JPH07316414A - Thermoplastic resin composition - Google Patents

Abstract

(57) [Abstract] [Purpose] To provide an inexpensive thermoplastic resin composition having excellent heat resistance, mechanical properties, and moldability. [Structure] (A) Modified polyphenylene ether modified with aminomethyl group, (B) (a) 5 ethylene units
0 to 99% by weight, and (b) the unsaturated carboxylic acid glycidyl ester unit or unsaturated glycidyl ether unit is 0.
1 to 30% by weight, (c) an ethylenically unsaturated ester compound unit consisting of 0 to 50% by weight of an epoxy group-containing ethylene copolymer, and (C) an aromatic polycarbonate as a main component, and a component (A). The ratio of the component (B) to the component (B) is 0.
1 to 70 parts by weight, and the ratio of the sum of the weight of the component (A) and the component (B) and the component (C) is (component (A) + component (B)) is 1 to 99% by weight relative to the component ( A thermoplastic resin composition in which C) is 99 to 1% by weight.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel thermoplastic resin composition which can be used for molded articles by injection molding or extrusion molding.

[0002]

2. Description of the Related Art Polyphenylene ether is a resin having excellent properties such as heat resistance, hot water resistance, dimensional stability, and mechanical and electrical properties, but on the other hand, its high melt viscosity makes it extremely processable. However, it has the drawbacks of poor chemical resistance, low impact resistance and the like.

As an attempt to improve the molding processability of polyphenylene ether, a method of blending polyphenylene ether with polystyrene is known. However, although this method improves the moldability of the polyphenylene ether, it causes a problem that the heat resistance of the polyphenylene ether is significantly reduced.

JP-A-57-108153 describes that a composition having excellent impact resistance can be obtained by blending polyphenylene ether with a copolymer of olefin and glycidyl methacrylate and / or glycidyl acrylate. However, problems still remain in the molding processability and heat resistance of the composition.

US Pat. No. 3,221,080 discloses a composition of polyphenylene ether and an aromatic polycarbonate resin, but the physical properties were not always sufficient. JP-A-2-654 discloses a composition comprising a graft-modified polyphenylene ether and an aromatic polycarbonate. Japanese Patent Application Laid-Open No. 63-291949 discloses a composition of polyphenylene ether, an aromatic polycarbonate and an unsaturated carboxylic acid derivative, and Japanese Patent Publication No. 5-14740 discloses a composition of 2,6-dialkylphenol and 2,3,6. -A composition consisting of polyphenylene ether, which is a copolymer with a trialkylphenol, and an aromatic polycarbonate is disclosed. In addition, Japanese Patent Publication No. 61-29984 discloses a composition obtained by blending a polyphenylene ether with a copolymer of an olefin and glycidyl methacrylate or glycidyl acrylate. However, in each case, the physical properties of the composition were not always sufficient.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to make use of the excellent mechanical properties and heat resistance of polyphenylene ether, and to improve the molding processability and impact resistance of an inexpensive thermoplastic resin. It is intended to provide a composition and a method for producing the same.

[0007]

The present inventors have arrived at the present invention as a result of intensive studies to solve these problems. That is, the present invention comprises the inventions described below.

(1) (A) Polyphenylene ether represented by the following structural unit (1)

[Chemical 2] (In the formula, R ₁ and R ₂ are each independently selected from hydrogen and a hydrocarbon group having 1 to 20 carbon atoms.) In the polyphenylene ether having a number average degree of polymerization of 20 to 1200, the number average polymerization is When the degree is X, the methyl group at the 2-position and / or the 6-position of the phenylene group is 0.
A modified polyphenylene ether modified with an aminomethyl group in a ratio of 02 / X to 1 / X, (B) (a) an ethylene unit of 50 to 99% by weight, (b)
0.1 to 30% by weight of unsaturated carboxylic acid glycidyl ester units or unsaturated glycidyl ether units, (c)
Ethylenically unsaturated ester compound unit 0 to 50% by weight
Which is composed of an epoxy group-containing ethylene copolymer consisting of (C) and an aromatic polycarbonate (C), and the mixing ratio of the component (A) and the component (B) is such that the component (B) is 100 parts by weight of the component (A). 0.1 to 70 parts by weight, and the ratio of the weight sum of the component (A) and the component (B) and the component (C) is (component (A) + component (B)) is 1 to 99% by weight. A thermoplastic resin composition in which the component (C) is 99 to 1% by weight.

Next, the present invention will be described in detail. The component (A) of the thermoplastic resin composition of the present invention has the general formula (2)

[Chemical 3] (In the formula, R ₁ , R ₂ , R ₃ , R ₄ and R ₅ are each independently a group consisting of hydrogen, a halogen atom, a hydrocarbon group having 1 to 6 carbon atoms and a substituted hydrocarbon group having 1 to 8 carbon atoms. At least one of which is a hydrogen atom and at least one of which is not a hydrogen atom, and at least one of phenol compounds represented by the formula (1) is oxygen or an oxygen-containing compound. It is a modified product of polyphenylene ether, which is a polymer obtained by oxidative polymerization with gas.

In the phenol compound represented by the general formula (2), specific examples of R ₁ , R ₂ , R ₃ , R ₄ and R ₅ are independently hydrogen, chlorine, bromine, fluorine and iodine, Methyl, ethyl, n- or iso-propyl, pri-, sec- or t-butyl, chloroethyl, hydroxyethyl, phenylethyl, benzyl,
Examples thereof include those selected from the group consisting of hydroxymethyl, carboxyethyl, methoxycarbonylethyl, cyanoethyl, phenyl, chlorophenyl, methylphenyl, dimethylphenyl, ethylphenyl and allyl groups.

Specific examples of the phenol compound represented by the above general formula (2) include o- or m-cresol,
2,6-, 2,5-, or 3,5-dimethylphenol, 2-methyl-6-phenylphenol, 2,6-diphenylphenol, 2,6-diethylphenol, 2
-Methyl-6-ethylphenol, 2,3,5- or 2,3,6-trimethylphenol, 3-methyl-6-
Examples thereof include t-butylphenol, thymol, 2-methyl-6-allylphenol and the like.

Of these phenolol compounds, preferred are 2,6-dimethylphenol and 2,6
-Diphenylphenol, 3-methyl-6-t-butylphenol and 2-methyl-6-allylphenol. Particularly, 2,6-dimethylphenol is preferable.

Component (A) of the thermoplastic resin composition of the present invention
As a polyphenylene ether that is a raw material polymer of
Polymer of 2,6-dimethylphenol or 2,6-diphenylphenol and a large amount of 2,6-dimethylphenol and a small amount of 3-methyl-6-t-butylphenol or 2,3,6-trimethylphenol Is preferable. A polymer of 2,6-dimethylphenol is particularly preferable.

Further, as the polyphenylene ether which is a raw material polymer of the component (A), a small amount of a phenol compound other than the above general formula (2), for example, bisphenol-A, tetrabromobisphenol-A, resorcin,
A copolymer of a polyvalent hydroxyaromatic compound such as hydroquinone or novolac resin and a large amount of the phenol compound represented by the general formula (2) can also be used.

The oxidative coupling catalyst used in the oxidative polymerization of the phenol compound is not particularly limited, and any catalyst having a polymerization ability can be used. For example, typical examples thereof include a catalyst containing cuprous chloride and a catalyst containing divalent manganese salts.

When the oxidative polymerization for obtaining polyphenylene ether is carried out at a temperature higher than 40 ° C. (high temperature polymerization),
It is known that there is a difference in the physical properties and the like of the obtained polymer when it is carried out at a temperature of not higher than 0 ° C (low temperature polymerization). As a method for producing polyphenylene ether as a raw material of the thermoplastic resin composition of the present invention, either high temperature polymerization or low temperature polymerization can be adopted.

The component (A) used in the thermoplastic resin composition of the present invention is the 2- and / or 6-position of the phenylene group in the polyphenylene ether having the structural unit represented by the general formula (1) obtained by the above production method. some of the position of the methyl group is modified polyphenylene ether having a structural unit modified to an amino methyl group (-CH ₂ NH _2). The structural unit in which a part of the methyl group is replaced with an aminomethyl group may be the terminal structural unit of the polyphenylene ether, or may be in the middle of the main chain instead of the terminal. Particularly, a structural unit in which a part of the methyl group is replaced with an aminomethyl group is a terminal structural unit of polyphenylene ether is preferable because it is easy to obtain it.

Component (A) of the thermoplastic resin composition of the present invention
The modified polyphenylene ether of is, when the number average degree of polymerization is X, 0.02 / X to 1 / X of the methyl group at the 2-position and / or the 6-position of the phenylene group, preferably 0.05 / X.
It is characterized in that X to 1 / X is modified to an aminomethyl group. When the aminomethyl group is less than 0.02 / X of the 2-position and 6-position methyl groups of the phenylene group, it is not preferable because the heat resistance and mechanical properties are not sufficiently improved when used as a component of the resin composition. .

As the raw material of the modified polyphenylene ether of the component (A), the structural unit represented by the general formula (1) has a number average of 20 to 1200, more preferably 30 to 10
A polyphenylene ether of 00 is used. If the number of structural units represented by the general formula (1) is out of this range, the processability of the resin becomes poor, or the mechanical properties become insufficient, which is not preferable. The modified polyphenylene ether having a structural unit in which the methyl group at the 2-position and / or the 6-position of the phenylene group in the polyphenylene ether used as the component (A) is modified to an aminomethyl group is the epoxy group-containing ethylene of the component (B). Provided is a thermoplastic resin composition which is highly reactive with a copolymer and has good properties.

Next, a method for producing the modified polyphenylene ether of the component (A) will be described. The modified polyphenylene ether of the component (A) can be produced by the following general formula (2).

[0021]

[Chemical 4] (In the formula, R ₃ , R ₄ , and R ₅ are each independently selected from hydrogen and a hydrocarbon group having 1 to 20 carbon atoms.) A nucleus-substituted phenol represented by the formula is polymerized using an oxidation coupling catalyst. In the method of formula (3)

[0022]

[Chemical 5] (In the formula, Q ₁ and Q ₂ are each independently selected from hydrogen, an alkyl group having 1 to 24 carbon atoms and an aralkyl group having 7 to 24 carbon atoms, provided that both Q ₁ and Q ₂ are hydrogen. And an amine represented by Q ₁ and Q _{2 each} being an alkylene group which is linked to form a ring).
Preferred is a method for producing a modified polyphenylene ether, which is characterized in that polymerization is carried out in the presence of 001 to 0.2 mol, and the obtained polyphenylene ether is melt-kneaded.

More specifically, in the method of polymerizing the nuclear-substituted phenols represented by the general formula (2) using an oxidative coupling catalyst, the polymerization is carried out in the presence of the amines represented by the general formula (3). To do. The amines are 0.001 to 1 mol with respect to 1 mol of the nuclear-substituted phenols used.
0.2 mol, preferably 0.005-0.05 mol is present. If the amount used is less than 0.001 mol with respect to 1 mol of the nuclear-substituted phenols, polyphenylene ether of excellent quality cannot be obtained, and if it is more than 0.2 mol, a polyphenylene ether having a practical molecular weight is used. Is not preferable because it cannot be obtained. In this way, a polyphenylene ether having the amines in its side chain can be obtained. Next, the nucleus-substituted phenols are those represented by the general formula (2), and the nucleus-substituted phenols can be used alone or in combination of two or more kinds.

Preferred nuclear-substituted phenols are 2,
6-dimethylphenol, 2,3,6-trimethylphenol and the like can be mentioned. Particularly, 2,6-dimethylphenol is preferable.

Next, as the amines represented by the general formula (3), specifically, n-propylamine, iso-propylamine, n-butylamine, iso-butylamine, sec-butylamine, n-hexylamine, n-
1 such as octylamine, 2-ethylhexylamine, cyclohexylamine, laurylamine, benzylamine
And secondary amines such as diethylamine, di-n-propylamine, di-n-butylamine, di-iso-butylamine, di-n-octylamine, piperidine and 2-pipecoline. The general formula (3)
Is also equivalent to the amine represented by the general formula (3), and examples of such polyamine include ethylenediamine, piperazine, and 1,3-dipiperidylpropane. Etc.

Specifically, a catalyst system in which an amine represented by the general formula (3) is combined with a known copper compound, manganese compound or cobalt compound and a ligand selected from bases is used. preferable. For example, JP-A-53-7
As described in JP-A-9993, a method of oxidatively coupling a phenolic monomer and oxygen in the presence of a catalyst composed of a manganese salt, a basic reaction medium and a secondary amine, or JP-A-63-54424. The method of oxidatively polymerizing a nuclear-substituted phenol with an oxygen-containing gas in an organic solvent in the presence of a catalyst as described in 1., a manganese compound containing one or more divalent manganese salts as a catalyst, At least one basic compound selected from Group IA metal hydroxides, alkoxides or phenoxides, Group IIA metal hydroxides, oxides, alkanolamines, and a catalyst system containing amines are used. There is a method of doing.

Thus, the following general formula (4)

[Chemical 6] (In the formula, Q ₁ and Q ₂ are each independently selected from hydrogen, an alkyl group having 1 to 24 carbon atoms and an aralkyl group having 7 to 24 carbon atoms, provided that both Q ₁ and Q ₂ are hydrogen. including those not included, also Q _1, Q ₂ are connected to form a ring an alkylene group by a group represented by.), the methyl group of 2-position and / or 6-position of the phenylene group A polyphenylene ether having a modified structural unit can be obtained.

The structural unit to which the secondary or tertiary amine is bonded may be the terminal structural unit of the polyphenylene ether, or may be not the terminal but the middle of the main chain. In particular, it is preferable that the structural unit is a terminal structural unit of polyphenylene ether because it is easy to obtain it.

Next, the polyphenylene ether having a secondary or tertiary amine bonded to the methyl group at the 2-position and / or the 6-position of the phenylene group thus obtained is melt-kneaded while devolatilizing. The modified polyphenylene ether of component (A) used in the thermoplastic resin composition of the present invention can be obtained. The melt-kneading is performed at a cylinder set temperature of 200 to 300 ° C., preferably 230 to 28.
It is preferable to perform at 0 ° C. Cylinder set temperature is 200 ℃
If it is less than the above range, the moldability of the raw material polyphenylene ether is poor, and if the cylinder set temperature exceeds 300 ° C., the polyphenylene ether is decomposed, which is not preferable.
For melt kneading, it is preferable to use a generally used kneading device such as a single-screw or twin-screw extruder and various kneaders.

It is also possible to blend a radical initiator at the time of melt-kneading and melt-knead. Further, the polyphenylene ether may be blended with a radical initiator in advance and melt-kneaded. Radical initiators preferably used include cumene hydroperoxide, t-butyl hydroperoxide, dimethyl-2,5-bis (hydroperoxy) hexane and 1,3-bis (t-
Butyl peroxyisopropyl) benzene, di-t-butyl peroxide, 2,6-di-t-butyl-4-methylphenol and the like.

Component (A) of the thermoplastic resin composition of the present invention
If desired, unmodified polyphenylene ether can be mixed and used. Further, the polyphenylene ether consisting only of the general formula (1), the 2-position and / or 6 of the phenylene group only by the group represented by the general formula (4).
Even if the modified polyphenylene ether having a structural unit in which the methyl group at the position is modified is used alone or in combination, the reaction with the epoxy group-containing ethylene copolymer of the component (B) is insufficient, which is not preferable. .

Component (A) of the thermoplastic resin composition of the present invention
Of modified polyphenylene ether and unmodified polyphenylene ether of η _{SP /} c (0.5 g / dl
Value measured at 25 ° C. for the chloroform solution of
The range of 0.30 to 0.65 dl / g is preferable. η _SP /
When c is less than 0.30 dl / g, the heat resistance of the composition remarkably decreases, and when η _SP / c exceeds 0.65 dl / g, the moldability of the composition deteriorates, which is not preferable.

Component (B) of the thermoplastic resin composition of the present invention
And the epoxy group-containing ethylene copolymer is (a) an ethylene unit of 50 to 99% by weight, and (b) an unsaturated carboxylic acid glycidyl ester unit or an unsaturated glycidyl ether unit of 0.1 to 30% by weight, preferably 0.5-20
The epoxy group-containing ethylene copolymer is composed of 0 to 50% by weight of (c) the ethylenically unsaturated ester compound unit. The compound which gives the unsaturated carboxylic acid glycidyl ester unit and the unsaturated glycidyl ether unit (b) in the epoxy group-containing ethylene copolymer (B) is
They are represented by the following general formulas (5) and (6), respectively.

[0034]

[Chemical 7] (R is a C2-C13 hydrocarbon group having an ethylenically unsaturated bond.)

[0035]

[Chemical 8] (R is a hydrocarbon group having 2 to 18 carbon atoms which has an ethylenically unsaturated bond, X is -CH ₂ -O- or

[Chemical 9] Is. ) Specific examples include glycidyl acrylate, glycidyl methacrylate, itaconic acid glycidyl ester, allyl glycidyl ether, 2-methylallyl glycidyl ether, and styrene-p-glycidyl ether.

In addition, the epoxy group-containing ethylene copolymer used in the present invention includes an unsaturated carboxylic acid glycidyl ester or unsaturated glycidyl ether, ethylene and (c) an ethylenic unsaturated ester compound as a ternary or more multi-component copolymer. Polymers can also be used. Examples of the ethylenically unsaturated ester compound (c) include vinyl acetate,
Examples thereof include vinyl propionate, methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, and other carboxylic acid vinyl esters, and α, β-unsaturated carboxylic acid alkyl esters. Particularly, vinyl acetate, methyl acrylate, and ethyl acrylate are preferable.

The epoxy group-containing ethylene copolymer (B) used in the present invention is, for example, a copolymer consisting of ethylene units and glycidyl methacrylate units, a copolymer consisting of ethylene units, glycidyl methacrylate units and methyl acrylate units. , A copolymer composed of an ethylene unit, a glycidyl methacrylate unit and an ethyl acrylate unit, a copolymer composed of an ethylene unit, a glycidyl methacrylate unit and a vinyl acetate unit, and the like. The melt index (JIS K6760) of the epoxy group-containing ethylene copolymer is preferably 0.5 to 100 g / 10 minutes, more preferably 2 to 5
It is 0 g / 10 minutes. The melt index may be outside this range, but the melt index is 100 g / 1
When it exceeds 0 minutes, it is not preferable in terms of mechanical properties when it is made into a composition, and when it is less than 0.5 g / 10 minutes, the compatibility with the modified polyphenylene ether of the component (A) is poor.

The epoxy group-containing ethylene copolymer is usually an unsaturated epoxy compound and ethylene in the presence of a radical generator at 500 to 4000 at 100 to 300 ° C. in the presence or absence of a suitable solvent or chain transfer agent. It is produced by a method of copolymerizing below. It can also be produced by a method of mixing an unsaturated epoxy compound and a radical generator with polyethylene and performing melt graft copolymerization in an extruder.

Component (C) of the thermoplastic resin composition of the present invention
The aromatic polycarbonate is an aromatic polycarbonate having a repeating structural unit represented by the general formula (7), which is obtained by reacting a dihydric phenol with a carbonate precursor such as phosgene, haloformate or carbonic acid ester.

[Chemical 10] (In the formula, A is a divalent aromatic group derived from a dihydric phenol.)

The dihydric phenol used here is a monocyclic or polycyclic aromatic compound and has two hydroxyl groups directly bonded to carbon in the aromatic ring. Specific examples of these dihydric phenols include 2,2-bis (4-hydroxyphenyl) propane (bisphenol A), hydroquinone, resorcin, 2,2-bis (hydroxyphenyl) pentane, and 2,4'-dihydroxy-diphenylmethane. , Bis (2-hydroxyphenyl) methane, bis (4-hydroxyphenyl) methane, bis (4-hydroxy-5-nitrophenyl) methane, 1,1-bis (4
-Hydroxyphenyl) ethane, 3,3-bis (4-hydroxyphenyl) pentane, 2,2-dihydroxydiphenyl, 2,6-dihydroxy-naphthalene, bis (4-hydroxyphenyl) sulfone, 2,4'-dihydroxydiphenyl Sulfone, 5-chloro-2,4'-
Dihydroxydiphenyl sulfone, bis (4-hydroxyphenyl) diphenyldisulfone, 4,4-dihydroxydiphenyl ether, 4,4'-dihydroxy-
Examples include 3,3'-dichlorodiphenyl ether and 4,4'-dihydroxy-2,5-diethoxydiphenyl ether. Preferably, bisphenol A and its nuclear substitution derivative are mentioned. These dihydric phenols may be used alone or as a mixture.

The aromatic polycarbonate used in the thermoplastic resin composition of the present invention is produced from the above-mentioned dihydric phenol as a raw material by a known method, that is, a transesterification method, a solution method, an interfacial polycondensation method, etc., and preferably. Viscosity average molecular weight 15,000 or more, more preferably 25,000
That is all. Specific polymerization methods of these are, for example, "ENCYCLOPEDIA OF POLYMER".
SCIENCE AND TECHNOLOGY "Volume 10 (John Wiley & Sons, In
c. , 1969) pp. 710-764 under the heading "Polycarbonate". Further, for these polycarbonates, copolymers such as the polycarbonate-styrene block copolymers disclosed in JP-B-48-25076 can be used.

In the thermoplastic resin composition of the present invention,
Inorganic fillers can be used if desired. As such an inorganic filler, calcium carbonate, talc, clay, silica, magnesium carbonate, barium sulfate, titanium oxide, alumina, gypsum, glass fiber, carbon fiber, alumina fiber, aluminum borate whiskers, potassium titanate fiber, etc. Is exemplified.

In the thermoplastic resin composition of the present invention, if necessary, an antioxidant, a heat stabilizer, a light stabilizer, a flame retardant, a lubricant, an antistatic agent, an inorganic or organic colorant, and a rust preventive agent. Various additives such as a crosslinking agent, a foaming agent, a fluorescent agent, a surface smoothing agent, a surface gloss improving agent, and a release improving agent such as a fluororesin can be added during the manufacturing process or in the subsequent processing process.

In the thermoplastic resin composition of the present invention,
The target thermoplastic resin composition can be obtained when the composition ratio of the component (A), the component (B) and the component (C) takes a value within a specific range.

The composition ratio of the modified polyphenylene ether of the component (A) to the epoxy group-containing ethylene copolymer of the component (B) in the thermoplastic resin composition of the present invention is 100 parts by weight of the component (A). (B) is 0.1 to 70
Parts by weight, preferably 1 to 40 parts by weight, more preferably 3 to 30 parts by weight. If the amount of the component (B) is less than 0.1 part by weight, the impact resistance improving effect of the composition is not recognized, and if the amount of the component (B) exceeds 70 parts by weight, the heat resistance and rigidity of the composition are deteriorated. Is not preferred.

In the thermoplastic resin composition of the present invention, the ratio of the weight sum of the components (A) and (B) to the component (C) is
The weight sum of the component (A) and the component (B) is 1 to 99% by weight, and the component (C) is 99 to 1% by weight. (Component (A)
If the + component (B) is less than 1% by weight, the heat resistance of the composition will be insufficient, and if it exceeds 99% by weight, the moldability of the composition will be deteriorated, which is not preferable.

As a method for producing the thermoplastic resin composition of the present invention, for example, a modified polyphenylene ether of the component (A) is obtained by melt-kneading an unmodified polyphenylene ether while devolatilizing it using a kneader. After
The epoxy group-containing ethylene copolymer of the component (B) and the aromatic polycarbonate of the component (C) are mixed therein and the mixture is kneaded together to produce the composition, or the modified polyphenylene ether of the component (A), the component ( The epoxy group-containing ethylene copolymer of B) and the aromatic polycarbonate of component (C) are each dissolved in a solvent and the respective components are mixed in a solution state, and the solvent is evaporated or the resin component is not dissolved in a solvent. And the like to precipitate the resin composition.

Further, unmodified polyphenylene ether is charged from the first feed port of the kneading extruder, and the polyphenylene ether is melt-kneaded in the kneading extruder between the first feed port and the second feed port to modify the polyphenylene ether. After producing the polyphenylene ether, the epoxy group-containing ethylene copolymer of the component (B), the aromatic polycarbonate of the component (C), and the like are added from the second feed port of the extrusion kneader to prepare the modified polyphenylene ether and the epoxy. Another example is a method of producing a thermoplastic resin composition of the present invention by melt-kneading a group-containing ethylene copolymer, the aromatic polycarbonate and the like in the kneading extruder. Alternatively, the components (A) and (B) may be previously kneaded, and then the component (C) may be kneaded, or another kneading order may be used.

[0049]

EXAMPLES The present invention will be described below with reference to examples, but these are merely examples and the present invention is not limited to these.

[Determination of amine in raw material polyphenylene ether and modified polyphenylene ether] Nitrogen content in total amine: About 1 g of sample was weighed and dissolved in 50 cc of chloroform, and 5 cc of acetic acid was added,
Potentiometric titration was performed using a potentiometer AT-310 (glass-calomel electrode, titrant 0.1 mol perchloric acid, (acetic acid solution)) manufactured by Kyoto Electronics Co., Ltd., and nitrogen in all amines was calculated according to the following formula. The content was determined. N _T = 0.0014 × A × C ₁ × 100 / S N _T : Nitrogen content (%) of all amines A: Titration amount (cc) S: Sample amount (g) C ₁ : Concentration of perchloric acid solution ( Mol / liter)

Nitrogen content in tertiary amine: about 1 g of sample
Was dissolved in 50 cc of chloroform, added with 5 cc of acetic anhydride, allowed to stand, added with 5 cc of acetic acid, and then subjected to potentiometric titration as in the case of titration of nitrogen content in all amines. The nitrogen content in it was determined. N ₃ = 0.0014 × B × C ₂ × 100 / S N ₃ : Nitrogen content in tertiary amine (%) B: Titration amount (cc) S: Sample amount (g) C ₂ : Perchloric acid solution Concentration (mol / liter)

Nitrogen content in secondary amine: about 1 g of sample
Was dissolved in 50 cc of chloroform, 0.5 cc of salicylaldehyde was added, the mixture was allowed to stand, and the titration reagent was changed to 0.1 mol / liter hydrochloric acid in 2-propanol. Then, the potentiometric titration was carried out, and the nitrogen content N ₂ , ₃ (%) of (secondary amine + tertiary amine) in the sample was first determined according to the following formula. N ₂ , ₃ = 0.014 x C x D x 100 / S C: Titration concentration of hydrochloric acid (mol / liter) D: Titration amount (cc) S: Sample amount (g) The nitrogen content N ₂ (%) of the secondary amine was determined. N ₂ = N ₂ , _3- N ₃

Nitrogen content in primary amine: The nitrogen content N ₁ (%) of the primary amine in the sample was determined according to the following formula. N ₁ = N _T −N ₂ −N ₃

[NMR measurement] AMX600 manufactured by Bruker
Resonance frequency of ¹ H is 60
0.14MHz, resonance frequency of ¹³ C is 150.92MH
Measurements were made at z. The sample was dissolved in CDCl ₃ , and the measurement temperature was 40 ° C. Chemical shifts are a case peak of CHCl ₃ in ¹ H-NMR and 7.24 ppm, ¹³ C-
In the case of NMR, the peak of ¹³ CDCl ₃ was calculated as 77.1 ppm. Note that the R-1 peaks are mainly attributed to Macromolecules, 2
Volume 3 1318-1329 (1990).

[Method of Measuring Physical Properties of Molded Article] Physical properties of the obtained composition are PS40E5 manufactured by Nissei Plastic Co., Ltd.
Using an ASE type injection molding machine, the molding temperature is 270 ° C to 34 ° C.
The molding was performed at 0 ° C. and a mold temperature of 80 to 110 ° C. on a molded product.

Melt index (MI) According to JIS K6760, load 10 kg, temperature 28
It was measured at 0 ° C. The unit is g / 10 min.・ Tensile test ASTM No. 4 tensile dumbbell is molded, and ASTM D63 is used.
Tensile strength and elongation were measured according to 8.

Bending elastic modulus The test piece (6.4 mm thick) was measured according to ASTM D790. -Heating deformation test (TDUL) A with a load of 18.6 kg for a test piece (6.4 mm thick)
It was measured according to STM D648.

Izod impact strength A test piece (3.2 mm thick) is JISK notched.
According to 7110, it was measured at room temperature.・ Mold shrinkage ratio The flow direction (MD) of the injection molded product and the direction (T
The dimension of D) was measured and determined as a ratio to the original size of the mold.

[Polyphenylene ether of component (A),
Modified Polyphenylene Ether] Reference Example 1 3420 g of xylene was added to a 10 liter capacity jacketed autoclave equipped with a stirrer, a thermometer, a condenser, and an air introduction tube reaching the bottom of the autoclave.
Methanol 1366 g, 2,6-dimethylphenol 1
222 g (10.02 mol) and sodium hydroxide 2
After charging 4 g to make a uniform solution, 33.8 g of diethanolamine and 27.7 g of di-n-butylamine were added to the solution.
(0.233 mol, 0.0233 mol based on 1 mol of 2,6-dimethylphenol) and 0.99 g of manganese chloride tetrahydrate were added to a solution of 100 g of methanol.

Then, while vigorously stirring the contents, air was blown into the contents at a flow rate of 5 l / min. The reaction temperature and pressure were maintained at 35 ° C. and 9 kg / cm ² , respectively. After 7 hours from the start of blowing air, the air supply was stopped and the reaction mixture was thrown into a mixture of 66 g of acetic acid and 4,900 g of methanol. The obtained slurry was filtered under reduced pressure to isolate wet polyphenylene ether. The isolated polyphenylene ether was washed with 7,200 g of methanol and then dried under reduced pressure at 150 ° C. overnight to obtain 1160 g of dried polyphenylene ether. The synthesis of polyphenylene ether was repeated 4 times by the completely same operation to obtain a total of 4640 g of dry polyphenylene ether. This polyphenylene ether had a number average molecular weight of 6000 and a number average degree of polymerization of 50. Hereinafter, the polyphenylene ether may be abbreviated as A-1. Table 1 shows the nitrogen contents of various amines of A-1. From the 2nd and 6th position of polyphenylene ether
It can be seen that 0.43% of the substituted methyl group at the position is substituted with the tertiary dibutylamino group.

100 parts by weight of polyphenylene ether A-1 and antioxidant Irganox 1330 (trade name)
After mixing 0.3 parts by weight and 0.2 parts of 2,6-di-t-butyl-4-methylphenol with a Henschel mixer,
Using a twin-screw extruder PCM-30 manufactured by Ikegai Iron Works Co., Ltd., the hopper was put into a place under a nitrogen atmosphere, the cylinder set temperature was 273 ° C., and the screw rotation speed was 80 rpm.
Then, kneading was performed while devolatilization was performed. The modified polyphenylene ether thus obtained had a number average molecular weight of 6,800 and a number average degree of polymerization of 56.7. Hereinafter, this modified polyphenylene ether may be abbreviated as A-2. Table 1 shows the nitrogen contents of various amines A-2. It can be seen that a modified polyphenylene ether in which the tertiary amine was significantly reduced and the primary amine was significantly increased as compared with the raw material polyphenylene ether was obtained.

[0062]

[Table 1]

From this, it is understood that 0.30% of the substituted methyl groups at the 2- and 6-positions of the polyphenylene ether are substituted with aminomethylene groups.

Two-dimensional HMQC N of A-1 and A-2
The MR spectra are shown in FIGS. 1 and 2, respectively. In FIGS. 1 and 2, the vertical axis shows the chemical shift of ¹³ C and the horizontal axis shows the chemical shift of ¹ H. In this spectrum, one signal is observed as two peaks split in the ¹ H axis direction because ¹³ C is not decoupled at the time of observation. The ¹³ C-NMR chemical shift of the signal is given at the peak position. ¹ H-NMR chemical shifts are given at the midpoints of the two split peak positions.
This is indicated by an arrow in the figure.

The attributions of the main peaks are as follows.
In the two-dimensional HMQC NMR spectrum of A-1, ¹³ C:
Signals with chemical shifts of 58.1 ppm, ¹ H: 3.62 ppm were found in the literature Macromolecule
s, 23 , 1318 (1990), a diphenylamine-bonded polyphenylene ether having a phenylene group of 2
Assigned to carbon and hydrogen of the methylene group at position 6 or 6 respectively. The intensity of this signal was significantly reduced in A-2, and ¹³ C: 36.3 ppm and ¹ H: 3.89 were newly added.
A signal with a chemical shift of ppm is observed. Reference Phytochem. , 18 , 1547 (1979)
Shows that the chemical shift of the carbon of the methylene group of the benzyl group to which the primary amine is bound is 39.4 ppm, and the literature Aldrich Library of NMR
It is known from Spectra, II , 1066 (1983) that the chemical shift of hydrogen of the methylene group of the benzyl group to which the primary amine is bound is 3.9 ppm. Therefore, ¹³ C found in A-2: 36.3 pp
m, ¹ H: A signal having a chemical shift of 3.89 ppm is assigned to carbon and hydrogen of the methylene group at the 2-position or 6-position of the phenylene group of the polyphenylene ether having a primary amine bonded thereto. This result is in agreement with the analysis result of the amino group by the above titration.

Used in the thermoplastic resin composition of the present invention,
Abbreviations and contents of the polyphenylene ether of the component (A) other than the above are as follows. A-3: Polyphenylene ether manufactured by Nippon Polyether Co., η _SP /C=0.3 A-4: Polyphenylene ether manufactured by Nippon Polyether Co., η _SP /C=0.6 A-5: Nippon Poly Polyphenylene ether manufactured by Ether Co., η _SP /C=0.4 Here, the reduced viscosity η _SP / C is a value measured at 25 ° C. for a chloroform solution of 0.5 g / dl of polyphenylene ether.

[Epoxy Group-Containing Ethylene Copolymer of Component (B)] Abbreviations and contents of the epoxy group-containing ethylene copolymer used as the component (B) of the thermoplastic resin composition of the present invention are as follows. . B-1: Sumitomo Chemical Co., Ltd. Bond First 7
M, E / GMA / MA = 64/6/30 weight ratio, MFR
= 9 B-2: Sumitomo Chemical Co., Ltd. Bond First 7
L, E / GMA / MA = 67/3/30 weight ratio, MFR
= 9 B-3: Bond First 2 manufactured by Sumitomo Chemical Co., Ltd.
C, E / GMA = 94/6, MFR = 3 B-4: Sumitomo Chemical Co., Ltd. Bond First 2
A, E / GMA / VA = 89/3/8 weight ratio, MFR =
3 Here, E is ethylene, GMA is glycidyl methacrylate, MA is methyl acrylate, and VA is vinyl acetate. The MFR was measured according to JIS K6760 under a load of 2.16 kg and a temperature of 190 ° C. The unit is g / 10 min.

[Aromatic Polycarbonate of Component (C)]
The abbreviations and contents of the aromatic polycarbonate used as the component (C) of the thermoplastic resin composition of the present invention are as follows. C-1: Polycarbonate CAL manufactured by Sumitomo Dow Co., Ltd.
IBRE 300-4, MFR = 4 C-2: Sumitomo Dow Co., Ltd. Polycarbonate CAL
IBRE 300-15, MFR = 15 C-3: Sumitomo Dow Co., Ltd. Polycarbonate CAL
IBRE 300-6, MFR = 6 MFR is 1.2 kg load according to JIS K6760,
It was measured at a temperature of 300 ° C. The unit is g / 10 min.

Examples 1 to 5 and Comparative Examples 1 to 7 The components shown in Table 2 were mixed together with a stabilizer in a Henschel mixer, and PCM-2 type (biaxial extruder) manufactured by Ikegai Tekko KK was used. Use cylinder set temperature 262
After kneading at 80 ° C and a rotation speed of 80 rpm, it is molded,
The physical properties of the obtained molded product were measured. The results are shown in Table 2.

Composition of Comparative Example 2 (A-2: B-1 = 9
0:10) was obtained by the above method and then the component C (C-
FIG. 3 shows the relationship between the Izod impact strength and the weight% of the component C (C-1) of the composition of the present invention obtained by adding and mixing 1) and kneading under the above conditions.

Examples 6 and 7 and Comparative Example 8 TEX44 SS-30BW-2V manufactured by Nippon Steel Co., Ltd.
Cylinder setting temperature 265 using the mold twin screw extruder
Kneading was carried out at a temperature of 300 ° C. and a screw rotation speed of 300 rpm.
At that time, the component (A) was supplied from the first feed port, and the components (B) and (C) were supplied from the second feed port in the compositions shown in Table 3 and kneaded. The obtained pellets were measured for physical properties after molding. The results are shown in Table 3.

From Tables 2 and 3 and FIG. 3, the thermoplastic resin composition of the present invention was excellent in mechanical properties such as heat resistance and impact resistance, molding processability, dimensional stability, and particularly excellent impact resistance. It turns out that it is a thermoplastic resin composition.

[0073]

[Table 2]

[0074]

[Table 3]

[0075]

The thermoplastic resin composition of the present invention is a resin composition having excellent mechanical properties, particularly impact resistance, high heat resistance, dimensional stability, moldability and appearance, and has such properties. It is used for molded products, sheets, tubes, films, fibers, laminates, coating materials and the like by making full use of injection molding and extrusion molding.

In particular, automobile parts such as bumpers, glove boxes, console boxes, brake oil tanks, radiator grills, cooling fans, lamp housings, air cleaners, instrument panels, fenders, door trims, rear end trims, door panels, wheel covers, It is used for interior / exterior materials such as side protectors, air intakes, garnishes, trunk lids, bonnets, sirocco fans, roofs, and mechanical parts that require heat resistance. Further, it is used as a motorcycle component, for example, a covering material, a muffler cover, a leg shield, or the like.

Further, it is used for a fiber optic cable coating material, and also for electric and electronic parts such as a housing, a chassis, a connector, a printed circuit board, a pulley, and other parts required to have excellent mechanical properties and heat resistance.

[Brief description of drawings]

FIG. 1 Two-dimensional H of polyphenylene ether (A-1)
1 shows an MQC NMR spectrum diagram.

FIG. 2 shows a two-dimensional HMQC NMR spectrum of modified polyphenylene ether (A-2).

FIG. 3 shows the relationship between the fraction of C-1 component in the thermoplastic resin composition of the present invention and Izod impact strength.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical indication C08L 69/00 LPQ

Claims (1)

[Claims] 1. A polyphenylene ether represented by the following structural unit (1): (In the formula, R ₁ and R ₂ are each independently selected from hydrogen and a hydrocarbon group having 1 to 20 carbon atoms.) In the polyphenylene ether having a number average degree of polymerization of 20 to 1200, the number average polymerization is When the degree is X, the methyl group at the 2-position and / or the 6-position of the phenylene group is 0.
A modified polyphenylene ether modified with an aminomethyl group in a ratio of 02 / X to 1 / X, (B) (a) an ethylene unit of 50 to 99% by weight, (b)
0.1 to 30% by weight of unsaturated carboxylic acid glycidyl ester units or unsaturated glycidyl ether units, (c)
Ethylenically unsaturated ester compound unit 0 to 50% by weight
An epoxy group-containing ethylene copolymer consisting of (C) and an aromatic polycarbonate (C) as the main components, and the blending ratio of the component (A) and the component (B) is 100.
The component (B) is 0.1 to 70 parts by weight with respect to parts by weight, and the weight sum of the component (A) and the component (B) and the ratio of the component (C) are (component (A) + component (B)). ) Is 1 to 99% by weight, and the component (C) is 99 to 1% by weight.