JPH03207755A - Poly(phenylene ether)-based resin composition - Google Patents

Abstract

PURPOSE:To obtain a polyphenylene ether-based resin composition suitable for housings, etc., of motorized tools, OA (office automation) devices, etc., having excellent heat resistance, electrical characteristics, molding properties, etc., by blending a poly(substituted) phenylene ether resin with a specific amount of a specific cyclic olefin-based random copolymer. CONSTITUTION:(A) A poly(substituted) phenylene ether resin is blended with (B) a cyclic olefin-based random copolymer which is a copolymer of ethylene and a cyclic olefin having a structural formula selected from formula I to formu la IV (l is 0 or positive integer; R<1> to R<18> are H, halogen or hydrocarbon) m is 0 or positive integer; q and r are 0, 1 or 2) and has 0.05-10dl/g intrinsic viscosity and >=70 deg.C softening temperature in the weight ratio of 98/2-2/98, preferably 95/5-5/95.

Description

[Detailed description of the invention] 50,000 liters of mitate! The present invention provides a poly(phenylene ether) containing a poly(phenylene ether) resin and a cyclic olefin resin.
The present invention relates to poly(phenylene ether)-based resin compositions that have excellent heat resistance, electrical properties, and moldability.

Poly(phenylene ether) resins such as poly(2,6-dimethylphenylene ether) resins or poly(substituted phenylene ether) resins [hereinafter may be collectively referred to as poly(phenylene ether)-based resins. It has excellent electrical properties such as low dielectric constant and dielectric loss tangent, high volume resistivity and high dielectric breakdown strength, and has low mold shrinkage. However, due to its high melt viscosity, moldability is poor.

Therefore, in order to improve moldability, poly(phenylene ether) resin compositions blended with polystyrene have been commercialized.

But polystyrene! Since the glass transition temperature is lower than that of poly(phenylene ether)-based resins such as poly(2,6-dimethylphenylene ether) resin, poly(phenylene ether)-based resin compositions that are a mixture of these resins are poly(2,6-dimethylphenylene ether) resins. There is a problem that the heat resistance is inferior to that of (6-dimethylphenylene ether) resin.

By the way, it is known that cyclic olefins having an ethylenic double bond in the ring have polymerizability9 and, for example, can undergo a copolymerization reaction with ethylene to obtain a cyclic olefin/ethylene random copolymer ( [F Showa 60-1
Publication No. 68708, Japanese Patent Publication No. 63-243111
JP-A-63-305111 Public Rebellion JP-A-63-223
Publication No. 013 (see Japanese Patent Application Laid-Open No. 185307/1999).

This cyclic olefin resin IL has excellent transparency, water resistance, and thermal properties. We have discovered that by blending poly(phenylene ether) into poly(phenylene ether) based resins, it is possible to obtain poly(phenylene ether) based resin compositions with even more excellent properties that can be used for various purposes. The purpose of the present invention is to provide a poly(phenylene ether) resin composition that has excellent heat resistance, electrical properties, and moldability while maintaining the excellent properties of the phenylene ether resin.

iri p nose 1 poly(phenylene ether) resin composition writing method according to the present invention [A] poly(phenylene ether) MIt resin, [B]
It is a copolymer of ethylene and a cyclic olefin represented by at least one of the structural formulas selected from the following formulas [r] to [rvl, and has an intrinsic viscosity [vl of 0.05 measured in decalin at 135°C]. ~1odl um Softening temperature (TMA
) is 70°C or higher, the composition ratio of poly(phenylene ether) resin [A] and cyclic olefin random copolymer [B] is 75 [A]
/[B] (weight ratio) is 9872 to 2/98.

(Formula II), 1 is 0 or a positive integer, and R1
~Rl KanL Each may be the same or different, and is an atom or group selected from the group consisting of a hydrogen atom, a halogen atom, and a hydrocarbon group, and R+s to R11 are bonded to each other to form a monocyclic or polycyclic ring. It may form a ring, and the monocyclic or polycyclic ring may have a double bond, and Rls and R16 or RIT and Rls may form an alkylidene group. good).

・[n(In the formula [n], m is O or a positive integer, and R1-
R1@44 They may be the same or different, and are atoms or groups selected from the group consisting of hydrogen atoms, halogen atoms, and hydrocarbon groups, even if R9 and R1 form an alkylidene group. good).

(In formula [m], n is 0 or a positive integer, and R1 to
RI& may be the same or different, and each is an atom or group selected from the group consisting of a hydrogen atom, a halogen atom, and a hydrocarbon group, and even if R11 and R+t form an alkylidene group. good).

...[N] (In the formula [rvl, p is an integer of 0 or 1 or more, and q
and rl-o, 1 or 2, R1-R18
each independently represents an atom or group from the group consisting of a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group, an aromatic hydrocarbon group, and an alkoxy group, and R8 (or R.) and R11 (or RT) represent the number of carbon atoms. They may be bonded through 1 to 3 alkylene groups, or may be bonded directly without any group. ) Since the poly(phenylene ether) resin composition according to the present invention is composed of a poly(phenylene ether) resin [A] and a specific cyclic olefin random copolymer [B], it has excellent heat resistance and electrical properties. It also has characteristics such as excellent moldability.

Moreover, by blending such a cyclic olefin random copolymer [B], the excellent properties of the poly(phenylene ether) resin [A] are not impaired.

Next, the poly(phenylene ether) resin composition according to the present invention will be specifically explained.

The poly(phenylene ether)-based resin composition according to the present invention is represented by poly(phenylene ether)-based 11 resin [A], ethylene, and one of the structural formulas selected from the above formulas [I] to [■]. It is characterized by containing a cyclic olefin random copolymer [B] which is a copolymer with a specific cyclic olefin.

The poly(phenylene ether) resin [A] constituting the poly(phenylene ether) resin composition of the present invention has a structure represented by the following formula [j].

R1@R* ... [il [In the formula, RIj Rlj R21 and R22 are each independently a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, a cyano group, a nitro group, an amino group, a phenoxy group or a sulfone group, and S is a positive is an integer. ] In the above formula [il, S is preferably 20 to 1000.

Specifically, the poly(phenylene ether) resin or poly(substituted phenylene ether) resin represented by the above-mentioned formula [il, poly-1,4-phenylene ether,
Poly-2,6-dimethyl-1,4-phenylene ether, poly-2,6-danityl-1,4-7-phenylene ether, poly-2,6-diprobyl-1,4-phenylene ether, poly-2- Methyl-6-ituprovir-1,
4-phenylene ether, poly-2,6-simethoxy 1,4-phenylene ether, poly-2,6-cycloalkyl group 1゜4-7 enylene ether, poly-2,6-
diphenyl-1゜4-phenylene ether, poly-2,
Examples include 6-cynitrile-1°4-7 enylene ether, poly-2,6-dichloro-1,4-phenylene ether, and poly-2,5-dimethyl-1,4-phenylene ether. These can be used alone or in combination of two or more.

These poly(phenylene ether) resins or poly(
Substituted phenylene ether) resin [A] Intrinsic viscosity [η] measured in chloroform at 30°C is 0.01 to 5 d
l/g, preferably 0.1 to 3 dl/g.

In addition, the softening temperature (
TMA) is 100℃ or less, preferably 150 to 250℃
It is desirable that it be within the range of .

Further, the glass transition temperature (Tg) of the poly(phenylene ether) resin [A] is 100°C or lower, preferably 15
It is desirable that the temperature is in the range of 0 to 250°C.

Cyclic olefin random copolymer [B] that constitutes the poly(phenylene ether) resin composition of the present invention +!
It is a cyclic olefin random copolymer composed of a structural unit (a) derived from ethylene and a structural unit (b) derived from a specific cyclic olefin.

The above cyclic olefin has at least the above formulas [I] to [■
] It is a cyclic olefin represented by one of the structural formulas selected from the following.

In the above formula [I], l is 0 or a positive integer, preferably 0 to 3. In the above formula [n], m is O or a positive integer, preferably O-3. In the above formula [m], n is O or a positive integer, preferably 0 to 3. In the above formula [y], p is 0 or an integer of 1 or more, preferably O
It is an integer of ~3.

And R1 to R18 (formula [Iko), R1 to R1・(
Formula [■]), R+, R12 (Formula [m]) or R1
-R111 (Formula [V]) JL Each may be the same or different, and is an atom or group selected from the group consisting of a hydrogen atom, a halogen atom, and a hydrocarbon group. Here, let's use it as a halogen atom! Mention may be made of fluorine, chlorine, bromine and iodine atoms. In addition, as hydrocarbon groups, an alkyl group having 1 to 10 carbon atoms and a cycloalkyl group having 5 to 15 carbon atoms can be mentioned.
Specific examples of alkyl groups include: methyl group ethyl group isopropyl group isobutyl n-amyl 5 neopentyl f, n-hexyl in-octyl in-decyl f
Specific examples of the cycloalkyl group include cyclohexyl group, methylcyclohexyl group, ethylcyclohexyl group, and the like.

In addition, in the above formula [r], RII and R111,
Or R1? and Rts may form an alkylidene group, and in the above formula [n], R9 and RIM may form an alkylidene group. In the above formula [m], R and RI2 may form an alkylidene group. may be formed. Such alkylidene groups usually include alkylidene groups having 3 to 10 carbon atoms,
Specific examples include ethylidene, propylidene, isopropylidene, butylidene, and isobutylidene.

In addition, in the above formula [N], R1 (or R8) and R''
(or R?) may be bonded via an alkylene group having 1 to 3 carbon atoms, or may be bonded directly without any group.

Furthermore, in the above formula [r], R''-R11 may be bonded to each other (together) to form a monocyclic or polycyclic ring, and the monocyclic or polycyclic ring has a double bond. You may do so.

The cyclic olefins represented by the above formulas [rl to [■]] can be easily produced by condensing cyclopentadiene and corresponding olefins or cyclic olefins by Diels-Alder reaction.

The above formula [eco ~ [■] cyclic olefin represented by L as a button Be specific Even if it is a play (Margin below) 1,12 5.1te・11]-3-dodese hmm hmm 8-ethylidene-9-iso One dodecene , 12・5.17・11]-3-dodecene ++, 1te, I・]-]3-dodese 8-isopropylide Which diene compounds include: 8-isopropylidene One dodecene ・I@]-3-dodecene such as pentacyclo [4,7,0,121,Of! 3.19+2] C1l.

[4,4,0,12・5.17・I@]-3-3-pentadecene derivative.

One dodecene Tetracyclo[4,4 0,12,S,1) 10]-3-dodece derivatives.

Kosen and further: Dai2.111], -4-eikosenatonohep9 Schiff O[7,8,0,13-',0"-
”, 1”-”, 011.181112.I@]-4-
Eicosene derivative; 21.1+121. QIJ, lI,
115.+s]-5-bentacocene3.21. QIJ, IQ, 11116]-5-bentacocene etc/f shift t7 [9,10,1,147,O
"-", 0"@, 0L221.113.2@, QI41
9.11S, l@] -5-/< :/Tacocene derivatives and the like can be mentioned.

can be mentioned.

Cyclic olefin random copolymer [:B] constituting the resin composition according to the present invention! L A car whose essential structural units are the structural unit (a) derived from ethylene and the structural unit (b) derived from the cyclic olefin. It may also contain other copolymerizable structural units derived from unsaturated monomers. Specific examples of unsaturated monomers that may be copolymerized include L propylene, 1-butene, 4-methyl-1.
- 3 or more carbon atoms such as pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, etc.
Examples include No. 20 a-olefins. One structural unit derived from these unsaturated monomers may be contained in an amount less than equimolar to the structural unit (a) derived from ethylene in the generated random copolymer.

In the cyclic olefin random copolymer [B] constituting the resin composition according to the present invention, the structural unit derived from ethylene (a) contains 40 to 85 moles of G, preferably 5
It is desirable that the content is in the range of 0 to 75 mol%.

Furthermore, the structural unit (b) derived from a cyclic olefin is 15
-60 mol list Preferably, it is desirable that it is contained in the range of 25 to 50 mol%. In the present invention, structural units (a) derived from ethylene and structural units (b) derived from cyclic olefins are randomly arranged to form a linear cyclic olefin random copolymer.

The intrinsic viscosity [17] of the cyclic olefin random copolymer [B] constituting the resin composition of the present invention measured in decalin at 135°C is 0.05 to 10 dl/g,
Preferably it is in the range of 0.08 to 5 dl/g.

Furthermore, the cyclic olefin random copolymer [B] constituting the resin composition according to the present invention has a softening temperature (TMA) of 7 as measured with a G-transfer thermomechanical analyzer.
0°C or less, preferably in the range of 90 to 250°C, more preferably in the range of 100 to 200°C.

Further, it is desirable that the glass transition temperature (Tg) of the cyclic olefin random copolymer CB constituting the resin composition according to the present invention is usually in the range of 50 to 230°C, preferably 70 to 210°C.

Further, the crystallinity of the cyclic olefin random copolymer [B] constituting the resin composition according to the present invention, determined by X-ray diffraction analysis, is 0 to 10%, preferably 0 to 7%.
It is particularly desirable that the content be in the range of 0 to 5%.

As the cyclic olefin random copolymer [B] constituting the resin composition according to the present invention, only a copolymer having physical properties within the above range may be used.ζ Some copolymers outside the above range may be used. In this case, it is sufficient that the physical properties of the cyclic olefin random copolymer [B] as a whole fall within the above range.

The cyclic olefin random copolymer [B] constituting the resin composition according to the present invention is disclosed in Japanese Patent Application Laid-Open No. 60-16870.
No. 8 public sail JP-A-61-120816 public sail JP-A No. 6
Publication No. 1-115912 Publication of JP-A-61-115916 Publication of JP-A-61-2/1308 JP-A-61-
2/2216 Publication Patent Publication No. 1982-252406 Publication
It can be manufactured by a method developed by the applicant of the present invention in JP-A No. 62-252407 and the like.

In the present invention, a part of the cyclic olefin random copolymer as described above may be modified with an unsaturated carboxylic acid such as brine maleic acid, glycidyl acrylate, or the like. Such a modified product +L is obtained by reacting the above-mentioned cyclic olefin resin with an unsaturated carboxylic acid, anhydride ruts thereof, and a derivative such as an alkyl ester of an unsaturated carboxylic acid or a glycidyl ester of an unsaturated carboxylic acid. can be manufactured. In this case, the content GL of structural units derived from the modifier in the modified cyclic olefin resin is usually 0.0.
01 to 5% by weight or less. Such a modified cyclic olefin resin +3 It can also be produced by blending a modifier with a cyclic olefin resin and graft polymerizing it to a desired modification rate - Preparing a modified product with a high modification rate in advance, and then It can also be produced by mixing this modified product with an unmodified cyclic olefin resin.

In the polyolefin resin composition of the present invention, the composition ratio of the poly(phenylene ether) resin component [A] and the cyclic olefin random copolymer component [B] is inverted by one [A]
The weight ratio of component/[B] acid component is 98/2 to 2/98, preferably 9515 to 5/95.

Further, in the present invention, when producing the above-mentioned cyclic olefin-based random copolymer, the above formulas [I] to [
Cyclic olefins other than the cyclic olefin represented by (2) can also be polymerized. Examples of such cyclic olefins include cyclobutene, cyclopentene, cyclohexene, 3,4-dimethylcyclohexene, 3-methylcyclohexene, 2-(2-methylbutyl)-1-cyclohexene, 2,
In addition to 3.3a, 7a-tetrahuman l:I-4,'I-j tanoh-IH-inde 3a, 5.6.7a-tetrahin, etc., draw 4.7-methano-IH-inte (hereinafter referred to as the margin), etc. Bicyclo[2,2,1]hept-2-ene derivatives such as; 5.10-dimethyltetraCH.

CHs CH.

C.H.

2,7.9-Trimethylthene5,8.9.10-Tetramethy8-methyltetrashif8-ethyltetrashif1@]-3-dodecene8-hexyltetrash1enJ-d-dodecene9-inbutyl-2 ,7-9,11,12-)dimethyl9-ethyl-11,12-dime9-inbutyl-11,12-dodecene,1-dodecene-3-dodecene8-methyl-9-ethylte8-chlorotetrasif8 -Promotitracif 8-FluorotetracyT.]-3-dodecene.1.]-]3-dodecene+4]-4-heptadecene 5.17 +1]-3-dodecenedecene7.II]-3-dodecene-3-dodecene Tetracyclo[4,4,0,1'・5. IT・I
-]-]3-dodecene derivative; Ptadecene (hereinafter blank) 15-ethyl octashif 1), Q2. ff, Italy, 14]-4~Heb2・lff1
-5-Tococentadecene and other octacyclo[8,8,0,1"・-14・Ding I
ll・i・, 11, etc.) Hexashifo C6+6tL1
""J""', 0"', 0'"-'a03-*rO",
1 Te]-5-F Ko-1! , R]-4-heptadecene derivative; R, I@, σL・Ql2. I? ], -5-Tococeneles, 11.1llI8. Ql, l, Ql20'']-5-
docosenbutacyclo-5-heneicosene derivatives; such as pentacyclo[6,6,1,18.,02. Te Q*, 14]
-4゜hexadecene derivatives; tricyclo[4,3,0,1''・S]-3-decene derivatives such as 5-methyl-tricyclo, hebutacyclo-5-icosene derivatives such as cosene, or he1
．． Tricyclo[4,4,0,12·”]-]3-undecene derivatives such as 6-dimethylbenta10-methyl-trisif-14,15-dimethylbent (to D: y 9 Schiff0 [6,5,
1,1"-", 0"-〒, O.-Is]-4-form; pentadecene derivatives, etc. can be mentioned.

(Left below) 1.3-dimethyl-benta Other cyclic olefins Can be used alone or in combination, usually 0 to 20 mol%
used in amounts of

Furthermore, the resin composition of the present invention also includes the above [A] and [
B] Adding rubber components to acid components and other ingredients to improve impact strength, heat-resistant stable ship, weather-resistant stable ship, anti-static ship
Anti-slip port anti-blocking port anti-fogging agents, lubricants, dyes, pigments, natural oils, synthetic oils, waxes, etc. can be blended in appropriate amounts. parable guard
One concrete example of a stabilizer added as an optional ingredient:
Tetrakis[methylene-3(3,5-di-t-butyl-
4-Hydroxyphenyl)propionate comethane, β
-(3,5-di-t-butyl-4-hydroxyphenyl)propionic acid alkyl ester, 2.2°-oxamido bis[ethyl-3(3,5-di-t-butyl-4-hydroxyphenyl)]propionate Phenolic antioxidants such as stearite, fatty acid metal salts such as calcium stearate, calcium 12-hydroxystearate, glycerin monostearate, glycerin monolaurate, glycerin distearate, pentaerythritol monostearate, pentaerythritol distearate , fatty acid esters of polyhydric alcohols such as pentaerythritol tristearate, and the like. These may be blended alone or in combination;
Examples include a combination of methylene-3(3,5-di-t-butyl-4-hydroxyphenyl)propionate comethane, zinc stearate, and glycerin monostearate.

In the present invention, it is particularly preferable to use a phenolic antioxidant and a fatty acid ester of a polyhydric alcohol in combination. Polyhydric alcohol fatty acid esters are preferred.

Such as fatty acid ester of polyhydric alcohol! Gourd Specifically GL glycerin monostearate, glycerin monolaurate, glycerin monomyristate,
Glycerin fatty acid esters such as glycerin monopalmitate, glycerin distearate, glycerin dilaurate, pentaerythritol monostearate, pentaerythritol monolaurate, pentaerythritol dilaurate, pentaerythritol distearate,
Fatty acid esters of pentaerythritol such as pentaerythritol tristearate are used.

Such a phenolic antioxidant is 0.0 parts by weight per 100 parts by weight of the poly(phenylene ether) resin composition.
The fatty acid ester of polyhydric alcohol is used in an amount of 1 to 10 parts by weight, preferably 0.05 to 3 parts by weight, and more preferably 0.1 to 1 part by weight. It is used in an amount of ~10 parts by weight, preferably 0.05 to 3 parts by weight.

Silica, diatomaceous earth, alumina, titanium oxide, magnesium oxide, pumice powder,
Pumice balloon, aluminum hydroxide, magnesium hydroxide Basic magnesium carbonate Dolomite, calcium sulfate, potassium titanate Barium sulfate, calcyl sulfite talc, clay Mica, asbestos, glass fibers Glass flakes, glass beads, silicic acid calcium,
Fillers such as montmorillonite, bentonite, graphite, aluminum powder, molybdenum sulfide, boron fibers, silicon carbide fibers, polyethylene fibers, polypropylene fibers, polyester fibers, and polyamide fibers may be blended.

As a method for producing the poly(phenylene ether)-based resin composition according to the present invention, a known method can be applied, and the poly(phenylene ether)-based resin component CAI and the cyclic olefin-based random copolymer [group, and optionally added Either the other components are mechanically blended using an extruder or kneader, or each component is simultaneously dissolved in a suitable hydrocarbon solvent such as hexane, heptane, decane, cyclohexane, benzene, toluene, or xylene. Examples include a method in which the mixture is dissolved separately and then the solvent is removed, and a method in which these two methods are combined.

Poly(phenylene ether) resin composition obtained by the above manufacturing method Poly(phenylene ether) resin component [A] More heat resistant (heat distortion temperature) than polystyrene
The cyclic olefin random copolymer [B] has a high mold shrinkage rate because it is substantially amorphous and has high heat resistance while maintaining the various properties of poly(phenylene ether) resin. , poly(
A phenylene ether) based resin composition is obtained.

Poly(phenylene ether) resin composition IL superior to the present invention Because it has the above-mentioned properties, it can be used in addition to conventional poly(phenylene ether)-based applications such as heat resistance, electrical properties,
It can be widely used in fields where moldability is required.

Examples of applications include electrician LOAIIIi, housings for cameras, pumps, etc., chassis, precision equipment, instrument panels, radiator grills,
Cluster grille, console box, garnish, foil cover, column cover fender bonnet,
Cover skin for automobile interior and exterior materials such as trunks, seats, connectors, coil bobbins, switches, etc. Bottle 凰
Foams such as cast film, biaxially stretched film, multilayer film, etc., extrusion foam imitation, and injectimin foam are listed.

i bean 2 shame 1 The above 9, according to the present invention! f, [A] Poly(phenylene ether) resin component is blended with [B] cyclic olefin random copolymer component Poly(phenylene ether) resin composition with excellent heat resistance, electrical properties, and moldability You can get things.

[Examples] Hereinafter, the present invention will be further explained with reference to Examples, but the present invention is not limited to these Examples.

Nasaka: Methods for measuring and evaluating various physical property values in the present invention are shown below.

(1) Melt flow index (MFRt) According to ASTM DI238, at a predetermined temperature T°C and a load of 2.
Measure with 16 kg (2) Preparation of test piece Use Toshiba Machine's injection molding machine 15-50EPN and the specified test piece mold ν＼ Mold the test piece under the following molding conditions. Molding conditions measured after leaving for 48 hours: cylinder temperature 280°C, mold temperature 80°C,
Injection pressure car secondary/secondary = 1000/800kg/cmf
fi injection speed (-next) 30mm/see, screw rotation speed 150rs (3) Bending test Test conducted according to ASTM D790 Test piece shape: 5X 1/2X 1/81 inch, distance between spans 1mm Test speed: 20mm/ min Test temperature = 23°C (4) Tensile test Test conducted in accordance with ASTM D638 Test piece shape: Type ■ Test speed: 50 mm/min Test temperature: 23°C (5) Heat distortion temperature (HDT) Conducted in accordance with ASTM D648 Test piece shape: 5X 1/4X 1/2t inch load
Weight: 264psi (6) Softening temperature (TMA) Thermo Mechanical A manufactured by DuPont
The thermal deformation behavior of a 1 mm thick sheet was measured using a nalyzer. That is, a quartz needle was placed on the sheet, a load of 49 g was applied, and the temperature was raised at a rate of 5°C/min, until the needle became 0.635 mm. The temperature at which it entered was defined as TMA.

(7) Glass transition temperature (Tg) and melting point (Tm) SE
Temperature increase rate 10 using DSC-20 manufactured by IKO Electronics Industry ■
Measured at °C/min.

(8) Rockwell hardness measured at 23°C according to ASTM D785 (9) Pencil hardness measured at 23°C according to JIS K 5400 (10
)Moldability Using an injection molding machine LS-50EPN manufactured by Toshiba Machine ■, injection molding was performed using a spiral length measuring mold (4.8 mm - semicircular) under the following conditions, and the spiral length of 20 cm or more was α Molding conditions with less than × marked as: Cylinder temperature: 250°C Mold temperature: 6
0℃ Injection pressure 1000kg/am! Delivery speed Medium speed Ill discharge 1 [A] Number average molecular weight of acid component in terms of polystyrene 1
Molecular weight distribution Mw/Mn-3 measured by 430 million GPC,
Intrinsic viscosity measured in chloroform solvent at 623°C [1]
2.0 seeds of poly-L4-(phenylene ether) resin with 0.49 dl/i [B] 13C acid component
- Ethylene content measured by NMR is 63 mol%.

MFR2a m”c is 32g/10mm Intrinsic viscosity [V] measured in decalin at 135°C is 0.48dl/g
, ethylene and 1.4.5.8-difi9/- with TMA at 150°C and Tg at 140°C (Tm not observed).
2.0 kg of pellets of random copolymer (ethylene/DMDF random copolymer) with 1,2,3,4,4a,4b,5,8,8a,9a-decahydrofluorene (hereinafter abbreviated as DMDF) After thorough mixing, the pellets were made into pellets using a twin-screw extruder (Ikegai PCII 45) at a cylinder temperature of 280°C and a pelletizer, and test pieces were prepared using the method described above to determine the physical properties. The evaluation results are shown in Table 1.

Table 1 shows the results of carrying out the same operation as in Example 1 except that the blending amount of [A] acid component CB] component was changed.

Ethylene and DMDF used as the [B] acid component in Example 1
Table 1 shows the results of the same operation except that a polystyrene resin was used instead of the random copolymer with (Comparative Example 1) or component [A] was used alone (Comparative Example 2).

Kanmukoshi A Added ethylene/propylene random copolymer (
Ethylene content: 80mOIXMFR2am”c:0
．． Intrinsic viscosity measured in decalin at 7g/10m at 135℃ [? ] :2. Zd14%: -54℃)20
The weight part is extracted using a twin-screw extruder (Ikegai Iron Works IL PCM 45).
) was melt-blended.To 1 kg of this resin, 3 g of hexene 25B was added to Nippon Oil Co., Ltd. and divinylbenzene was added at a rate of 3 g, and the mixture was thoroughly mixed. PCM 45) was used to carry out the reaction in the melt at a cylinder temperature of 230°C, and the mixture was pelletized using a pelletizer. Table 1 shows the results of the same operation as in Example 1 except that the obtained resin was used in place of the [B] acid component in Example 1.

In place of the ethylene/DMDF copolymer used in Example 1,
A copolymer of ethylene and another cyclic olefin was used as the [B] acid component. The physical properties of the [B] acid component used are shown in Table 2. Table 1 shows the results obtained by carrying out the same operation as in Example 1 except for using these [B] acid components.

Claims (1)

[Claims] (1) [A] poly(phenylene ether) resin or poly(substituted phenylene ether) resin, [B] ethylene, and at least the following formulas [I] to [IV]
] It is a copolymer with a cyclic olefin represented by one of the structural formulas selected from It is made of a cyclic olefin random copolymer having a temperature of 70°C or higher, and the composition ratio of poly(phenylene ether) resin or poly(substituted phenylene ether) resin [A] and cyclic olefin random copolymer [B] is [ A]/[B] (weight ratio) is a poly(phenylene ether) resin composition having a weight ratio of 98/2 to 2/98. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ ... [I] (In the formula [I], l is 0 or a positive integer, and R^
1~R^1^0 may be the same or different, and are atoms or groups selected from the group consisting of hydrogen atoms, halogen atoms, and hydrocarbon groups, and R^1^5~R^ 1^8 may be bonded to each other to form a monocycle or polycycle, and the monocycle or polycycle may have a double bond, and R^1^5 and R With ^1^6 or R^1^7
and R^1^8 may form an alkylidene group). ▲There are mathematical formulas, chemical formulas, tables, etc.▼ ... [II] (In formula [II], m is 0 or a positive integer, and R^1
~R^1^0 may be the same or different, and are atoms or groups selected from the group consisting of hydrogen atoms, halogen atoms, and hydrocarbon groups, and R^9 and R^1^0 may form an alkylidene group). ▲There are mathematical formulas, chemical formulas, tables, etc.▼ ... [III] (In formula [III], n is 0 or a positive integer, and R^
1 to R^1^2 may be the same or different, and are atoms or groups selected from the group consisting of hydrogen atoms, halogen atoms, and hydrocarbon groups, and R^1^1 and R^ 1^2 may form an alkylidene group). ▲There are mathematical formulas, chemical formulas, tables, etc.▼ ... [IV] (In formula [IV], p is 0 or an integer of 1 or more, q and r are 0, 1 or 2, and R^1 ~R^1^5
each independently represents an atom or group from the group consisting of a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group, an aromatic hydrocarbon group, and an alkoxy group, and R^5 (or R^6
) and R^9 (or R^7) may be bonded via an alkylene group having 1 to 3 carbon atoms, or may be bonded directly without any group. )