JPH09165508A - Polyphenylene ether resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject composition comprising a specific resin (mixture) and a rosin (ester), excellent in melt flowability, moldability and heat resistance, and useful for moldings requiring good rigidity, heat resistance and dimensional stability, such as automotive parts and electronic or electric parts. SOLUTION: This resin composition comprises (A) 1-100 pts.wt. of a polyphenylene ether resin such as a polymer of the formula [R1 -R4 are each H, an alkyl, an alkoxy, a halogen, phenyl; (n) is a polymerization degree,] (B) 99-0 pts.wt. of a polystyrene resin, and (C) (C1 ) a purified stable rosin having a Gardner color scale of <=2, especially <=1, or (C2 ) a rosin ester compound obtained from the component C1 and an alcohol compound or epoxy compound (e.g. having an aromatic ring) preferably in an amount of 0.1-50 pts.wt. per 100 pts.wt. of the total amount of the components A and B.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a polyphenylene ether resin composition.

[0002]

2. Description of the Related Art Polyphenylene ether resins are excellent in various properties such as heat resistance and rigidity, and are attracting attention as engineering plastics. However, because of their high melt viscosity, they require high temperatures for melt molding. However, various problems such as discoloration, oxidation and deterioration occur. Therefore, conventionally, polyphenylene ether resins have been put to practical use as a composition in which a polystyrene resin is blended to improve molding processability (for example, US Pat. No. 3,383,435). However, it is difficult to say that the melt fluidity of a resin composition containing such a polystyrene resin is sufficient.

Therefore, various measures have been taken in order to improve the melt fluidity of the polyphenylene ether resin composition. For example, JP-A-55-118956, JP-B-57-13584 and JP-A-58-12.
9050, JP-A-58-129051, JP-A-59-126460, JP-A-47-3136.
Japanese Patent Laid-Open Publication No. 2003-242242 discloses that low molecular weight hydrocarbon resin such as rosin, aromatic petroleum resin, cyclopentadiene resin, aromatic / cyclopentadiene copolymer resin or coumarone-indene resin is added to polyphenylene ether resin. It has been proposed and improvements in melt flowability are observed. However, the addition of the low molecular weight hydrocarbon resin has a drawback that the heat resistance originally possessed by the obtained polyphenylene ether resin cannot be satisfied.

[0004]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a polyphenylene ether resin composition having excellent melt fluidity, moldability and heat resistance.

[0005]

Means for Solving the Problems As a result of intensive studies to solve the above-mentioned problems of the prior art, the present inventors have found that a composition comprising a polyphenylene ether-based resin and a polystyrene-based resin has a specific rosin group. The present invention has been completed by finding that a composition obtained by adding rosin ester and / or rosin ester meets the above-mentioned object.

That is, the present invention provides 1 to 100 parts by weight of a polyphenylene ether resin (A) and 99 to 0 parts by weight of a polystyrene resin (B), and a purified and stabilized rosin having a Gardner color tone of 2 or less, or the purified and stable rosin. The present invention relates to a polyphenylene ether-based resin composition comprising a rosin ester (C) comprising a modified rosin and an alcohol compound and / or an epoxy compound.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The polyphenylene ether resin (A) (hereinafter referred to as the component (A)) used in the present invention is not particularly limited and various known resins can be used. For example, general formula (1):

[0008]

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(Wherein R ¹ , R ² , R ³ and R ⁴ are each independently a hydrogen atom, an alkyl group, an alkoxy group,
A polymer represented by a halogen atom or phenyl, and n is an integer representing the degree of polymerization.

The method for producing the polymer represented by the above general formula (1) is not particularly limited, and for example, US Pat.
The phenols may be reacted according to the method described in US Pat. No. 4, U.S. Pat. No. 3,257,357 or US Pat. No. 3,257,358. As phenols,
For example, 2,6-dimethylphenol, 2,6-diethylphenol, 2,6-dipropylphenol, 2,
6-dibutylphenol, 2,6-dilaurylphenol, 2,6-diphenylphenol, 2-methyl-6-
Ethylphenol, 2-methyl-6-cyclohexylphenol, 2-methyl-6-tolylphenol, 2-methyl-6-methoxyphenol, 2-methyl-6-butylphenol, 2,6-dimethoxyphenol, 2,
Examples include 3,6-trimethylphenol, 2,3,5,6-tetramethylphenol, 2,6-diethoxyphenol and the like. The polymer represented by the general formula (1) is
The phenol may be a polymer of one kind alone or a copolymer of two or more kinds combined.

As a preferred specific example of the polymer represented by the above general formula (1), R ¹ and R ² have 1 to 4 carbon atoms.
An alkyl group or a phenyl group of R ³ and R ^3
4 is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. For example, poly (2,6-dimethyl-
1,4-phenylene) ether, poly (2,6-diethyl-1,4-phenylene) ether, poly (2-methyl-6-ethyl-1,4-phenylene) ether, poly (2-methyl-6-) Propyl-1,4-phenylene) ether, poly (2,6-propyl-1,4-phenylene) ether, poly (2-ethyl-6-propyl-1,
4-phenylene) ether, poly (2,6-diphenyl-1,4-phenylene) ether and the like can be mentioned. Further, a copolymer containing a part of alkyl tri-substituted phenol, for example, 2,3,6-trimethylphenol in the polyphenylene ether repeating unit may be used.

Further, as the component (A) in the present invention,
A copolymer obtained by grafting a styrene compound on the polymer represented by the general formula (1) can also be used. Specific examples of the grafted polyphenylene ether include various copolymers obtained by graft-polymerizing styrene compounds such as styrene, α-methylstyrene, vinyltoluene, and chlorostyrene as the polyphenylene ether resin. To be

The weight average molecular weight of the component (A) is not particularly limited, but usually the weight average molecular weight is 100.
0-300000, preferably 1000-1000
00 and an intrinsic viscosity of about 0.005 to 3 dl / g (chloroform, 25 ° C.), preferably 0.005 to 1 d
1 / g.

Polystyrene resin (B) used in the present invention
There is no particular limitation on (hereinafter referred to as the component (B)), and various known ones can be used. For example, general formula (2):

[0015]

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(Wherein R ⁵ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R ⁶ represents a halogen atom or an alkyl group having 1 to 4 carbon atoms, and p represents an integer of 0 to 5) , And q is an integer representing the degree of polymerization),
Those having at least 25% by weight in the polymer of repeating structural units derived from an aromatic vinyl compound.

More specifically, examples of the component (B) include aromatic vinyl compounds such as styrene, vinyltoluene, α-methylstyrene, α-methyl-p-methylstyrene, chlorostyrene and bromostyrene. A homopolymer using one kind or a copolymer combining two or more kinds, or a polymer of the aromatic vinyl compound as a homopolymer of a conjugated diene compound such as butadiene, isoprene or chloroprene, or a conjugated diene compound. Examples thereof include copolymers with unsaturated nitrile compounds or aromatic vinyl compounds, and those modified with various rubber components such as natural rubber. In the present invention, among the specific examples of the component (B), polystyrene or rubber-reinforced polystyrene containing 70% by weight or more of styrene and 30% by weight or less of diene rubber is preferable. The component (B) may be any one obtained by any of emulsion polymerization, suspension polymerization, bulk polymerization and solution polymerization.

The weight average molecular weight of the component (B) is not particularly limited, but usually the weight average molecular weight is 100.
It is about 0 to 1,000,000.

In the present invention, as described above, (A)
Use of a specific rosin and / or a specific rosin ester (C) (hereinafter referred to as the component (C)) for the purpose of improving the melt flowability of the resin composition comprising the component and the component (B) Is required. The rosin of the component (C) means a Gardner color tone of 2 or less, preferably 1
The following purified and stabilized rosin, and specific examples thereof include purified and stabilized rosin obtained by distilling a stabilized rosin such as disproportionated rosin, hydrogenated rosin and dehydrogenated rosin to remove unsaponifiable matters and impurities. Class is applicable. More specifically, JP-A-63-186783, JP-A-64-85265, JP-A-3-277675, and JP-A-5-17.
Various examples described in Japanese Patent Application Laid-Open No. 1112 and Japanese Patent Application Laid-Open No. 5-2716222 can be exemplified.

Examples of the rosin ester of the component (C) include various reaction products composed of the following alcohol compound and / or epoxy compound and the purified and stabilized rosin. The rosin ester has a Gardner color tone of 2 or less, preferably 1 or less.

The alcohol compound is not particularly limited and various known polyhydric alcohols can be used. For example,
Ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propanediol, 1,3-
Propanediol, 1,3-butanediol, 1,4-
Butanediol, neopentyl glycol, pentanediol, 3-methyl-1,5-pentanediol, 1,
Bisphenol A, various known saturated and unsaturated dihydric alcohols such as 6-hexanediol, octanediol, 1,4-butynediol, and dipropylene glycol
Dihydric alcohols obtained by adding ethylene oxide or propylene oxide to ethylene; trihydric alcohols such as glycerin, trimethylolethane, and trimethylolpropane; tetrahydric alcohols such as pentaerythritol; ethylene oxide, propylene oxide, tetrahydrofuran, etc. Examples include polyether diols such as polymers and copolymers. These alcohol compounds may be used alone or in combination of two or more. Among these alcohol compounds, those having an aromatic ring are particularly preferable in terms of heat resistance of the resulting polyphenylene ether resin composition.

The epoxy compound is not particularly limited and various known monoepoxy compounds and polyepoxy compounds can be used. Examples of the monoepoxy compound include alkyl glycidyl ethers such as n-butyl glycidyl ether and 2-ethylhexyl glycidyl ether;
Examples thereof include aryl glycidyl ethers such as phenyl glycidyl ether; monocarboxylic acid glycidyl esters such as versatic acid glycidyl ester; monocarboxylic acid glycidyl esters such as the rosin glycidyl ester; styrene oxide and cyclohexene oxide. As the diepoxy compound, for example, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, triethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, dipropylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether,
Non-cyclic aliphatic diglycidyl ethers such as polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether and 1,6-hexanediol diglycidyl ether; 2,2-bis (4-hydroxyphenyl) propane diglycidyl ether, bis (4-hydroxyphenyl) methane diglycidyl ether, 1,1-bis (4-hydroxyphenyl) ethane diglycidyl ether, 2,2-bis (4-hydroxycyclohexyl) propane diglycidyl ether, 3,
Aromatic or cyclic fatty acids such as 3 ', 5,5'-tetramethyl-4,4'-dihydroxybiphenyl diglycidyl ether and 2,2'-bis (4- (β-hydroxypropoxy) phenyl) propane diglycidyl ether Group diglycidyl ethers; diepoxy compounds such as cycloaliphatic cyclic oxiranes such as 3,4-epoxycyclohexylmethyl, 3,4-epoxycyclohexanecarboxylate, and vinylcyclohexenedioxide. Examples of the triepoxy compound include trimethylolpropane triglycidyl ether and trishydroxyethyl isocyanurate triglycidyl ether. Further, as the tetraepoxy compound,
For example, 1,1,2,2-tetra (4-hydroxyphenyl) ethane tetraglycidyl ether and the like can be mentioned. Examples of other polyepoxy compounds include sorbitol polyglycidyl ether and polyglycidyl ether of phenol novolac type resin. These epoxy compounds may be used alone or in combination of two or more. Among these epoxy compounds, those having an aromatic ring are particularly preferable from the viewpoint of heat resistance of the resulting polyphenylene ether resin composition.

The reaction between the alcohol compound and / or the epoxy compound and the purified and stabilized rosin is not particularly limited and can be easily carried out by using known reaction conditions. For example, the reaction between the alcohol compound and the purified and stabilized rosin is usually carried out in the equivalent ratio [-OH (eq) /-of the hydroxyl group of the alcohol compound and the carboxyl group of the rosin.
COOH (eq)] is adjusted to about 0.8 to 2.0, and then heated to about 150 ° C. to 280 ° C. under an inert gas stream, and known esterification is performed while distilling generated water out of the system. Esterification may be performed in the presence or absence of a catalyst. Further, as a specific example of the reaction between the epoxy compound and the rosin, it is calculated that one epoxy group of the epoxy compound corresponds to two hydroxyl groups, and the equivalent ratio of the hydroxyl group to the carboxyl group of the rosin [-OH (Eq) /-COOH (e
q)] is about 0.8 to 2.0 and then 1
The esterification reaction may be continued until the acid value becomes 5 or less, preferably 3 or less at 20 to 280 ° C. Examples of the catalyst include trimethylamine, triethylamine, tributylamine, benzyldimethylamine, pyridine, 2
-Amine-based catalysts such as methylimidazole, quaternary ammonium salts such as benzyltrimethylammonium chloride, Lewis acids, boric acid esters, organic metal compounds, organic acid metal salts, trialkylphosphines and triarylphosphines can be used.

The softening point of the component (C) of the present invention is 6
About 0 to 160 ° C. is preferable. More preferably, 70
~ 140 ° C. When the softening point exceeds 160 ° C., the effect of improving the melt viscosity of the obtained polyphenylene ether resin composition becomes insufficient, while the softening point is 60
When the temperature is lower than 0 ° C, the effect of improving the heat resistance of the polyphenylene ether resin composition becomes insufficient. The molecular weight of the component (C) is usually about 300 to 10,000, and preferably 300 to 5,000.
When the number average molecular weight exceeds 10,000, the effect of improving the melt viscosity of the polyphenylene ether resin composition becomes insufficient.

The polyphenylene ether resin composition of the present invention comprises 1 to 100 parts by weight of the component (A) and the component (B).
It is composed of 99 to 0 parts by weight of the component and the component (C).
The preferable mixing ratio of the components (A) and (B) is (A)
The component (B) is 90 to 5 parts by weight (the total amount of both components is 100 parts by weight) with respect to 10 to 95 parts by weight of the components. (C)
The blending amount of the components is 100 in total of the components (A) and (B).
It is usually 0.1 to 50 parts by weight, preferably 0.1 to 30 parts by weight, based on parts by weight. When the content of the component (C) is less than 0.1 parts by weight, the melt fluidity cannot be improved. On the other hand, when it exceeds 50 parts by weight, the polyphenylene ether resin inherently has various heat resistance and rigidity. However, it is not preferable in any case.

As described above, in the present invention, it is essential to use the component (C) in order to improve properties such as melt fluidity, but it is conventionally known as long as it does not depart from the object of the present invention. It does not matter if the modifier is used in combination. Examples of known modifiers (hereinafter referred to as (D) component) include, for example,
Examples thereof include C5-based petroleum resin, C9-based petroleum resin, C5 / C9-based petroleum resin, coumarone-indene resin, terpene resin, terpene-styrene resin, terpene-phenol resin, and hydrides thereof. The compounding amount of the component (D) is usually less than 30% by weight of the amount of the component (C) used.

Further, the polyphenylene ether resin composition of the present invention comprises (A) in order to improve impact strength.
The following optional components may be blended in a ratio of 70 parts by weight or less, preferably 50 parts by weight or less based on 100 parts by weight of the total of the components and the component (B). Examples of the optional component (hereinafter referred to as (E) component) include polyethylene, polypropylene, ethylene / propylene copolymer, ethylene / butene-1 copolymer, ethylene / propylene / dicyclopentadiene copolymer, ethylene / Propylene / 5-ethylidene-2-norbornene copolymer, ethylene / propylene / 1,4 hexadiene copolymer, ethylene / vinyl acetate copolymer, ethylene / butyl acrylate copolymer,
In the presence of olefin rubber such as ethylene / α, β-unsaturated carboxylic acid and acid anhydride copolymer, ethylene / α, β-unsaturated carboxylic acid glycidyl ester copolymer and diene rubber-like polymer A graft copolymer obtained by polymerizing a vinyl-based monomer mixture containing methyl methacrylate and acrylonitrile as essential components, a vinyl-based hydrocarbon block in which A and A'are polymerized, and a conjugate in which B is polymerized Examples thereof include an ABAA 'type block copolymer which is a diene block and a hydrogenated ABAA' type block copolymer in which the diene block B part is hydrogenated.

In addition to the essential components (A), (B), (C) and the optional components (D) and (E), the aromatic vinyl resin composition of the present invention is also a component. , Various known additives such as stearic acid, behenic acid,
Metal salts thereof (calcium, magnesium, zinc, etc.), ethylenebisstearic acid amide, etc. can also be added. Also, colorants, antioxidants, antistatic agents,
Reinforcing agents and fillers such as flame retardants, pigments, dyes, glass fibers, metal fibers, metal flakes, carbon fibers, etc., heat stabilizers, UV absorbers, light stabilizers, plasticizers, plasticizers and the like can be added.

The method for producing the polyphenylene ether resin composition of the present invention is not particularly limited, and a generally known method can be adopted. That is, the polyphenylene ether-based resin (A), the polystyrene-based resin (B) and the component (C) in the form of pellets, powders or fragments are uniformly mixed using a high-speed stirrer or the like and then have sufficient kneading ability. Various methods such as a method of melt-kneading with a single-screw or multi-screw extruder or a method of melt-kneading with a Banbury mixer or a rubber roll machine can be adopted.

[0030]

According to the present invention, it is possible to provide a polyphenylene ether resin composition which is excellent in melt flowability, moldability and heat resistance. The polyphenylene ether-based resin composition of the present invention can be used as an engineering plastic in automobile parts, electronic / electrical device parts and their manufacturing processes, and is required to have rigidity, heat resistance, dimensional stability and the like. It can be used for various molded products.

[0031]

EXAMPLES The present invention will be described in more detail below with reference to production examples, examples and comparative examples, but the present invention is not limited to these examples. Below, unless otherwise specified
Parts and percentages are by weight.

Production Example 1 (Preparation of purified and stabilized rosin) (1) Disproportionation reaction 1000 parts of unpurified Chinese gum rosin with acid value of 172, softening point of 75 ° C., color tone Gardner 6 and 5% palladium carbon (hydrous content) (50%), 0.3 part was added, and the mixture was stirred under a nitrogen blanket at 280 ° C. for 4 hours to carry out a disproportionation reaction.
A disproportionated rosin having an acid value of 157, a softening point of 77 ° C. and a color tone Gardner 8 was obtained. (2) Purification The disproportionated rosin was distilled under a nitrogen blanket under a reduced pressure of 3 mmHg to purify the main distillate shown in Table 1 having an acid value of 178.3, a softening point of 85 ° C. and a general constant of color Gardner 4. Disproportionate rosin. (3) Hydrogenation reaction 200 parts of the above-mentioned purified disproportionated rosin and 0.4 part of 5% palladium carbon (water content 50%) were charged into a shaking autoclave to remove oxygen in the system, and then the system was hydrogenated. At 1
Pressurize to 00 kg / cm ² and raise the temperature to 260 ℃,
Hydrogenation reaction is carried out for an hour, acid value 169.1, softening point 8
6.0 ° C, color tone Gardner 1 or less (Hazen color 5
0) purified stabilized rosin (C-1) was obtained.

Production Example 2 (Preparation of Purified and Stabilized Rosin) (1) Dehydrogenation Reaction 200 parts of the purified disproportionated rosin obtained in Production Example 1 (2) and 5% palladium carbon (hydrated) as a dehydrogenation catalyst. Rate 50
%) 0.2 part was charged into a shaking autoclave, and nitrogen substitution was carried out to remove oxygen in the system, then the temperature in the system was raised to 260 ° C., and dehydrogenation reaction was carried out at the same temperature for 3 hours, A purified and stabilized rosin (C-2) having an acid value of 171.7, a softening point of 87 ° C. and a color tone of Gardner 1 or less (Hazen color 120) was obtained.

Production Example 3 (Preparation of purified stabilized rosin) (1) Hydrogenation reaction Unpurified Chinese gum rosin 1000 described in Production Example 1 (1)
Parts and 2 parts of 5% palladium carbon (water content 50%) as a hydrogenation catalyst were charged into a shaking autoclave to remove oxygen in the system, and then 100 kg / cm ^{2 of} hydrogen in the system.
The mixture is heated to 260 ° C. with stirring, and hydrogenated at the same temperature for 3 hours to give an acid value of 167 and a softening point of 74 ° C.
A crude hydrogenated rosin having a color Gardner 5 was obtained. (2) Purification The above crude hydrogenated rosin was distilled under a nitrogen blanket under a reduced pressure of 3 mmHg to give an acid value of 175.2, a softening point of 83 ° C., and a main distillation fraction shown in Table 2 having a general constant of color Gardner 2. Was purified hydrogenated rosin. (3) Dehydrogenation reaction 200 parts of the above-mentioned purified hydrogenated rosin and 0.2 part of 5% palladium carbon (water content 50%) as a dehydrogenation catalyst were placed in a shaking autoclave, and the atmosphere was replaced with nitrogen. After removing the oxygen of the above, the temperature of the system was raised to 250 ° C., the dehydrogenation reaction was performed at the same temperature for 3 hours, and the acid value was 172.6.
A purified and stabilized rosin (C-3) having a softening point of 84 ° C. and a color tone of Gardner 1 or less (Hazen color 80) was obtained.

Production Example 4 (Preparation of Purified and Stabilized Rosin Ester) 500 parts of the purified disproportionated rosin obtained in Production Example 1 (2) was charged into a flask, heated to 180 ° C. under a nitrogen blanket, and melted and stirred. After adding 60 parts of glycerin at 200 ° C. to 280
The temperature is raised to ℃, and the esterification is performed at the same temperature for 12 hours.
A purified disproportionated rosin ester having an acid value of 3.4, a softening point of 99 ° C. and a color tone Gardner 5 was obtained. The rosin ester was subjected to a hydrogenation reaction under the same reaction conditions as in Production Example 1 (3) to obtain a purified and stabilized rosin ester having an acid value of 8.5, a softening point of 99 ° C. and a color tone of Gardner 1 or less (Hazen color 150). C-
4) was obtained.

Production Example 5 (Preparation of Purified and Stabilized Rosin Ester) The purified and stabilized rosin (C-2) 500 obtained in Production Example 2
Part, 336 parts of bisphenol A propylene oxide 2 mol adduct (hydroxyl value 318) were charged into a flask,
By reacting for 12 hours at 250 ° C. under nitrogen stream, acid value 2.0, softening point 90.0, color tone Gardner 1 to
2 purified and stabilized rosin ester (hereinafter, rosin (C-
5)) was obtained.

Production Example 6 (Preparation of Purified and Stabilized Rosin Ester) The purified and stabilized rosin (C-1) 2 obtained in Production Example 1 (3)
00 parts, 2,2-bis (4-hydroxyphenyl) propane diglycidyl ether (epoxy equivalent 183.9)
83.5 parts and 0.071 part of triphenylphosphine were charged into a flask, reacted at 150 ° C. for 4 hours under a nitrogen stream, and further reacted at 250 ° C. for 5 hours to give an acid value of 0.1 and a softening point. 101 ° C, color tone Gardner 1
The following (Hazen color 175) purified stabilized rosin ester (C-6) was obtained.

Comparative Production Example 1 The crude disproportionated rosin obtained in Production Example 1 (1) was used.
Hereinafter, this is referred to as C-7.

Comparative Production Example 2 The crude disproportionated rosin obtained in Production Example 1 (1) was used to carry out a hydrogenation reaction under the same hydrogenation conditions as in Production Example 1 (3) to give an acid value of 157. 0.3, a softening point of 79 ° C., and an unpurified stabilized rosin (C-8) having a color tone of Gardner 4 was obtained.

Comparative Production Example 3 The crude disproportionated rosin obtained in Production Example 1 (1) was used for dehydrogenation under the same dehydrogenation conditions as in Production Example 2 (1) to obtain an acid value. 158, a softening point of 80 ° C., and an unpurified stabilized rosin (C-9) having a color tone of Gardner 5 was obtained.

Comparative Production Example 4 Using the crude disproportionated rosin obtained in Production Example 1 (1), this was esterified under the same esterification conditions as in Production Example 6, and then Production Example 3 (1). Hydrogenation was carried out under the same conditions as the hydrogenation conditions of 1. to obtain an unpurified stabilized rosin ester (C-10) having an acid value of 8.1, a softening point of 88 ° C. and a color tone Gardner 6.

Comparative Production Example 5 The crude disproportionated rosin obtained in Production Example 1 (1) was used for esterification and hydrogenation under the same esterification conditions and hydrogenation conditions as in Production Example 4. The crude rosin ester (C-11) having an acid value of 8.5, a softening point of 95 ° C. and a color tone Gardner 7 was obtained.

Examples 1 to 6 Polyphenylene ether resin (A) {intrinsic viscosity [η]
(Chloroform, 25 ° C.) 0.48 dl / g poly (2,6-dimethyl-1,4-phenylene) ether}
70 parts, polystyrene-based resin (B) {rubber modified polystyrene, manufactured by Mitsubishi Chemical Corporation, trade name HT644} 30 parts and (C) component were blended in the use ratio shown in Table 3, mixed with a blender, and biaxial The mixture was melt-kneaded through an extruder and pelletized.

Comparative Example 1 Pelletization was performed in the same manner as in Example 1 except that the component (C), C-1 was not used.

Comparative Examples 2 to 5 Pellets were formed in the same manner as in Example 1 except that various resins shown in Table 3 were used instead of C-1 which was the component (C).

Comparative Examples 6 to 10 In Example 1, instead of C-1 which is the component (C),
As shown in Table 3, C-7 obtained in Comparative Production Examples 1-5
Pelletization was performed in the same manner as in Example 1 except that C-11 was used.

The pelletized polyphenylene ether resin compositions obtained in Examples 1 to 6 and Comparative Examples 1 to 10 were used in the following tests. Table 3 shows the evaluation results.

(Melt Fluidity) The melt viscosity (300 ° C.) was measured using the above various pellets. In addition, the numerical value was described as a relative value when Comparative Example 1 (when the component (C) is not added) is set to 100 (actual measurement value 5200 ps). That is, when the value is larger than 100, the melt viscosity is high and the melt fluidity is poor, and when the value is smaller than 100, the melt viscosity is low and the melt fluidity is good.

(Heat resistance) The above various pellets were injection molded at a mold temperature of 70 ° C. by an injection molding machine set at a cylinder temperature of 250 to 300 ° C., and there was no coloring during molding, and 18.6 kg / cm 2. Under the stress of ² , at a temperature of 120 ° C., no deformation was evaluated as ◯, and other deformation was evaluated as x.

[0050]

[Table 1]

[0051]

[Table 2]

[0052]

[Table 3]

It can be seen from Table 3 that the compositions of Examples 1 to 6 have better melt flowability and heat resistance than the compositions of Comparative Examples 1 to 10.

──────────────────────────────────────────────────続 き Continuation of the front page (51) Int.Cl. ⁶ Identification code Agency reference number FI Technical display location C08L 93/04 LSK C08L 93/04 LSK

Claims (4)

[Claims] 1. A polyphenylene ether resin (A) 1
-100 parts by weight and polystyrene resin (B) 99-0
A polyphenylene ether resin, characterized by comprising: parts by weight, and a purified and stabilized rosin having a Gardner color tone of 2 or less, or a rosin ester (C) comprising the purified and stabilized rosin and an alcohol compound and / or an epoxy compound. Composition. 2. The polyphenylene ether resin composition according to claim 1, wherein the purified and stabilized rosin and rosin ester as the component (C) have a Gardner color tone of 1 or less. 3. The polyphenylene ether resin composition according to claim 1, wherein in the rosin ester of the component (C), the alcohol compound and the epoxy compound have an aromatic ring. 4. The polyphenylene ether resin according to claim 1, wherein the compounding amount of the component (C) is 0.1 to 50 parts by weight based on 100 parts by weight of the total of (A) and (B). Composition.