JPH05186682A - Polyphenylene ether resin composition - Google Patents

Abstract

PURPOSE:To provide the subject composition containing a polyphenylene ether resin, a poly(substituted-phenylene ether) resin and a specific cycloolefin resin and having excellent heat-resistance, electrical properties, mechanical properties and mo ldability. CONSTITUTION:The objective composition contains (A) a polyphenylene ether resin and/or a poly(substituted-phenylene ether) resin (e.g. poly-1,4-phenylene ether) and (B) a cycloolefin resin having an intrinsic viscosity [eta] of 0.05-10dl/g measured in decalin at 135 deg.C and a softening point (TMA) of >=0 deg.C and selected from a copolymer of ethylene and a cycloolefin of formula (p and q are 0 or integer of >=1; m and n are 0-2; R<1> to R<19> are H, halogen, etc.), a ring-opened polymer of the cycloolefin or its hydrogenated product at a weight ratio (A/B) of 98/2 to 2/98. The compound of formula is e.g. 5-phenyl-bicyclo[2.2.1]hept-2-ene.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a poly (phenylene ether) resin composition containing a polyphenylene ether resin, a cyclic olefin resin, and a soft polymer. More specifically, the present invention relates to a polyphenylene ether resin composition having excellent heat resistance, electrical characteristics, mechanical characteristics and moldability.

[0002]

TECHNICAL BACKGROUND OF THE INVENTION A polyphenylene ether resin such as a poly (2,6-dimethylphenylene ether) resin or a poly-substituted phenylene ether resin [hereinafter, may be collectively referred to as a polyphenylene ether resin. ] Has excellent electric properties such as low dielectric constant and dielectric loss tangent, high volume resistivity and high dielectric breakdown strength, excellent heat resistance, and low molding shrinkage. However, since this polyphenylene ether-based resin has a high melt viscosity, there is room for improvement in its moldability. Therefore, in order to improve moldability, a polyphenylene ether resin composition blended with polystyrene has already been commercialized.

However, polystyrene has a lower glass transition temperature than polyphenylene ether-based resins such as poly (2,6-dimethylphenylene ether) resin, and therefore, for example, polyphenylene ether-based resin, which is a typical polyphenylene ether-based resin, is used.
The resin composition in which polystyrene is mixed with the (2,6-dimethylphenylene ether) resin has a problem that the heat resistance is lower than that of the poly (2,6-dimethylphenylene ether) resin.

By the way, it is known that a cyclic olefin having an ethylenic double bond in the ring has a polymerizing property and can be copolymerized with ethylene to obtain a cyclic olefin / ethylene copolymer. (Example: JP-A-60-168708
Publications, 63-243111, 63-305111, 63-223013.
No. and No. 1-185307, etc.).

Such a cyclic olefin resin has the transparency, water resistance and thermal properties required as an optical material, but as a result of further studies by the present inventor, Among them, a cyclic olefin resin having a repeating unit derived from a specific cyclic olefin having an aromatic group (aromatic group-containing cyclic olefin resin)
It was found that a polyphenylene ether resin composition having more excellent properties, which can be used in various applications, can be obtained by blending the above with a polyphenylene ether resin.

The aromatic group-containing cyclic olefin resin itself is already known (see Japanese Patent Laid-Open No. 1-185307).
Further, this publication also describes blending such a cyclic olefin resin having an aromatic group with another resin. However, although this publication shows the characteristics of the aromatic group-containing cyclic olefin resin alone, it does not suggest the characteristics when mixed with other resins.

[0007]

It is an object of the present invention to provide a polyphenylene ether resin composition having excellent heat resistance, electrical properties, mechanical properties and moldability while maintaining the excellent properties of the polyphenylene ether resin. ..

Further, the present invention provides a polyphenylene ether resin composition which is excellent in heat resistance, electrical characteristics and moldability while maintaining the excellent characteristics of the polyphenylene ether resin, and in which mechanical characteristics are remarkably improved. The purpose is to

[0009]

SUMMARY OF THE INVENTION A first polyphenylene ether resin composition according to the present invention comprises [A] polyphenylene ether resin and / or poly (substituted phenylene ether) resin, [B] ethylene and the following formula [I]: The intrinsic viscosity [η] measured in decalin at 135 ° C. selected from the group consisting of a copolymer with a cyclic olefin represented by the formula, a ring-opening polymer of a cyclic olefin and a hydrogenated product thereof is from 0.05 to 10 dl /
g, and a cycloolefin resin having a softening temperature (TMA) of 0 ° C. or higher at a weight ratio ([A] / [B]) within the range of 98/2 to 2/98.

The second polyphenylene ether resin composition according to the present invention is [A] polyphenylene ether resin and / or poly (substituted phenylene ether).
In a decalin at 135 ° C. selected from the group consisting of a resin, a copolymer of [B] ethylene and a cyclic olefin represented by the following formula [I], a ring-opening polymer of a cyclic olefin, and a hydrogenated product thereof. The measured intrinsic viscosity [η] is 0.05 to 10d
[A] / containing a cyclic olefin resin having a l / g and a softening temperature (TMA) of 0 ° C. or higher, and a [C] soft polymer.
The blending weight ratio of [B] is within the range of 98/2 to 2/98, and the blending weight ratio of ([A] + [B]) / [C] is 9
It is characterized by being in the range of 5/5 to 50/50.

[0011]

[Chemical 3]

However, in the above formula [I], p and q are 0 or integers of 1 or more, and m and n are 0, 1
Or 2 and R ^{1 to} R ¹⁹ are each independently an atom selected from the group consisting of a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group and an alkoxy group. Or R ⁹ and R ¹³ or R ¹⁰ and R ¹¹ may be bonded directly or via an alkylene group having 1 to 3 carbon atoms, and when n = m = 0, R ¹⁵ and R ¹⁵ R ¹² or R ¹⁵ and R ¹⁹ may be bonded to each other to form a monocyclic or polycyclic aromatic ring.

The first polyphenylene ether resin composition of the present invention comprises a polyphenylene ether resin [A] and a specific cyclic olefin resin [B] having an aromatic group.
(Ie, a cyclic olefin-based random copolymer, a cyclic olefin ring-opening polymer or a hydrogenated product thereof),
Excellent heat resistance, electrical properties, mechanical properties and moldability.

The second polyphenylene ether-based resin composition of the present invention contains the soft polymer [C] in addition to the above-mentioned first polyphenylene ether-based resin composition. Mechanical properties such as properties are further improved.

[0015]

DETAILED DESCRIPTION OF THE INVENTION Next, the polyphenylene ether resin composition of the present invention will be specifically described.

The first polyphenylene ether resin composition of the present invention comprises a polyphenylene ether resin [A] and a specific cyclic olefin resin [B]. The polyphenylene ether resin [A] constituting the polyphenylene ether resin composition of the present invention has a structure represented by the following formula [i].

[0017]

[Chemical 4]

However, in the above formula [i], R ²⁰ , R
²¹ , R ²² and R ²³ 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,
s is a positive integer.

In the above formula [i], s is 20 to 100.
It is preferably 0. That is, as shown in the above formula [i], the polyphenylene ether-based resin used in the present invention may be a polyphenylene ether having no substituent on the phenylene group, or a polyphenylene ether having a substituent. May be. Further, it may be a mixture of both.

Specific examples of the polyphenylene ether resin or polysubstituted phenylene ether resin represented by the above formula [i] include poly-1,4-phenylene ether,
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-isopropyl-1,4-phenylene ether, poly-2,6-dimethoxy- 1,4-phenylene ether, poly-2,6-dichlorothymer
-1,4-phenylene ether, poly-2,6-diphenyl-1,4-
Examples include phenylene ether, poly-2,6-dinitrile-1,4-phenylene ether, poly-2,6-dichloro-1,4-phenylene ether and poly-2,5-dimethyl-1,4-phenylene ether. Be done. These may be used alone or in combination of two or more.

Regarding these polyphenylene ether resins or poly-substituted phenylene ether resins [A], 3
The intrinsic viscosity [η] measured in chloroform at 0 ° C is usually in the range of 0.01 to 5 dl / g, preferably 0.1 to 3 dl / g.

The softening temperature (TMA) of the above polyphenylene ether resin [A] or polysubstituted phenylene ether resin [A] measured by a thermo mechanical analyzer is usually 100 ° C. or higher, preferably 150 to 250 ° C. Is within the range.

Furthermore, the glass transition temperature (Tg) of the above polyphenylene ether resin or polysubstituted phenylene ether resin [A] is usually 100 ° C. or higher, preferably 150 to 250 ° C.

Next, the cyclic olefin resin [B] constituting the polyphenylene ether resin composition of the present invention will be described. The cyclic olefin resin [B] constituting the polyphenylene ether resin composition of the present invention is a resin having a repeating unit derived from a cyclic olefin having an aromatic ring as represented by the formula [I].

The structural unit (a) derived from ethylene and the structural unit (b) derived from the cyclic olefin represented by the formula [I] are randomly bonded to the cyclic olefin resin [B]. Cyclic olefin random copolymers, ring-opening copolymers of the cyclic olefin represented by the formula [I] (ring-opening copolymers), and hydrogenated products of the ring-opening polymers.

This cyclic olefin can be represented by the following formula [I].

[0027]

[Chemical 5]

However, in the above formula [I], p is 0.
Alternatively, it is a positive integer, preferably 0 to 3. In the above formula [I], m and n are each independently 0, 1 or 2. Further, q is 0 or a positive integer, preferably 0 or 1.

Then, R ^{1 to} R ¹⁹ are, independently of each other,
It is an atom or a group selected from the group consisting of a hydrogen atom, a halogen atom and a hydrocarbon group. Here, examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Moreover, as an example of a hydrocarbon group, a C1-C10 alkyl group, a C5-C15 cycloalkyl group, and a C6-C12 aromatic hydrocarbon group can be mentioned.

Specific examples of the alkyl group include methyl group, ethyl group, isopropyl group, isobutyl group, n-amyl group, neopentyl group, n-hexyl group, n-octyl group,
Examples thereof include n-decyl group and 2-ethylhexyl group. Specific examples of the cycloalkyl group include cyclohexyl group, methylcyclohexyl group, ethylcyclohexyl group and the like. Further, specific examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group and a biphenyl group.

In the above formula [I], R ⁹ or R
^The carbon atom to which ¹³ is bound or the carbon atom to which R ¹⁰ or R ¹¹ is bound may be bound to each other via an alkylene group having 1 to 3 carbon atoms, and is not bound to any group. May be directly bonded to.

Further, when n = m = 0, R ¹⁵ and R ¹² or R ¹⁵ and R ¹⁹ may combine with each other to form a monocyclic or polycyclic aromatic ring. Preferred examples in this case include the groups described below in which R ¹⁵ and R ¹² further form an aromatic ring when n = m = 0.

[0033]

[Chemical 6]

In the above formula, q has the same meaning as in formula [I]. Specific examples of the cyclic olefin represented by the formula [I] include the compounds described below.

[0035]

[Chemical 7]

[0036]

[Chemical 8]

[0037]

[Chemical 9]

[0038]

[Chemical 10]

[0039]

[Chemical 11]

[0040]

[Chemical 12]

The cyclic olefin represented by the above formula [I] can be produced by condensing cyclopentadiene and the corresponding olefin or cyclic olefin by the Diels-Alder reaction.

In the cyclic olefin random copolymer used as the cyclic olefin resin [B] constituting the resin composition of the present invention, the structural unit (a) derived from ethylene is usually 40 to 97 mol%. , Preferably 50-9
It is contained in an amount in the range of 5 mol%, and the structural unit (b) derived from the cyclic olefin is usually contained in an amount of 3 to 60 mol%, preferably 5 to 50 mol%.

In the cyclic olefin random copolymer, the repeating units derived from ethylene and the repeating units derived from cyclic olefin are arranged randomly and substantially linearly. The fact that the cyclic olefin-based random copolymer is substantially linear and does not have gel-like cross-linking can be confirmed by completely dissolving the random copolymer in 135 ° C. decalin. it can.

The cyclic olefin random copolymer is obtained by polymerizing, for example, ethylene and a cyclic olefin in a hydrocarbon medium in the presence of a catalyst formed from a hydrocarbon-soluble vanadium compound and a halogen-containing organoaluminum compound. Can be manufactured by.

In carrying out such polymerization, for example, JP-A-
60-168708, 61-120816, 61-115912, 61-11
5916, 61-271308, 61-272216, 62-252406
No. 62-252407 and the like can be used.

In such a cyclic olefin random copolymer, for example, at least a part of the cyclic olefin represented by the above formula [I] forms a structure represented by the following formula [IA] and is derived from ethylene. It is considered that the repeating units are randomly bonded.

[0047]

[Chemical 13]

However, in the above formula [IA], R ^{1 to} R
¹⁹ , and p, q, m and n have the same meanings as in formula [I]. The cyclic olefin random copolymer has a structural unit (a) derived from ethylene and a structural unit (b) derived from the cyclic olefin represented by the above formula [I] as essential structural units. The random copolymer may have a constitutional unit derived from another copolymerizable unsaturated monomer, if necessary, within a range in which the characteristics are not impaired. Examples of the unsaturated monomer which is added as necessary and may be copolymerized specifically include propylene, 1-butene, and 4-methyl-1-.
Examples thereof include pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, and other α-olefins having 3 to 20 carbon atoms. .. The constitutional unit derived from these unsaturated monomers may be contained in an amount of less than equimolar to the constitutional unit (a) derived from ethylene in the resulting random copolymer.

Further, the cyclic olefin random copolymer as described above is a cyclic olefin other than the cyclic olefin represented by the above formula [I] (other cyclic olefins) within a range not impairing the physical properties of the copolymer. It is also possible to have a structural unit derived from Examples of such a cyclic olefin include cyclobutene, cyclopentene, cyclohexene, 3,4-dimethylcyclohexene, 3-methylcyclohexene, 2- (2-methylbutyl) -1-cyclohexene, 2,3,3a, 7a-tetrahydro- In addition to 4,7-methano-1H-indene and 3a, 5,6,7a-tetrahydro-4,7-methano-1H-indene, the compounds described below can be used.

[0050]

[Chemical 14]

[0051]

[Chemical 15]

[0052]

[Chemical 16]

[0053]

[Chemical 17]

[0054]

[Chemical 18]

[0055]

[Chemical 19]

[0056]

[Chemical 20]

[0057]

[Chemical 21]

[0058]

[Chemical formula 22]

[0059]

[Chemical formula 23]

[0060]

[Chemical formula 24]

[0061]

[Chemical 25]

[0062]

[Chemical formula 26]

[0063]

[Chemical 27]

[0064]

[Chemical 28]

[0065]

[Chemical 29]

[0066]

[Chemical 30]

Such other cyclic olefins can be used alone or in combination, and
It is used in an amount of 0 to 20 mol%. Among the cyclic olefin-based resins used in the present invention, the cyclic olefin ring-opening polymer includes a homocyclic ring-opening polymer of the cyclic olefin represented by the above formula [I] and a ring-opening polymer obtained by copolymerizing a plurality of cyclic olefins. There are ring copolymers.

The ring-opening polymer and ring-opening copolymer used as the cyclic olefin resin [B] in the present invention are prepared by ring-opening polymerization of the above-mentioned cyclic olefins alone or in combination. be able to.

That is, a ring-opening polymer or a ring-opening copolymer is prepared by subjecting the cyclic olefin represented by the above formula [I] to ring-opening polymerization in the presence of a ring-opening polymerization catalyst. Examples of the ring-opening polymerization catalyst used here include:
Ruthenium, rhodium, osmium, indium, platinum, molybdenum and other metal halides, nitrates of these metals or acetylacetone compounds of these metals, and a catalyst comprising a reducing agent such as alcohols or tin compounds, and Examples of the catalyst include halogen compounds of metals such as titanium, vanadium, zirconium, tungsten and molybdenum, acetylacetone compounds of these metals, and metal aluminum compounds.

When the above ring-opening polymer is prepared, in addition to the cyclic olefin represented by the above formula [I] within the range that does not impair the characteristics of the cyclic olefin resin,
Still other cyclic olefins can be used.

Examples of other cyclic olefins that can be used here include cyclobutene, cyclopentene,
Cyclooctene, cyclononene, methylcyclopentene, methylcycloheptene, methylcyclooctene, methylcyclononene, methylcyclodecene, ethylcyclopentene, ethylcycloheptene, ethylcyclooctene, ethylcyclononene, dimethylcycloheptene, dimethylcyclooctene, Mononuclear olefins having 4 or more carbon atoms such as dimethylcyclononene, dimethylcyclodecene, cyclooctadiene and cyclodecadiene, and other cyclic olefins exemplified in the description of the cyclic olefin random copolymer are Can be mentioned. Further, as a molecular weight modifier, an alkene such as propylene, 1-butene, 1-pentene or 1-hexene can be used as a copolymerization component.

In such a ring-opening polymer, for example, at least a part of the cyclic olefin represented by the above formula [I] is considered to have a structure represented by the following formula [IB].

[0073]

[Chemical 31]

However, in the above formula [IB], R ^{1 to} R
¹⁹ , and p, q, m and n have the same meanings as in formula [I]. The hydrogenated product of the ring-opening polymer used as the cyclic olefin resin [B] in the present invention is
It is obtained by hydrogenating the cyclic olefin ring-opening polymer prepared as described above. For hydrogenation of the ring-opening polymer, a usual hydrogenation method performed in the presence of a hydrogenation catalyst can be adopted.

As the hydrogenation catalyst used here,
A hydrogenation catalyst such as a heterogeneous catalyst or a homogeneous catalyst generally used in hydrogenating an olefin compound can be used.

Specific examples of the heterogeneous catalyst include metals such as nickel, palladium and platinum, and solids obtained by supporting these metals on a carrier such as carbon, silica, diatomaceous earth, alumina and titanium oxide. Catalyst (eg, nickel / silica, nickel / diatomaceous earth, palladium / carbon, palladium / silica, palladium /
Diatomaceous earth, palladium / alumina, etc.). Further, as an example of the homogeneous catalyst, there are VIII of the periodic table.
Group III metal based catalysts, examples of such catalysts are nickel compounds such as cobalt naphthenate / triethylaluminum, cobalt octenoate / n-butyllithium, nickel acetylacetonate / triethylaluminum or cobalt compounds. And Periodic Table I
To organic metal compounds formed from Group III metals, and Rh compounds can also be used.

The hydrogenation reaction using the hydrogenation catalyst as described above can be carried out in either a heterogeneous system or a homogeneous system, depending on the type of the catalyst. The reaction conditions in such a system are usually set under hydrogen at 1 to 150 atm, and usually at a temperature of 0 to 180 ° C, preferably 20 to 100 ° C. The hydrogenation rate under such conditions can be adjusted by appropriately setting conditions such as hydrogen pressure, reaction temperature, reaction time, catalyst concentration, etc., but the double bond present in the main chain of the polymer Of these, 50% or more, preferably 80% or more, and more preferably 90% or more are hydrogenated.

In such a hydrogenated ring-opening polymer,
For example, at least a part of the cyclic olefin represented by the above formula [I] is considered to have a structure represented by the following formula [IC].

[0079]

[Chemical 32]

However, in the above formula [IC], R ^{1 to} R
¹⁹ , and p, q, m and n have the same meanings as in formula [I]. In the cyclic olefin-based resin, the cyclic olefin represented by the formula [I] used as a raw material has a structure represented by the above formulas [IA], [IB] and [IC], for example. It can be confirmed from the ¹³ C-NMR measurement result of the resin.

The intrinsic viscosity [η] of the cyclic olefin resin [B] constituting the resin composition of the present invention measured in decalin at 135 ° C. is in the range of 0.05 to 10 dl / g and further 0. It is preferably 0.08 to 5 dl / g.

The softening temperature (TMA) of the cyclic olefin resin [B] constituting the resin composition of the present invention measured by a thermo mechanical analyzer is 0 ° C. or higher,
Further, the softening temperature (TMA) is 10 to 250 ° C, especially 10 to
It is preferably in the range of 200 ° C.

The glass transition temperature (Tg) of the cyclic olefin resin [B] constituting the resin composition of the present invention measured by DSC is usually in the range of -20 to 230 ° C, preferably -10 to 210 ° C. It is in. Furthermore, the crystallinity of this cyclic olefin resin [B] measured by X-ray diffraction is usually 0 to 40%, preferably 0 to 7
%, Particularly preferably 0 to 5%.

In the present invention, at least a part of the above cyclic olefin resin, especially the cyclic olefin random copolymer is modified with an unsaturated carboxylic acid such as maleic anhydride or a modifier such as glycidyl acrylate. May be. The cyclic olefin-based resin may be a modified product obtained by reacting a multi-sensitive monomer such as divinylbenzene in the presence of a radical reaction initiator. Such a modified product is a cyclic olefin resin as described above, an unsaturated carboxylic acid, an anhydride thereof,
And an alkyl ester of an unsaturated carboxylic acid or a derivative such as a glycidyl ester of an unsaturated carboxylic acid. The content of the structural unit derived from the modifier in the modified product of the cyclic olefin resin [B] in this case is usually 0.0
It is from 01 to 5% by weight. Such a modified product of a cyclic olefin-based resin can be produced by blending a cyclic olefin-based resin with a modifying agent so as to have a desired modification ratio and graft-polymerizing the modified product, or a modified product with a high modification ratio is prepared in advance. It can also be produced by preparing and then mixing the modified product with an unmodified cyclic olefin resin.

In the first polyphenylene ether resin composition of the present invention, the polyphenylene ether resin [A] and the cyclic olefin resin [B] are in a weight ratio,
It is contained in 98/2 to 2/98 ([A] component / [B] component). In the present invention, the weight ratio of [A] component / [B] component is preferably in the range of 95/5 to 5/95. By blending the components [A] and [B] in the amounts described above, the heat resistance, mechanical properties and moldability of the composition are improved.

The second polyphenylene ether resin composition of the present invention further contains a soft polymer [C] in addition to the above polyphenylene ether resin [A] and cyclic olefin resin [B]. ..

As the soft polymer [C] used in the present invention, (i) a soft polymer having a repeating unit derived from a cyclic olefin, (ii) an α-olefin copolymer, (ii)
i) α-olefin / diene copolymer, (iv) aromatic vinyl hydrocarbon / conjugated diene soft copolymer, and (v)
A soft polymer or copolymer of isobutylene or isobutylene / conjugated diene may be mentioned.

The soft polymer [C] will be described below. Soft having repeating units derived from cyclic olefins
Soft polymer (i) having a repeating unit derived from a cyclic polymer (i) cyclic olefin, ethylene, and the cyclic olefin,
It is a copolymer formed from an α-olefin as an optional component. Here, as the α-olefin, for example, propylene, 1-butene, 4-methyl-1-butene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1- Mention may be made of C3-C20 α-olefins such as octadecene and 1-eicosene. Among these, α- with 3 to 20 carbon atoms
Olefin is preferred. Further, cyclic olefins and cyclic dienes such as norbornene, ethylidene norbornene and dicyclopentadiene can also be used together.

In the soft polymer (i) having a repeating unit derived from a cyclic olefin, the repeating unit derived from ethylene is usually 40 to 99 mol%, preferably 50 to 90 mol%, particularly preferably 75-90
It is contained in an amount within the range of mol%. The repeating unit derived from α-olefin is usually contained in an amount within the range of 0 to 45 mol%, preferably 0 to 35 mol%. The repeating unit derived from a cyclic olefin is contained in an amount of usually 1 to 40 mol%, preferably 1 to 20 mol%, more preferably 2 to 15 mol%.

In this soft polymer (i), the repeating unit derived from ethylene, the repeating unit derived from an α-olefin other than ethylene, and the repeating unit derived from a cyclic olefin are randomly arranged. , And they are arranged substantially linearly.
This soft polymer (i) has a substantially linear structure,
This copolymer does not have a cross-linked structure
It can be confirmed by completely dissolving it in decalin.

The soft polymer (i) having a repeating unit derived from this cyclic olefin has a glass transition temperature (Tg) of usually 0 ° C. or lower, preferably, unlike the above-mentioned cyclic olefin resin [A]. -10 ℃ or less, 135 ℃
Intrinsic viscosity [η] measured in decalin of 0.1 is usually 0.
It is from 01 to 10 dl / g, preferably from 0.8 to 7 dl / g. The crystallinity of the soft polymer (i) measured by the X-ray diffraction method is usually 0 to 10%, preferably 0 to 7%, particularly preferably 0 to 5%.

The soft polymer (i) having a repeating unit derived from this cyclic olefin is described in JP-A-60-168708,
61-120816, 61-115912, 61-271308, 61-
It can be produced by appropriately selecting the conditions according to the method proposed by the present applicant in each publication such as 272216 and 62-252406.

At least a part of the soft polymer having repeating units derived from the cyclic olefin may be modified with an unsaturated carboxylic acid such as maleic anhydride or a modifier such as glycidyl acrylate. The cyclic olefin-based soft polymer may be a modified product obtained by reacting a multi-sensitive monomer such as divinylbenzene in the presence of a radical reaction initiator.

Α-Olefin-based Copolymer (ii) α-Olefin Used as the Soft Polymer [C] in the Present Invention
The olefin copolymer (ii) is an amorphous or low crystalline copolymer composed of at least two kinds of α-olefins. Specific examples include ethylene / α-olefin copolymers and propylene / α-olefin copolymers.

The α-olefin constituting the ethylene / α-olefin copolymer is usually one having 3 to 20 carbon atoms, and specific examples include propylene, 1-butene and 4-methyl-olefin. 1-butene, 1-hexene, 1-octene, 1
Mention may be made of decene and mixtures thereof.
Of these, α-olefins having 3 to 10 carbon atoms are preferable, and propylene or 1-butene is particularly preferable.

The molar ratio of the repeating unit derived from ethylene to the repeating unit derived from α-olefin in the ethylene / α-olefin copolymer (ethylene /
The α-olefin) varies depending on the type of the α-olefin, but is usually 40/60 to 95/5. When propylene is used as the α-olefin, the above molar ratio is usually 30/70, preferably 40/60 to
95/5, particularly preferably 50/50 to 90/10, when using an α-olefin having 4 or more carbon atoms as the α-olefin, usually 50/50 to 95/5, preferably 80 / 20 to 95/5.

The α-olefin constituting the propylene / α-olefin copolymer is usually an α-olefin having 4 to 20 carbon atoms, and specific examples thereof include 1-butene and 4-methyl-1. Mention may be made of -pentene, 1-hexene, 1-octene, 1-decene and mixtures thereof. Of this,
Particularly, α-olefin having 4 to 10 carbon atoms is preferable.

In the propylene / α-olefin copolymer as described above, the molar ratio of the repeating units derived from propylene to the repeating units derived from α-olefin (propylene / α-olefin) is α- Normally 50/50 to 95, although it depends on the type of olefin
/ 5. The above molar ratio is such that the α-olefin has 5 carbon atoms.
In the case of the above α-olefin, 80/20 to 9
It is preferably 5/5.

The α-olefin soft polymer (i
The intrinsic viscosity [η] measured in i) at 135 ° C decalin is
It is usually in the range of 0.2 to 10 dl / g, preferably 1 to 5 dl / g. Further, its density is usually 0.82 to 0.96.
g / cm ^3, preferably in the range of 0.84~0.92g / cm ^3.

This α-olefin soft polymer (ii) is
It may be graft-modified with an unsaturated carboxylic acid or its derivative. The graft modification rate in this case is usually 0.01 to 5% by weight, preferably 0.1 to 4% by weight. Examples of unsaturated carboxylic acids or derivatives used herein are acrylic acid, maleic acid, fumaric acid, tetrahydrophthalic acid, itaconic acid, citraconic acid, crotonic acid, isocrotonic acid and nadic acid.
Unsaturated carboxylic acids such as ^TM (endocis-bicyclo [2,2,1] hept-5-ene-2,3-dicarboxylic acid) or halides, amides, imides, anhydrides and esters of these unsaturated carboxylic acids And the like. Specific examples of the above unsaturated carboxylic acid derivative include maleyl chloride, maleimide, maleic anhydride, citraconic anhydride, maleic acid monomethyl ester, maleic acid dimethyl ester and glycidyl maleate.

Among these, maleic acid and maleic anhydride, nadic acid ^TM and nadic acid anhydride are particularly preferable.
^TM is preferred. As a method for modifying the α-olefin-based soft polymer using the above graft monomer,
Various conventionally known methods can be adopted. For example, a method of melting an α-olefin soft polymer and adding a graft monomer to the melt to perform graft polymerization, dissolving the α-olefin soft polymer in a solvent, and adding the graft monomer to this solution. A method such as a method of graft polymerization can be adopted. When adopting the above grafting method, it is preferable to use a radical initiator. By using the radical initiator, the graft reaction can be efficiently performed.

The graft reaction as described above is usually carried out at 60
It is carried out at a temperature within the range of ~ 350 ° C. The radical initiator is usually used in an amount within the range of 0.001 to 1 part by weight with respect to 100 parts by weight of the α-olefin soft polymer.

The α-olefin soft polymer may be a modified product obtained by reacting a multi-sensitive monomer such as divinylbenzene in the presence of a radical reaction initiator.

The radical initiator used in the above modification is not particularly limited, and compounds usually used in the graft polymerization reaction can be used. That is,
Examples of radical initiators that can be used here are organic peroxides or organic peresters [eg,
Benzoyloxyperoxide, dichlorobenzoyl peroxide, dicumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di (peroxide benzoate) hexyne-3,1,4-bis (tert-butylperoxyisopropyl) ) Benzene, lauroyl peroxide, tert-butyl peracetate, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexyne-3,2,5-dimethyl-
2,5-di (tert-butylperoxy) hexine, tert-butylperbenzoate, tert-butylper-sec-octoate, tert-butylperpivalate, cumylperpivalate and tert-butylperdiethylacetate]; azo Examples thereof include compounds [eg, azobisisobutyronitrile and dimethylisoisobutyrate].
Of these, dicrimyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexyne-3,2,5-dimethyl-2,5-di (tert- Dialkyl peroxides such as gutylperoxy) hexyne and 1,4-bis (tert-butylperoxyisopropyl) benzene are preferably used.

Α-Olefin / diene copolymer (iii) α used as the soft polymer [C] in the present invention
Examples of the -olefin / diene copolymer (iii) include ethylene / α-olefin / diene copolymer rubber and propylene / α-olefin / diene copolymer rubber.

In preparing these copolymer rubbers, α-olefins having 3 to 20 carbon atoms are usually used. Examples of this α-olefin include propylene and 1-
Examples include butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene and mixtures thereof. Of these, α-olefins having 3 to 10 carbon atoms are preferable. However, in the case of the propylene / α-olefin / diene copolymer rubber, the α-olefin having 4 to 20 carbon atoms is used.

Further, examples of the diene component constituting these copolymer rubbers include 1,4-hexadiene, 1,6-octadiene, 2-methyl-1,5-hexadiene, 6-methyl-1,5. -Chain non-conjugated dienes such as heptadiene and 7-methyl-1,6-octadiene, cyclohexadiene, dicyclopentadiene, methyltetrahydroindene, 5-vinylnorbornene, 5-ethylidene-2-norbornene, 5-methylene-
Cyclic non-conjugated dienes such as 2-norbornene, 5-isopropylidene-2-norbornene and 6-chloromethyl-5-isopropenyl-2-norbornene, and 2,3-diisopropylidene-5-norbornene, 2-ethylidene -3-isopropylidene-5-norbornene, 2-propenyl-2,2-norbornadiene and the like can be mentioned.

The molar ratio of the repeating units derived from ethylene and the repeating units derived from α-olefin (ethylene / α-olefin) in the ethylene / α-olefin / diene copolymer rubber is α-olefin. Usually, 50/50 to 95 /
5, preferably 50/50 to 90/10.

The content of the repeating unit derived from the diene component in these copolymer rubbers is usually 0.5 to 10 mol%, preferably 0.5 to 5 mol%. In the propylene / α-olefin / diene copolymer rubber as described above, the molar ratio of the repeating unit derived from propylene to the repeating unit derived from α-olefin (propylene / α-olefin) is α -
Generally 50 /, although it depends on the type of olefin
It is in the range of 50 to 95/5. When 1-butene is used as the α-olefin, the molar ratio between the repeating unit derived from propylene and the repeating unit derived from 1-butene is 50/50 to 90 /.
It is preferably in the range of 10, and when an α-olefin having 5 or more carbon atoms is used as the α-olefin, a repeating unit derived from propylene and α-olefin are used.
The molar ratio with the repeating unit derived from the olefin is
It is preferably in the range of 80/20 to 85/5.

The crystallinity of such an α-olefin / diene copolymer measured by the X-ray diffraction method is usually in the range of 0 to 10%, preferably 0 to 5%. Also, regarding α-olefin / diene copolymer, 135 ° C
Intrinsic viscosity [η] measured in decalin of 0.1 is usually 0.
It is in the range of 1 to 10 dl / g, preferably 1 to 5 dl / g.
Furthermore, the iodine value is usually in the range of 1-30, preferably 5-25.

Aromatic vinyl hydrocarbon / conjugated diene soft
Copolymer (iv) Aromatic vinyl hydrocarbon / conjugated diene soft copolymer (iv) used as the soft polymer [C] in the present invention
Are random copolymers, block copolymers or hydrides of aromatic vinyl hydrocarbons and conjugated diene compounds. Specific examples include styrene / butadiene block copolymer rubber, styrene / butadiene / styrene block copolymer rubber, styrene / isoprene block copolymer rubber, styrene / isoprene / styrene block copolymer rubber, hydrogenated styrene.・ Butadiene / styrene block copolymer, hydrogenated styrene / isoprene
Examples thereof include styrene block copolymer rubber and styrene / butadiene random copolymer rubber.

In the styrene-butadiene copolymer rubber, the molar ratio of the repeating unit derived from styrene to the repeating unit derived from butadiene is 0/1.
It is preferably in the range of 00-60 / 40.

In the styrene / butadiene / styrene block copolymer rubber, the molar ratio of the repeating unit derived from styrene to the repeating unit derived from butadiene is usually within the range of 0/100 to 60/40. is there. And the degree of polymerization of each component is 0-5, styrene
It is about 000, and butadiene is often about 10 to 20,000.

In the styrene / isoprene block copolymer rubber, the molar ratio of the repeating unit derived from styrene to the repeating unit derived from isoprene is usually 0/100 to 60/40.

In the styrene / isoprene / styrene block copolymer rubber, the molar ratio of the repeating unit derived from styrene to the repeating unit derived from isoprene is usually 0/100, preferably 60/40. Within range. The polymerization degree of each component is about 0 to 5,000 for styrene and 10 to 20, for isoprene.
It is about 000.

The hydrogenated styrene / butadiene / styrene block copolymer is a copolymer rubber obtained by partially hydrogenating the double bonds remaining in the above styrene / butadiene / styrene block copolymer rubber. The weight ratio of the styrene portion to the rubber portion in the polymer is usually 0/100 to
Within the range of 60/40.

The hydrogenated styrene / isoprene / styrene block copolymer rubber is the above-mentioned styrene / isoprene / styrene rubber.
It is a copolymer rubber in which the double bond remaining in the styrene block copolymer is partially hydrogenated. The weight ratio of the styrene portion to the rubber portion in this copolymer rubber is usually within the range of 0/100 to 60/40.

The weight average molecular weight of such an aromatic vinyl hydrocarbon / conjugated diene type soft copolymer measured by GPC (gel permeation chromatography, solvent: orthodichlorobenzene, temperature: 140 ° C.) is Usually, it is in the range of 500 to 2,000,000, preferably 10,000 to 1,000,000.

Isobutylene or isobutylene conjugated diene
The soft polymer or copolymer (v) made of ene (v) The isobutylene-based soft polymer or copolymer (v) used as the soft polymer [C] is specifically polyisobutylene rubber or polyisoprene rubber. Polybutadiene rubber or isobutylene / isoprene copolymer rubber is used.

The properties of the soft polymers (ii) to (v) are the same as those of the cyclic olefinic soft polymer (i), and these soft polymers have a decalin content of 135 ° C. The intrinsic viscosity [η] measured in is usually 0.01
-10 dl / g, preferably 0.08 to 7 dl / g, and the glass transition temperature (Tg) is usually 0 ° C or lower, preferably -10 ° C or lower, particularly preferably -20 ° C or lower. ..
The crystallinity measured by the X-ray diffraction method is 0-10.
%, Preferably 0 to 7%, particularly preferably 0 to 5%.

The soft polymers [C] exemplified in the above (i) to (v) can be used alone or in combination. In the second resin composition of the present invention, the first
The resin composition (i.e. [A] + [B]) and the soft polymer [C] are in a weight ratio of 95/5 to 50/50, preferably 90/10 to 60/40 (([A] + [B] component / [C] component). By blending the components [A], [B] and [C] in such a blending weight ratio, the mechanical properties such as impact resistance are remarkably improved.

In the first and second polyphenylene ether resin compositions of the present invention, in addition to the above-mentioned components [A] and [B], and further the component [C], a heat resistance stabilizer, a weather resistance stabilizer and an antistatic agent are provided. Agent, slip agent, anti-blocking agent,
Antifogging agents, lubricants, dyes, pigments, natural oils, synthetic oils, waxes and the like can be added, and the mixing ratio is an appropriate amount. For example, as a stabilizer to be added as an optional component, specifically, tetrakis [methylene-3 (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane,
β- (3,5-di-t-butyl-4-hydroxyphenyl) propionic acid alkyl ester, 2,2'-oxamide bis [ethyl-3 (3,5-di-t-butyl-4-hydroxyphenyl)] Phenolic antioxidants such as propionate, fatty acid metal salts such as zinc stearate, calcium stearate and calcium 12-hydroxystearate, glycerin monostearate, glycerin monolaurate, glycerin distearate, pentaerythritol monostearate, pentaerythritol Examples thereof include fatty acid esters of polyhydric alcohols such as distearate and pentaerythritol tristearate. These may be blended alone or in combination. An example of the combination is tetrakis [methylene-3 (3,5-
Di-t-butyl-4-hydroxyphenyl) propionate]
Examples thereof include a combination of methane with zinc stearate and glycerin monostearate.

In the present invention, it is particularly preferable to use a phenolic antioxidant and a polyhydric alcohol fatty acid ester in combination, and the polyhydric alcohol fatty acid ester is one of the alcoholic hydroxyl groups of the trihydric or higher polyhydric alcohol. The part is preferably a polyhydric alcohol fatty acid ester esterified.

Specific examples of the fatty acid ester of polyhydric alcohol include glycerin monostearate, glycerin monolaurate, glycerin monomyristate, glycerin monopalmitate, glycerin distearate, glycerin dilaurate and the like. Fatty acid esters of pentaerythritol such as fatty acid ester, pentaerythritol monostearate, pentaerythritol monolaurate, pentaerythritol dilaurate, pentaerythritol distearate, pentaerythritol tristearate and the like are used.

Such a phenolic antioxidant is usually 0.01 to 10 parts by weight, preferably 0.05 to 3 parts by weight, based on 100 parts by weight of the polyphenylene ether resin composition.
It is used in an amount of 0.1 part by weight, more preferably 0.1 to 1 part by weight, and the fatty acid ester of polyhydric alcohol is usually 0.01 to 10 parts by weight, preferably 0.1 part by weight to 100 parts by weight of the composition. Used in an amount of 05-3 parts by weight.

The first and second polyphenylene ether resin compositions of the present invention include silica, diatomaceous earth, alumina, titanium oxide, magnesium oxide, pumice powder, and pumice balloon as long as the object of the present invention is not impaired. , Aluminum hydroxide, magnesium hydroxide, basic magnesium carbonate, dolomite, calcium sulfate, potassium titanate,
Barium sulfate, calcium sulfite, talc, clay, mica, asbestos, glass fiber, glass flake, glass beads, calcium silicate, montmorillonite, bentonite, graphite, aluminum powder, molybdenum sulfide, boron fiber, silicon carbide fiber, polyethylene fiber, polypropylene Fillers such as fibers, polyester fibers and polyamide fibers may be added.

The polyphenylene ether resin composition of the present invention can be manufactured by a known method.
For example, a polyphenylene ether resin component [A] and a cyclic olefin resin [B], a soft polymer [C], and optionally other components are mechanically blended using an extruder, a kneader or the like. how to,
Alternatively, each component is simultaneously dissolved in a suitable good solvent (eg, a hydrocarbon solvent such as hexane, heptane, decane, cyclohexane, benzene, toluene and xylene), or separately dissolved solutions are prepared and then mixed,
Then, a method of removing the solvent, a method of combining these two methods, and the like can be mentioned.

The cyclic olefin resin [B], which is one component of the resin composition of the present invention, has an aromatic group and therefore has very good compatibility with the polyphenylene ether resin component [A]. There is. Furthermore, a soft polymer [C],
Particularly, the styrene-based soft polymer is a resin composition ([A] +
Excellent compatibility with [B]). The resin composition of the present invention comprising such components [A] and [B] and further component [C] has the following characteristics.

The cyclic olefin resin [B], which has a higher TMA softening temperature than polystyrene conventionally used for modifying polyphenylene ether, has higher heat resistance (heat distortion temperature) than polystyrene and is substantially amorphous. Due to the quality, the molding shrinkage shows a small value. Therefore, in the resin composition of the present invention in which the cyclic olefin resin [B] having such characteristics is blended with the polyphenylene ether resin component [A], the polyphenylene ether resin is essentially excellent. Heat resistance, electrical characteristics and moldability are improved while maintaining the characteristics.

When the cyclic olefin resin [B] having a TMA temperature of less than 70 ° C. is used, the polyphenylene ether resin composition of the present invention has a toughness higher than that of polystyrene in the polyphenylene ether resin component [A]. high,
In addition, since the cyclic olefin resin [B] having a small molding shrinkage is blended because it is substantially amorphous, the tensile properties of the polyphenylene ether resin are maintained while maintaining the excellent properties inherently possessed by the polyphenylene ether resin. Mechanical properties such as elongation and impact strength, electrical properties, and moldability are improved.

Further, by blending the soft polymer [C], the mechanical strength is further improved. Since the polyphenylene ether-based resin composition of the present invention has the above-mentioned various properties, it can be widely used in fields in which heat resistance, electrical properties, moldability, etc. are required in addition to conventional polyphenylene ether-based applications. it can.

Examples of applications of the polyphenylene ether resin composition of the present invention include housings for electric tools, office automation equipment, cameras and pumps; chassis; precision instrument parts; instrument panels, radiator grills, clusters. Automotive interior and exterior materials such as grills, console boxes, garnishes, foil covers, column covers, fenders, bonnets and trunks; sheets; cases or covers such as connectors, coil bobbins and switches; bottles; cast films, biaxially stretched films and Films such as multilayer films; foams such as extruded foams and injection foams.

[0133]

EFFECTS OF THE INVENTION The polyphenylene ether resin composition of the present invention comprises [A] a polyphenylene ether resin component and [B] a specific cyclic olefin resin having an aromatic group. Excellent formability and mechanical properties.

Further, the second composition of the present invention containing the soft polymer [C] has the above-mentioned excellent properties and further improved mechanical properties such as impact strength.

[0135]

EXAMPLES The present invention will now be described in more detail with reference to examples, but the present invention is not limited to these examples.

The methods of measuring and evaluating various physical properties in the present invention are shown below. (1) Melt flow index (MFR _T ) Measured at a predetermined temperature T ° C. and a load of 2.16 Kg according to ASTM D1238. (2) Preparation of test piece Using an injection molding machine IS-50EPN manufactured by Toshiba Machine Co., Ltd. and a predetermined die for a test piece, molding was performed under the following molding conditions. After molding, the test piece was left standing at room temperature for 48 hours and then measured. Molding conditions: cylinder temperature 280 ° C, mold temperature 80 ° C, injection pressure primary / secondary = 1000 / 800Kg / cm ² injection speed (primary) 30mm / sec, screw rotation speed 15
0 rpm (3) Bending test Measured according to ASTM D790. Test piece shape: 5 × 1/2 × 1/8 ^t inch, span distance 51 mm Test speed: 20 mm / min Test temperature: 23 ° C. (4) Tensile test Measured according to ASTM D638. Test piece shape: Type IV Test speed: 50 mm / min Test temperature: 23 ° C. (5) Heat distortion temperature (HDT) Measured according to ASTM D648. Test piece shape: 5 × 1/4 × 1/2 ^t inch Load: 264 psi (6) Softening temperature (TMA) Measured by thermal deformation behavior of a 1 mm thick sheet using a Thermo Mechanical Analyzer manufactured by DuPont. That is,
Place a quartz needle on the sheet, apply a load of 49 g, and 5 ℃ /
The temperature at which the needle penetrated into the sheet by 0.635 mm after raising the temperature at the speed of min was defined as TMA. (7) Glass transition temperature (Tg) and melting point (Tm) Temperature rising rate of 10 ° C / m using DSC-20 manufactured by SEIKO Electronic Industry Co., Ltd.
Measured in. (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 IS-50EPN manufactured by Toshiba Machine Co., Ltd., injection molding was performed under the following conditions using a spiral length measuring mold (4.8 mmφ semicircle), and a spiral length of 20 cm or more The ones were evaluated as ◯, and those less than were evaluated as x.

Molding conditions: Cylinder temperature 250 ° C. Mold temperature 60 ° C. Injection pressure 1000 Kg / cm ² Delivery speed Medium speed (11) Izod impact strength Measured at 23 ° C. according to ASTM-D-256. (With notch)

[0138]

Example 1 As the component [A], the number average molecular weight was 14300 in terms of polystyrene, and the molecular weight distribution M was measured by GPC.
w / Mn = 3.46, pellets of poly-1,4- (phenylene ether) resin having an intrinsic viscosity [η] of 0.49 dl / g measured in a chloroform solvent at 23 ° C. 2.0 kg, as a [B] component Ethylene content measured by ¹ H-NMR is 61.7 mol%, MFR ₂₆₀ ^° _C. is 15 g / 10 min, 135 ° C. intrinsic viscosity [η] is 0.61 dl / g, TMA is 169 ° C. , A random copolymer of ethylene with Tg of 152 ° C (Tm is not observed) and 1,4-methano-1,4,4a, 9a-tetrahydrofluorene (hereinafter abbreviated as MTHF) (ethylene / MTHF random copolymerization). After thoroughly mixing 2.0 kg of pellets (combined), a twin-screw extruder (Ikegai Tekko KK, PCM 45
), Melt blending at a cylinder temperature of 280 ° C.,
Pelletized with a pelletizer.

Using the obtained pellets, test pieces were prepared by the above-mentioned method, and their physical properties were evaluated. The results are shown in Table 1.

[0140]

Examples 2 and 3 Compositions (pellets) were produced in the same manner as in Example 1 except that the compounding amounts of the components [A] and [B] were changed as shown in Table 1. A test piece was prepared using and the physical properties were evaluated.

The results are shown in Table 1.

[0142]

Comparative Example 1 A composition (pellet) was prepared in the same manner as in Example 1 except that a polystyrene resin was used in place of the ethylene / MTHF random copolymer used as the component [B], and this pellet was used. To create a test piece,
This physical property was evaluated.

The results are shown in Table 1.

[0144]

Comparative Example 2 A composition (pellet) was prepared in the same manner as in Example 1 except that the ethylene-MTHF random copolymer as the component [B] was not used and the component [A] was used alone.
Was manufactured, a test piece was prepared using this pellet, and its physical properties were evaluated.

The results are shown in Table 1.

[0146]

Example 4 80 parts by weight of the ethylene / MTHF random copolymer used in Example 1 was mixed with an ethylene / propylene random copolymer (soft polymer, ethylene content: 80 mol%, MFR ₂₃₀ ^° _C .: 0. Intrinsic viscosity [η] measured in decalin at 135 ° C., 7 g / 10 min, 2.2 dl / g, Tg: −5
20 parts by weight of 4 ° C.), a twin-screw extruder (PC made by Ikegai Tekko KK, PC
Melt blended with M 45). Furthermore, for 1 kg of this blended resin, an organic peroxide (NOF
(Perhexin 25B manufactured by Co., Ltd.) and divinylbenzene at a ratio of 3 g were added and mixed well. This mixture was subjected to a reaction under melting at a cylinder temperature of 230 ° C. with a twin-screw extruder (PCM 45, manufactured by Ikegai Tekko Co., Ltd.), pelletized with a pelletizer, and ethylene / MTHF random modified with divinylbenzene. Copolymer pellets were produced.

A composition (pellet) was prepared in the same manner as in Example 1, except that the ethylene-MTHF random copolymer modified with divinylbenzene prepared as described above was used in place of the component [B]. It manufactured, the test piece was created using this pellet, and this physical property was evaluated.

The results are shown in Table 1.

[0149]

Example 5 Instead of the ethylene / MTHF copolymer used as the component [B] in Example 1, ethylene and 5-phenyl-bicyclo [2.2.1] hept-2-ene (hereinafter P
hBH) and a copolymer (ethylene content: 8)
7.8 mol%, PhBH content: 12.2 mol%, intrinsic viscosity [η]: 0.67 dl / g, MFR ₂₆₀ ^° _C : 13 g / 10 min,
A composition (pellet) was produced in the same manner except that TMA: 23 ° C. and Tg: 2 ° C. were used and the mixing ratio (weight) of the [B] component and the [A] component was changed to 20/80. Then, a test piece was prepared using this pellet, and its physical properties were evaluated.

The results are shown in Table 1. Comparing this result with the result of Comparative Example 2, the composition prepared in this Example 5 showed very good toughness. That is, as compared with the result of Comparative Example 2 in which the component [A] was used alone, the tensile elongation of the composition obtained in this Example 5 was significantly improved. This tensile elongation is one of the measures of toughness,
The improved tensile elongation indicates that the toughness of the resin is improved.

[0151]

Example 6 Used as the component [B] in Example 1.
Instead of the ethylene / MTHF copolymer
PhBH random copolymer (ethylene content: 62.5 m
%, PhBH content: 37.5 mol%, intrinsic viscosity
[Η]: 0.70 dl / g, MFR₂₆₀ ^o _C: 13g / 10 minutes,
TMA: 123 ° C, Tg: 102 ° C)
The mixing ratio (weight) of the component [B] and the component [A] is 20/80.
A composition (pellet) is manufactured in the same manner except that
Then, a test piece is prepared using this pellet, and its physical properties are
evaluated.

The results are shown in Table 1.

[0153]

Example 7 80 parts by weight of the resin composition used in Example 6 was mixed with SEBS polymer (soft polymer, hydrogenated product of styrene / butadiene / styrene block copolymer, styrene content: 33).
% By weight, specific gravity 0.92, solution viscosity at 25 ° C .: 2000 cp
20 parts by weight of s (polymer concentration: 20% by weight, toluene solution) made by Shell Co., Ltd., Kraton G1651) was heated at a cylinder temperature of 2 by a twin-screw extruder (PCM 45 made by Ikegai Tekko KK).
The mixture was melt-blended at 30 ° C. and pelletized with a pelletizer. Using the obtained pellets, test pieces were prepared by the method described above, and the physical properties were evaluated.

The results are shown in Table 1. As is clear from Table 1, the mechanical properties are remarkably improved by incorporating a small amount of SEBS polymer.

[0155]

[Table 1]

Continuation of front page (51) Int.Cl. ⁵ Identification number Reference number in the office FI Technical display location C08L 65/00 LNY 8215-4J (72) Inventor Moriya Satoru 1 Gowaki, Waki-cho, Yamaguchi Prefecture No. 2 Mitsui Petrochemical Industry Co., Ltd. (72) Inventor Akira Todo 6 1-2 1-2 Waki, Waki Town, Kuga District, Yamaguchi Prefecture Mitsui Petrochemical Industry Co., Ltd.

Claims (3)

[Claims] 1. A copolymer of [A] a polyphenylene ether resin and / or a poly (substituted phenylene ether) resin, [B] an ethylene and a cyclic olefin represented by the following formula [I], and a cyclic olefin: A cyclic olefin system having an intrinsic viscosity [η] of 0.05 to 10 dl / g and a softening temperature (TMA) of 0 ° C. or higher measured in decalin at 135 ° C. selected from the group consisting of ring polymers and hydrogenated products thereof. A resin and a polyphenylene ether resin composition in a weight ratio within a range of 98/2 to 2/98; [In the formula [I], p and q are 0 or an integer of 1 or more, m and n are 0, 1 or 2, and R ^{1 to} R ^1
19 independently represents an atom or a group selected from the group consisting of a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group and an alkoxy group, and R ⁹ and R ¹³ or R ¹⁰ and R ¹¹ may be bonded directly or via an alkylene group having 1 to 3 carbon atoms, and when n = m = 0, R ¹⁵ and R ¹² or R ¹⁵ and R ¹⁹ and May combine with each other to form a monocyclic or polycyclic aromatic ring]. 2. A copolymer of [A] polyphenylene ether resin and / or poly (substituted phenylene ether) resin, [B] ethylene and a cyclic olefin represented by the following formula [I], and a cyclic olefin copolymer. A cyclic olefin system having an intrinsic viscosity [η] of 0.05 to 10 dl / g and a softening temperature (TMA) of 0 ° C. or higher measured in decalin at 135 ° C. selected from the group consisting of ring polymers and hydrogenated products thereof. The resin and the [C] soft polymer are contained, the blending weight ratio of [A] / [B] is in the range of 98/2 to 2/98, and ([A] + [B]) / [ The compounding weight ratio of C] is in the range of 95/5 to 50/50, and a polyphenylene ether-based resin composition; [In the formula [I], p and q are 0 or an integer of 1 or more, m and n are 0, 1 or 2, and R ^{1 to} R ^1
19 independently represents an atom or a group selected from the group consisting of a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group and an alkoxy group, and R ⁹ and R ¹³ or R ¹⁰ and R ¹¹ may be bonded directly or through an alkylene group having 1 to 3 carbon atoms, and when n = m = 0, R ¹⁵ and R ¹² or R ¹⁵ and R
¹⁹ may combine with each other to form a monocyclic or polycyclic aromatic ring]. 3. The polyphenylene ether resin composition according to claim 2, wherein the soft polymer is a styrene soft polymer.