and phosphorus oxychloride. Bromine compounds represented by decabromo biphenyl ether, hexabromo biphenyl, pentabromotoluene, decabromo biphenyl ether, hexabromobenzene, brominated polystyrene, etc.; Nitrogen-containing compounds such as melamine derivatives. Flame retardant aids may also be used, examples include antimony, borosilicate,
Examples include zinc or iron compounds. Furthermore, other additives include ultraviolet absorbers such as sterically hindered phenols, phosphite compounds, and sterically hindered amine compounds; lubricants such as polyethylene wax, polypropylene wax, and paraffin; titanium oxide;
Examples include pigments such as zinc sulfide. In addition, when particularly required, inorganic fillers such as glass fiber, milled 7-iper, glass powder, asbestos, wollastonite, mica, and talc; organic fillers such as carbon fiber, polyimide fibers, aramid fibers, etc. It is also possible to use fillers together.

〔Effect of the invention〕

The polyphenylene ether resin composition obtained by the present invention is a resin 11 that exhibits excellent mechanical properties typified by an extremely high modulus of elasticity, and can be used as a metal substitute.

〔Example〕

The present invention will be explained in more detail below using reference examples, comparative examples, and examples, but the present invention is not limited to these examples.

In addition, the abbreviations in Tables 1, 2, and 3 represent the following compounds.

mTDA: meta-toluylene diamine pPDA: paraphenylene diamine mPDA: meta-phenylene diamine I PC: isophthalic acid chloride TPC: terephthalic acid chloride 2.5-NDC: 2.6-naphthalic acid chloride 4.4' -DADPE: 4 .4'-Diaminodiphenyl ether Example 1 Intrinsic viscosity measured in chloroform at 25°C is 0.47
(dl/g) of 2,6-dimethylphenol polymer (one-terminal hydroxy type polyphenylene ether) 100.8
Dissolve F in chloroform 2j, add methatoluylene diamine (Tokyo Kasei (M) reagent 48.8 g (0.4 mol) and distilled water 21 in which sodium hydroxide 32.9 is dissolved. Sodium lauryl sulfate 20.9 A 400-g solution of 400% of water and 6 g of tetra-n-butylammonium bromide are added and stirred vigorously for 5 minutes.Then, isophthalic acid chloride (manufactured by Mitsubishi Gas Chemical) 81.29 (
A solution of 0.4 mol) dissolved in chloroform 2j was quickly added at room temperature and stirred vigorously for 20 minutes. After the reaction is completed, methanol 201 is added to the reaction mixture to precipitate the polymer.

After filtration, wash the polymer with a large plate of water, methanol, and then dry. The yield of polymer after drying is 96.5%
Met. When 2.0 g of the dried polymer was accurately weighed and Soxhlet extraction was performed using chloroform as a solvent, 1
．． 20 g of raffinate was obtained.

From this, the amount of polyphenylene ether reacted with polyamide was calculated to be 15.8.96. Reaction rates were determined in the same manner for the following examples.

The obtained polymer was processed using a 20111 small extruder for 30
The pellets were pelletized at 0° C., and then dumbbell pieces were molded using a 50-ton injection molding machine, and a tensile test was conducted to measure tensile strength and tensile elongation. Further, a 10 x 10 flat plate was molded, and a test piece of 3 m thick and 13 x 9 Q mm was cut out from this in the flow direction of the resin and in the direction perpendicular to the flow, and the bending elastic modulus was measured in both directions. We also measured the heat distortion temperature. The results are shown in Table 1.

Example 2 100.8 g of the one-terminal hydroxy type polyphenylene ether of Example 1, 43.3 g (0.4 mol) of metaphenylenediamine (reagent manufactured by Tokyo Kasei Co., Ltd.), and 81.29 (0.4 mol) of isophthalic acid chloride were added. Example 1 was repeated using The results are shown in Table 1.

Example 3 One-terminal hydroxy type polyphenylene ether of Example 1 100.8. Example 1 was repeated using 43.39 (0.4 mol) of L-paraphenylene diamine (reagent manufactured by Tokyo Kasei Co., Ltd.) and 81.29 (0.4 mol) of terephthalic acid chloride (manufactured by Mitsubishi Gas Chemical Co., Ltd.). The results are shown in Table 1.

Example 4 One-terminal hydroxy type polyphenylene ether of Example 1 100.89, metatolylenediamine 36.7.
9 (0.3 mol), paraphenylenediamine 10.8
9 (0.1 mol), isophthalic acid chloride 81.2
Example 1 was repeated using g (0.4 mol). The results are shown in Table 1.

Example 5 One-terminal hydroxy type polyphenylene ether of Example 1 100, 89', metatolylenediamine 48.
89 (0.4 mol), isophthalic acid chloride 40.
6g (0.2 mol), terephthalic acid chloride 40.
Example 1 was resized using 6KII (0.2 mol). The results are shown in Table 1.

Example 6 One-terminal hydroxy type polyphenylene ether of Example 1 100.8. ! i+, metaphenylenediamine 43
．． 39<0.4 mol), isophthalic acid chloride 40
．． 69 (0.2 mol), terephthalic acid chloride 40
．． Example 2 was repeated using 69 (0.2 mol). The results are shown in Table 1.

Example 7 100.8 g of the one-terminal hydroxy type polyphenylene ether of Example 1, 48.89 g of metatolylene diamine
C0.4 mol), isophthalic acid chloride 40.6g
(0.2 mol), 2,6-naphthalene dicarboxylic acid chloride (Mitsubishi Gas Chemical Co., Ltd.) 50.69 (0.2 mol).The results are shown in Table 1. Ta.

Example 8 100.8 g of the single-end hydroxy type polyphenylene ether of Example 1, 36.7 g of methatoluylene diamine.
Example 2 was repeated using 9 (0.3 mol), 4,4'-diaminodiphenyl ether 2 (1 (0.1 mol), and 81.2 g (0.4 mol) of isophthalic acid chloride. The results are shown in Table Shown in 1.

Reference Example 1 A double-terminated hydroxy type polyphenylene ether was produced by the following method.

Toluene Y1.
35/, Cul 2.34g, and n-butylamine 153g, maintained at 38℃, air blown at 60d/
2.6-dimethylphenol 219°69 and 3,5.3',5'-
A solution of 4.3% tetramethylbisphenol A in 900 g of toluene was added dropwise from a dropping funnel over a period of 1 hour. After the dropwise addition is completed, the reaction is allowed to proceed for 0.5 hour while maintaining the temperature. The polymer was reprecipitated with HCl/methanol, separated from p and dried. The molecular weight of the obtained polyphenylene ether with hydroxyl terminals is 1 in terms of weight average molecular weight.
It was 5000.

Example 9 Polyphenylene ether 309 with both terminal hydroxyl terminals of Reference Example 1 and 70.89 mol of polyphenylene ether with one terminal hydroxyl terminal of Example 1 were dissolved in chloroform 21, and 48.8 g (0.4 mol) of metatoluylene diamine, Add 21 parts of distilled water in which 32 g of sodium hydroxide has been dissolved. A solution of sodium lauryl sulfate 209 dissolved in 400 ml of water and tetra-n-butylammonium chloride 69 are added and stirred vigorously for 5 minutes. Next, a solution of 81.2 g (0.4 mol) of isophthalic acid chloride dissolved in 21 ml of chloroform is quickly added at room temperature, and the mixture is vigorously stirred for 20 minutes. After the reaction is complete,
Methanol 20j is added to the reaction mixture to precipitate the polymer. After filtration, the polymer is washed with a large amount of water and methanol, and then dried. The reaction rate was calculated in the same manner as in Example 1.

The obtained polymer was processed using a 20111 small extruder for 30
The material was pelletized at 0° C., and then a test piece was prepared in the same manner as in Example 1 using a 50 mm injection molding machine and its physical properties were measured. The results are shown in Table 2.

Examples 10 to 16 Examples 2 to 7 were repeated except that the one-end hydroxy type polyphenylene ether of Examples 2 to 7 was changed to the combination of the both-end hydroxy type polyphenylene ether of Reference Example 1 in the same manner as in Example 8. . The results are shown in Table 2.

Reference Example 2 A polyphenylene ether with hydroxyl terminals at both ends was obtained using the same method as in Reference Example 1, but with a reaction time of 1.5 hours after completion of the dropwise addition. The molecular weight of the obtained polyphenylene ether with hydroxyl terminals was 28,000 in terms of weight average molecular weight.
Met.

Example 17 100.8 g of the polyphenylene ether with hydroxyl terminals at both ends of Reference Example 2, mettatoluylene diamine 48.8.
! i' (0.4 mol), isophthalic acid chloride 81
．． 2! Example 1 was repeated using j (0.4 mol). The results are shown in Table 2.

Example 18 Double-terminated hydroxy-type polyphenylene ether of Reference Example 2 100.8&, metaphenylenediamine 43.3.
9 (0.4 mol), isophthalic acid a-ride 81.2
Example 1 was repeated using g (0.4 mol). The results are shown in Table 2.

Reference Example 3 Polyamide was manufactured by the following method. Metatolylenediamine 48.8)? Distilled water 21 in which sodium hydroxide 32& is dissolved is added to (0.4 mol). A solution of 20 g of sodium lauryl sulfate dissolved in 400 g of water and 6.9 g of tetra-n-butylammonium bromide are added and stirred vigorously for 5 minutes. A solution of 81.29 (0.4 mol) of inphthalic acid chloride dissolved in 21 mol of chloroform was quickly added at room temperature and stirred vigorously for 20 minutes. After the reaction is completed, methanol 201 is added to the reaction mixture to precipitate the polymer. After filtration,
After washing the polymer with a large amount of water and methanol, dry it.

Reference Examples 4 to 10 In the same manner as Reference Example 3, polyamides of Examples 2 to 8 were separately manufactured.

Comparative Example 1 was repeated using the polyamide of Reference Examples 4-10. The results are shown in Table 3.

Comparative Example 9 Single terminal hydroxy type polyphenylene ether 100.89 of Example 1 and Depon, Toshi, Kevlar (structure: aromatic polyamide Kevlar (trade name: Ke-vlar)
49) Using a 201rl small extruder, 100g
A composition was produced by melt-kneading at 00°C, but it could not be made into strands.

Comparative Example 1 Single terminal hydroxy type polyphenylene ether 100.89 of Example 1 and polyamide 1 obtained in Reference Example 3
00g was melt-kneaded at 300°C using a 2011 small extruder to produce a composition.

In the same manner as in Example 1, the physical properties after injection molding were measured.

The results are shown in Table 3.

Comparative Example 10 Single terminal hydroxy polyphenylene ether 141.1.9 of Example 1 and DuPont Toshi Kevlar (structure aromatic polyamide Kevlar (trade name Ke-vlar)
49) Using a 20 fml small extruder, 60 g was melt-kneaded at 300°C to produce a composition, and the physical properties after injection molding were measured in the same manner as in Comparative Example 1. The results are shown in Table 3.

Comparative Examples 2 to 8 A new 4th line is inserted between the 3rd line and the 4th line on page 3 of the 8° amendment statement of contents.

Procedural amendment (formality) %formula% Display of incidents 1990 Patent application No. 2172 issue 2゜ name of invention Novel resin composition 3゜ person who makes corrections Relationship with the incident

Claims (1)

[Claims] (A) is a polyphenylene ether (B) is a compound having an aromatic diamino compound residue represented by the general formula (I) ▲ There are numerical formulas, chemical formulas, tables, etc. ▼ (I) [here R_1: Phenylene, naphthalene, which may be the same or different, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲mathematical formulas,
There are chemical formulas, tables, etc.▼{X: S, SO_2, CO, O, C(R_3)_2(R_3:
Hydrogen, halogen, carbon number 1, which may be the same or different
to 8 aliphatic or aromatic hydrocarbon groups)} R_2: A substituent on the aromatic ring, which may be the same or different halogen, an aliphatic group having 1 to 8 carbon atoms, or
Aromatic hydrocarbon group, a: represents 0 or an integer from 1 to 8. [Here, R_4: Phenylene which may be the same or different , Naphthalene, ▲Mathematical formulas, chemical formulas, tables, etc.▼, ▲Mathematical formulas,
There are chemical formulas, tables, etc. ▼ Hydrogen group)} R_5: A substituent on an aromatic ring, which may be the same or different, a halogen, an aliphatic group having 1 to 8 carbon atoms, or
Aromatic hydrocarbon group, b: represents 0 or an integer from 1 to 8. ] When an aromatic polyamide obtained by polycondensation of (A) polyphenylene ether, general formula (I),
A resin composition obtained by copolymerizing one or more selected from the aromatic polyamide group (B) obtained by polycondensing a compound having an aromatic diamino compound residue and an aromatic dicarboxy compound residue (II). thing.