JP2945992B2 - Heat resistant resin composition - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a novel polyphenylene ether resin composition excellent in heat resistance, thin-wall molding processability, and impact resistance.

(Prior art and problems) Polyphenylene ether (hereinafter referred to as PPE) has excellent mechanical properties, electrical properties, heat resistance, and transparency, but has a high melt viscosity during heating and is difficult to mold. There is a problem that there is.

U.S. Patent No.
No. 3,383,435 describes that PPE and a styrene-based polymer
PS) is shown. If PS is blended to a level where sufficient moldability is obtained by this method, a new problem arises in that the heat resistance of PPE is greatly reduced and the mechanical properties such as impact strength and tensile strength are also significantly reduced. I do.

JP-A-47-3136 discloses improvement of elastic modulus, tensile strength and hardness by adding a high melting point hydrocarbon resin.

JP-A-58-129051 discloses that a composition comprising PPE, an impact modifier and a low molecular weight hydrocarbon resin has a low melt viscosity, a high heat deflection temperature and an impact strength. However, it does not include the improvement of PPE itself, and its effect is insufficient.

On the other hand, many methods have been proposed for grafting a styrene compound to PPE to graft a high molecular weight PS to PPE to improve processability (for example, JP-B-52-38596 and JP-B-59-11605). . In order to accelerate the grafting reaction of styrene onto the PPE chain, these compounds regulate the amount of styrene, reaction temperature, mixing conditions, etc. in the presence of a radical generator to promote the grafting reaction of high molecular weight PS onto the PPE chain. ing.

Further, JP-A-63-152628 discloses that PPE is converted to carbon-
There has been proposed a method of producing a PPE having excellent color tone by melt-kneading at a temperature equal to or higher than the glass transition temperature of the PPE in the presence of a compound having a carbon double bond in the absence of a radical generator.

Also, JP-A-63-108059 discloses that the fluidity of PPE,
For the purpose of improving the oxidation stability, a composition comprising a reaction product of a specific compound having a carbon-carbon double bond and PPE is disclosed.

Although the processability of PPE is improved by these methods, it is not at a satisfactory level. In particular, in applications where thin wall formability is required, improvement is still required.

(Means for solving the problem) Under these circumstances, the moldability, thermal stability,
As a result of intensive research on heat-resistant resin with excellent impact resistance,
This has led to the present invention.

That is, the present invention comprises: (I) an average of 0.01 or more cyclized terminal groups represented by the following general formula (a) based on 100 phenylene ether units constituting the resin and 100 general formulas (a '). A polyphenylene ether resin having a number average molecular weight in the range of 1,000 to 100,000, and (II) an aromatic petroleum resin, a hydrogenated terpene resin, a cumarone-indene resin, and a cyclopentadiene resin. Styrene resin, cyclopentadiene-indene resin, phenol-
Coumarone-a low molecular weight hydrocarbon resin having a number average molecular weight of 500 to 2700 selected from indene resin or a mixture thereof 40 to 40
A heat-resistant resin composition comprising 1% by weight. Also, (In the formula, R _{1 to} R ₅ and R ₁₂ are each independently hydrogen, carbon 1
To 20 alkyl groups, substituted alkyl groups (substituents are halogen, hydroxyl group, amino group, lower alkoxy group), halogen groups, aryl groups having 6 to 20 carbon atoms or substituted aryl groups (substituents are lower alkyl groups , A halogen, a hydroxyl group, an amino group, or a lower alkoxy group), and R _{6 to} R ₉ are each independently hydrogen, an alkyl group having 1 to 20 carbon atoms, or a substituted alkyl group (substituents are halogen, hydroxyl group , An amino group or a lower alkoxy group), a lower alkenyl group, a substituted alkenyl group such as 1-hydroxy-3-propenyl, a halogen group, an aryl group having 6 to 20 carbon atoms,
Substituted aryl group (substituent is lower alkyl group, halogen,
A hydroxyl group, an amino group, a lower alkoxy group), an alkoxy group, an N-lactam group, a carboxylic acid group,
It is a carboxylic anhydride group, a carboxylic ester group, a carboxylic amide group, a nitrile group, an acyloxy group or an acyl group.

R ₆ and R ₇ , and R ₈ and R ₉ may be independently bonded to each other to form a ring having a spiro ring structure. R ₆ and R ₈ are a methyl group or hydrogen, R ₇ and R ₈ are not simultaneously a methyl group, and R ₁ and R ₈ are hydrogen or an ester residue having 3 to 18 carbon atoms. It is a carboxylate group which is a hydrocarbon group, and is characterized in that R ₇ and R ₉ are not simultaneously a carboxylate group. The carboxylic acid ester group described above is characterized in that the ester residue is a stearyl group.

In other words, the present inventors have improved thermal processing and impact resistance by combining a specific low-molecular-weight hydrocarbon resin with PPE having a specific structure whose molding processability and thermal stability have been improved. Workability is greatly improved, and PP
E The present inventors have found that a composition maintaining the original heat resistance can be obtained, and have reached the present invention.

In the polyphenylene ether resin used in the present invention, the cyclized terminal group represented by the general formula (a) is added on average to 0.01 per 100 phenylene ether units constituting the resin.
It is necessary to contain more than one.

When the average molecular weight is such that it is used as an engineering resin (about 10,000 to 30,000), the number of cyclized terminal groups is preferably 0.15 or more on average per 100 phenylene ether units. More preferably, the average is 0.2 or more.

There is no particular upper limit, and the larger the number, the more preferable in terms of thermal oxidation deterioration.

This polyphenylene ether resin generally has a repeating unit excluding its terminal group. The phenylene ether unit is defined as containing a phenylene ether unit, and is not particularly limited. A typical example is the following formula (b): (Wherein, R _{1 to} R ₅ are each independently hydrogen, an alkyl group having 1 to 20 carbon atoms, a substituted alkyl group (substituents are halogen, hydroxyl, amino, lower alkoxy), halogen groups And at least one phenylene ether unit represented by the formula: wherein the substituent is selected from a lower alkyl group, a halogen, a hydroxyl group, an amino group and a lower alkoxy group.
Consists of seeds.

When the basic skeleton of such a polyphenylene ether resin is produced by oxidative coupling polymerization of an industrially advantageous phenol, R ₁ is a lower alkyl group such as methyl, ethyl, propyl, isopropyl, n-butyl or phenyl. , Naphthyl and the like are preferable, and R _{2 to} R ₅ are preferably hydrogen or a lower alkyl group.

The most preferred combination is when R ₁ is a methyl group or a phenyl group and R _{2 to} R ₅ are hydrogen, when R ₁ and R ₂ are a methyl group and R _{3 to} R ₅ are hydrogen. In particular, it is preferable that R ₁ is a methyl group, R _{2 to} R ₅ are hydrogen, and the phenylene ether unit accounts for 90 to 100% of all units.

The most preferable monomers corresponding to the phenylene ether unit having R _{1 to} R ₅ satisfying these conditions include (i) 2,6-dimethylphenol, (ii) 2-methyl-6-phenylphenol, and (iii) 2 , 3,6-trimethylphenol and the like. A homopolymer of the monomer (i) or the monomer (ii), or a copolymer of the monomer (i) with the monomer (ii) and / or the monomer (iii) is preferably used as the polyphenylene ether polymer as the resin basic skeleton of the present invention. .

Further, in the polyphenylene ether resin of the present invention,
As long as it does not contradict the purpose of improving the thermal stability, various other phenylene ether units which have been conventionally proposed to be allowed to exist in the polyphenylene ether resin may be included as a partial structure. Japanese Patent Application No. 63-12 / 1988 describes an example of a proposal to coexist in a small amount.
No. 698 and JP-A-63-301222,
Examples thereof include a 2- (dialkylaminomethyl) 6-methylphenylene ether unit and a 2- (N-alkyl-N-phenylaminomethyl) 6-methylphenylene ether unit.

Also included are polyphenylene ether resins in which a small amount of diphenoquinone or the like is bonded in the main chain.

The molecular weight of the polyphenylene ether resin used in the present invention is 1,000 to 100,000 in number average molecular weight.
The preferred range is about 6,000 to 60,000. Especially,
Approximately 1
It is a thing of 0,000-30,000. In addition, the number average molecular weight of the present invention is a number average molecular weight in terms of polystyrene obtained by gel permeation chromatography using a calibration curve of standard polystyrene.

In the cyclized terminal group (a) of the polyphenylene ether resin used in the present invention, R _{1 to} R ₅ each independently represent hydrogen, an alkyl group having 1 to 20 carbon atoms, or a substituted alkyl group (substituent is halogen, hydroxyl group , An amino group or a lower alkoxy group), a halogen group, an aryl group having 6 to 20 carbon atoms or a substituted aryl group (the substituent is a lower alkyl group, a halogen, a hydroxyl group, an amino group or a lower alkoxy group). And R _{6 to} R ₉ each independently represent hydrogen, an alkyl group having 1 to 20 carbon atoms, a substituted alkyl group (substituents are halogen, hydroxyl, amino, lower alkoxy), lower alkenyl, 1- Substituted alkenyl groups such as hydroxy-3-propenyl, halogen groups, aryl groups having 6 to 20 carbon atoms, substituted aryl groups (substituents are lower alkyl groups, halogen, hydroxyl groups; Amino group, a lower alkoxy group),
It is an alkoxy group, N-lactam group, carboxylic acid group, carboxylic acid anhydride group, carboxylic acid ester group, carboxylic acid amide group, nitrile group, acyloxy group or acyl group.
Incidentally, R ₆ , R ₇ , R ₈ and R ₉ are each independently, the terminal is free or R ₆ and R ₇ , R ₈ and R ₉ are each independently bonded to form a spiro ring structure. A ring may be formed.

In the above definitions of R _{1 to} R ₅ , the alkyl group has 1 to 1 carbon atoms.
20, preferably alkyl having 1 to 10 carbon atoms. Examples of the substituent of the substituted alkyl include a halogen such as fluorine, chlorine, and bromine; a hydroxyl group; an amino group; and a lower alkoxy group. Aryl is aryl having 6 to 20 carbon atoms. Examples of the substituent of the substituted aryl include a lower alkyl group; halogen such as fluorine, chlorine, and bromine; a hydroxyl group; an amino group; and a lower alkoxy group.

In the definition of R _{6 to} R ₉ , the alkyl group has 1 to 20 carbon atoms,
Preferably it is 1-10 alkyl, more preferably lower alkyl. Examples of the substituent of the substituted alkyl include a halogen such as fluorine, chlorine, and bromine; a hydroxyl group; an amino group; and a lower alkoxy group.
Alkenyl is preferably lower alkenyl such as ethylenyl and 3-propenyl. Representative examples of substituted alkenyl are
1-hydroxy-3-propenyl. Aryl is aryl of 6 to 20 carbons. Examples of the substituent of the substituted aryl include a lower alkyl group; a lower alkoxy group; a halogen such as fluorine, chlorine, and bromine; a hydroxyl group; an amino group;
An aminoalkyl group such as an aminomethyl group can be mentioned.

The aryl group means an aromatic ring group in a broad sense, and includes, in addition to aryl in a narrow sense, a heteroaromatic ring group such as a pyridyl group and a triazyl group. A typical example of N-ratatum is N-2
-Pyrrolidonyl, N-ε-caprolactamyl and the like. Representative examples of carboxylic acid amides include carbamoyl, phenylcarbamoyl, seryl, and the like.
Preferred examples of the carboxylic anhydride are acetoxycarbonyl and benzoyloxycarbonyl. Representative examples of carboxylic esters include methoxycarbonyl, ethoxycarbonyl, allyloxycarbonyl, and the like. Representative examples of the acyl group include acetyl and benzoyl, and preferred examples of acyloxy include acetoxy and benzoyloxy.

As for R _{6 to} R ₉ , it is preferable from the viewpoint of stability that two to three, particularly three of them are hydrogen. In this case, the other group is preferably selected from an aryl group, a substituted aryl group, a carboxylic acid group, a carboxylic acid anhydride group, a carboxylic acid ester group, a carboxylic acid amide group, a nitrile group, and an N-lactam group. In particular, the case where at least one of R ₈ and R ₉ is an aryl group or an aryl group is preferable from the viewpoint of stability against thermal oxidative deterioration and the production method described later.

Representative examples of aryl or substituted aryl groups in the definitions of R _{6 to} R ₉ include phenyl, tolyl, chlorophenyl, naphthyl, 4-pyridyl, 3,5-diamino- (s)
-A triazyl group or the like.

The structure and amount of such a cyclized terminal group can be measured using a nuclear magnetic resonance spectrum. Since the polyphenylene ether resin having the cyclized terminal group (a) has the cyclized terminal group, when it is melted (molded), the formation of the transition structure represented by the following general formula (e) is smaller than that of the conventional polyphenylene ether resin. It has excellent properties such that the molecular weight does not substantially change in addition to the extremely small amount.

(Wherein, R _{1 to} R ₅ are each independently hydrogen, an alkyl group, a substituted alkyl group, a halogen group, an aryl group or a substituted aryl group.) The stabilized polyphenylene ether resin is produced as follows. can do.

That is, general formula (c); (Wherein, R _{1 to} R ₅ are the same as defined in the formula (a), and R ₁₀ and R ₁₁ each independently represent hydrogen, an alkyl group, or a substituted alkyl group, but they are both hydrogen. The polyphenylene ether polymer having a terminal group represented by the general formula (d): (Wherein, R _{6 to} R ₉ are the same as those defined in the formula (a).) A compound having a carbon-carbon double bond (hereinafter referred to as an unsaturated compound) represented by the following formula: It can be produced by heating to a temperature higher than the glass transition temperature of the polyphenylene ether polymer in the absence.

The alkyl group or substituted alkyl group in R ₁₀ and R ₁₁ in the formula (c), preferably a (C ₁ -C ₂₀ ) alkyl group, (C ₁ -C ₂₀ )
₂₀₎ hydroxy group, (C ₂ ~C ₂₂₎ alkoxyalkyl group, (C ₃ ~C ₂₂₎ acyloxyalkyl group or a (C ₄
To C ₂₀ ) a polyalkylene ether group.

The polyphenylene ether having such a terminal group (c) can be prepared by oxidative coupling polymerization or co-polymerization of a phenol compound having at least one benzylic hydrogen at the ortho position of a hydroxyl group in the presence of a catalyst containing a primary or secondary amine. It is obtained by polymerization (for example, US Pat. No. 4,788,277).

In this case, the obtained polymer is obtained as a mixture of a polyphenylene ether having a terminal group represented by the general formula (c) and a polyphenylene ether having a terminal structure in which a primary or secondary amine is not bonded at a benzyl position. However, in the present invention, it can be used without separation. The use ratio of the former and the latter is not particularly limited, but is preferably 0.4 or more, particularly preferably 0.9 or more, as expressed by the ratio of the number of terminal groups of the former / the number of terminal groups of the latter.

The amount of the reaction between the polyphenylene ether having a terminal group represented by the general formula (c) and the unsaturated compound represented by the general formula (d) in the present invention is preferably represented by the general formula (c) The unsaturated compound of the general formula (d) may be used in an amount of about 2 to 50 equivalents to the polyphenylene ether having a terminal group.

When the stabilized polyphenylene ether resin of the present invention is produced, as the unsaturated compound (d), R ₈ and / or R ₈ are used in order to stabilize the generated intermediate radical (f), for example, in the form of biradil (g). Alternatively, R ₉ is preferably an aryl or substituted aryl group.

Preferred specific examples of the unsaturated compound (d) include styrene, α-methylstyrene, chlorostyrene, methylstyrene, stilbene, cinnamon alcohol, benzalacetone, ethyl cinnamate, nitrile cinnamate, and 4-vinylpyridine , 2-vinyl-3,5-diamino- (s) -triazine and the like.

As the unsaturated compound (d), a compound containing no aromatic ring can be used. Specific examples of such unsaturated compounds (d) include acrylic acid; methyl, ethyl, propyl, butyl, isobutyl, t-butyl,
-Ethylhexyl, octyl, isodecyl, lauryl,
Acrylic esters such as lauryl-tridecyl, tridecyl, cetyl-stearyl, stearyl, cyclohexyl, benzyl ester; acrylamide, acrylonitrile, methacrylic acid; methyl methacrylate, ethyl,
Methacrylic esters such as propyl, butyl, isobutyl, t-butyl, 2-ethylhexyl, octyl, isodecyl, lauryl, lauryl-tridecyl, tridecyl, cetyl-stearyl, stearyl, cyclohexyl, benzyl ester; methallylamide, methacrylonitrile, itacone Acids; itaconic acid dimethyl, diethyl,
Itaconic acid diesters such as dibutyl, di-2-ethylhexyl, dinolyl, dioctyl ester; itaconic acid monoesters such as itaconic acid monomethyl, monoethyl, monobutyl, mono-2-ethylhexyl, mononolyl, monooctyl ester; itaconic anhydride N-vinyl compounds such as N-vinylpyrrolidone; vinyl ethers such as butyl vinyl ether;

In the production of the stabilized polyphenylene ether resin of the present invention, a polyphenylene ether-based polymer is used.
Before heating to a glass transition temperature of 180 ° C. or higher, it is preferable to mechanically mix with the unsaturated compound (d).

The method of mixing is not particularly limited, but a method of dry blending with a Henschel mixer or the like, a method of drying after melt blending, a method of dissolving unsaturated compound (d) in polyphenylene ether but dissolving unsaturated compound (d), for example, After dissolving in a solvent such as methanol or pentane and impregnating the polyphenylene ether-based polymer having a terminal group (c) in the form of powder, a method of drying and removing the solvent may be used.

The polyphenylene ether-based polymer and the unsaturated compound (d) mechanically mixed as described above are then mixed with the glass transition temperature of the polyphenylene ether-based polymer (about 208
℃) or more. A preferred temperature range is 20-150 ° C above the glass transition temperature, more preferably 5 ° C.
0-120 ° C. Although the heating time cannot be unconditionally determined in relation to the temperature, the heating may be carried out for a time sufficient for completing the desired reaction. Generally, it is about 1 minute to 1 hour, preferably about several minutes. There is no point in making it too long.

Since the reaction for forming the cyclized terminal group (a) is usually sufficiently fast at a temperature higher than the glass transition temperature, it is better not to apply unnecessary heat excessively. Further, as described above, the heating needs to be performed in the absence of the radical polymerization initiator.

Examples of the low molecular weight hydrocarbon resin used in the present invention include an aromatic petroleum resin obtained by polymerizing an unsaturated hydrocarbon mixture in cracked naphtha obtained by cracking petroleum, and an unsaturated polycyclic unsaturated compound formed by dry distillation of coal. Coumarone-indene resins derived from hydrocarbon mixtures, other hydrogenated terpene resins, cyclopentadiene-styrene resins, cyclopentadiene-indene resins, phenol-coumarone-indene resins and mixtures thereof are used.

The blending ratio of the stabilized polyphenylene ether containing a specific cyclized end group and the low molecular weight hydrocarbon resin is 60%.
~ 99% by weight / 40-1% by weight is suitable. Preferably 75
-98% by weight / 25-2% by weight, more preferably 85-97% by weight / 15-3% by weight.

Such a composition can be prepared by blending and extruding and granulating the polyphenylene ether resin containing a cyclized terminal group simultaneously with or after the production.

A vinyl aromatic resin may be added to this composition as long as the characteristics are not impaired.

Examples of the vinyl aromatic resin include a homopolymer of styrene and a copolymer with another ethylenically unsaturated monomer as long as the compatibility of the composition is not impaired.

Examples of specific comonomers include α-methylstyrene, acrylonitrile, methacrylonitrile, acrylates, methacrylates, maleic anhydride, N-alkylmaleimides, N-arylmaleimides, vinyloxazoline and the like. is there.

Further, a polystyrene-based polymer containing a rubber-like elastic material, a styrene-butadiene-based block copolymer, a duylene-isoprene-based block copolymer, and a hydrogenated additive thereof may be used.

In addition to the above, the resin composition of the present invention can be used by appropriately adding an inorganic filler such as glass fiber, various stabilizers, a plasticizer, a flame retardant, a pigment, and the like according to a known method.

(Examples) Hereinafter, the present invention will be described specifically with reference to Examples.
The present invention is not limited by these examples.

 In addition, each measurement was performed on condition of the following.

Polymer viscosity: 0.5% chloroform solution was measured at 30 ° C. using an Ubbelohde viscosity tube and expressed as ηsp / c.

¹ H-nuclear magnetic resonance spectrum: Measured by using CDCl ₃ as a solvent with GX-270 manufactured by JEOL Ltd. and using tetramethylsilane as a standard.

Gel permeation chromatography (GP
C): Measured with HL-802RTS manufactured by Toyo Soda Kogyo Co., Ltd.

As a calibration curve in GPC, one prepared using standard polystyrene is used.

Free phenolic OH groups in the polymer; measured according to the method of EHUD SHCHORI and the like [described in Journal of Applied Polymers Science; Applied Polymer Symposium, 34, 103-117, (1978)].

 Melt flow rate: Measured at 280 ° C under a load of 10 kg.

Heat distortion temperature: Measured under a load of 18.6 kg / cm ² according to ASTM D-648.

Thin-wall formability: A 1.6-mm-thick tansack-type test piece (127 mm x 127 mm) is formed and measured at a forming pressure required for full shot.

 The lower the molding pressure, the better the thin-wall moldability.

 Izod impact strength; measured according to ASTM D-256.

Examples 1 and 2 and Comparative Example 1 The raw material polyphenylene ether was prepared according to US Pat.
According to the method described in the specification of Japanese Patent Application No. 7 (Japanese Patent Application No. 62-77070), 2,6-xylenol is produced by oxidative coupling polymerization in the presence of dibutylamine.

The resulting polyphenylene ether has a viscosity of 0.545 and a glass transition temperature of about 208 ° C. As a result of analysis by ¹ H-nuclear magnetic resonance spectrum, formula (i): It is confirmed that there are 0.32 terminal groups per 100 main repeating units (h) below.

It is also confirmed that the amount of free phenolic hydroxyl groups is 0.34 per 100 main repeating units (h).

After adding 10 parts by weight of styrene to 100 parts by weight of this polyphenylene ether and uniformly blending with a Henschel mixer, the screw diameter is 30 mmφ in a twin-screw extruder (PCM-30 manufactured by Ikegai Iron Works Co., Ltd.). Melt and knead at 300 ° C and pelletize through a water bath.

As a result of analyzing the pellet thus obtained by ¹ H-nuclear magnetic resonance spectrum, the following formula (j) was obtained; Of the main repeating unit (h)
The presence of 0.25 is confirmed from the signal area value of 5.02 ppm.

It is also confirmed that the amount of free phenolic hydroxyl groups is 0.45 per 100 main repeating units (h). The number average molecular weight determined by GPC is 24,500, and the viscosity is 0.547.

The terminally cyclized polyphenylene ether pellets and an aromatic petroleum resin (Neopolymer 170 S: Mw = 2700 manufactured by Nippon Petrochemical) as a low molecular weight hydrocarbon resin were mixed at the ratio shown in Table 1, and again mixed in a twin screw extruder. At 300 ° C. and pelletized.

This pellet is injected into an injection molding machine (IS80EP manufactured by Toshiba Machine Co., Ltd.)
The sample was molded at 330 ° C. under N) to prepare a test piece, which was evaluated.

As a comparative example, a case where no aromatic petroleum resin was added was also performed. Table 1 shows the results.

The compositions of Examples 1 and 2 have excellent heat resistance and thin moldability.

Comparative Example 2 A polyphenylene ether having the same terminal group (i) as used in Example 1 was prepared, except that styrene was not used.
Extruded into pellets under the same conditions.

 The results of analysis of the pellets are as follows.

Number average molecular weight 26,000 Melt viscosity (ηsp / c) 0.672 Free phenolic OH group 0.58 Further, the pellets were made into a composition exactly as in Example 1 and evaluated. Table 2 shows the results.

The combination of ordinary polyphenylene ether and aromatic petroleum resin is inferior in thin-wall moldability.

Examples 4 to 6 In the compositions of Examples 1 and 2, except that a hydrogenated terpene resin (Clearon P125: Mn = 700, manufactured by Yasuhara Yushi Kogyo Kogyo Co., Ltd.) was used as the low molecular weight hydrocarbon resin, the compositions were evaluated and evaluated in exactly the same manner. .

 Table 3 shows the evaluation results.

(Effect of the Invention) In the present invention, by blending a modified stabilized polyphenylene ether and a low-molecular-weight hydrocarbon resin, excellent heat resistance and impact resistance are maintained, and furthermore, unprecedented thin-wall moldability is obtained. A unique polyphenylene ether-based resin composition having the following is obtained.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification symbol FI C08L 57:02) (C08L 71/12 45:02) (56) References JP-A-2-276823 (JP, A) JP JP-A-62-257958 (JP, A) JP-A-59-230053 (JP, A) JP-A-3-86756 (JP, A) JP-A-51-73560 (JP, A) JP-A-58-129051 (JP, A) JP-A-61-233056 (JP, A) JP-B-7-76296 (JP, B2) JP-T-63-500803 (JP, A) JP-T-55-500636 (JP, A) (58) Surveyed fields (Int.Cl. ⁶ , DB name) C08L 71/00-71/14 C08L 65/00-65/04 C08G 65/00-65/48

Claims (3)

(57) [Claims] (I) An average of 0.01 or more cyclized terminal groups represented by the following general formula (a) per 100 phenylene ether units constituting a resin, represented by the general formula (a '): A polyphenylene ether resin having a number average molecular weight in the range of 1,000 to 100,000, 60 to 99% by weight, and (II) an aromatic petroleum resin, a hydrogenated terpene resin, a cumarone-indene resin, and cyclopentadiene-styrene. resin,
A heat-resistant resin composition comprising 40 to 1% by weight of a low molecular weight hydrocarbon resin having a number average molecular weight of 500 to 2700 selected from cyclopentadiene-indene resin, phenol-coumarone-indene resin or a mixture thereof. . (In the formula, R _{1 to} R ₅ and R ₁₂ are each independently hydrogen, carbon 1
To 20 alkyl groups, substituted alkyl groups (substituents are halogen, hydroxyl group, amino group, lower alkoxy group), halogen groups, aryl groups having 6 to 20 carbon atoms or substituted aryl groups (substituents are lower alkyl groups , A halogen, a hydroxyl group, an amino group, or a lower alkoxy group), and R _{6 to} R ₉ are each independently hydrogen, an alkyl group having 1 to 20 carbon atoms, or a substituted alkyl group (substituents are halogen, hydroxyl group , An amino group or a lower alkoxy group), a lower alkenyl group, a substituted alkenyl group such as 1-hydroxy-3-propenyl, a halogen group, an aryl group having 6 to 20 carbon atoms,
Substituted aryl group (substituent is lower alkyl group, halogen,
A hydroxyl group, an amino group, a lower alkoxy group), an alkoxy group, an N-lactam group, a carboxylic acid group,
It is a carboxylic anhydride group, a carboxylic ester group, a carboxylic amide group, a nitrile group, an acyloxy group or an acyl group. R ₆ and R ₇ , and R ₈ and R ₉ may be independently bonded to each other to form a ring having a spiro ring structure. ) Wherein R ₆ and R ₈ is a methyl group or hydrogen, and R ₆
R ₈ is not a methyl group at the same time, R ₇ and R ₉ are hydrogen,
The heat resistance according to claim 1, wherein the ester residue is a carboxylate group having a hydrocarbon group having 3 to 18 carbon atoms, and R ₇ and R ₉ are not simultaneously a carboxylate group. Resin composition. 3. The heat-resistant resin composition according to claim 1, wherein the ester residue of the carboxylic acid ester group according to claim 2 is a stearyl group.