JPH08113702A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE: To obtain an inexpensive thermoplastic resin composition useful as a bumper, taking advantage of excellent mechanical properties and heat resistance, having improved moldability and processability and impact resistance, by blending a polyphenylene ether, etc., in a specific ratio. CONSTITUTION: This thermoplastic resin composition consists essentially of (A) a polyphenylene ether, (B) a (rubber-modified) alkenyl aromatic resin, (C) an epoxy group-containing ethylene copolymer comprising (i) 50-99wt.% of an ethylene unit, (ii) 0.1-30wt.% of an unsaturated carboxylic acid glycidyl ester unit or an unsaturated glycidyl ether unit and (iii) 0-50wt.% of an ethylenic unsaturated ester compound unit and (D) an aromatic polycarbonate in the ratios of 1-99wt.% of the component A and 99-1wt.% of the component B, 0.1-70 pts.wt. of the component D based on 100 pts.wt. of the total weight of the component A and the component C and the ratio of the component D to the component A to the component C is 99-1wt.% of the component D to 1-99wt.% of the component A to the component C. The component A is preferably composed of a structural unit of the formula.

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. 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 molding processability 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, aromatic polycarbonate and an unsaturated carboxylic acid derivative, and Japanese Patent Publication No. 5-14740 discloses 2,6-dialkylphenol and 2,3,6. -Compositions of polyphenylene ethers which are copolymers with trialkylphenols and aromatic polycarbonates are disclosed. Further, Japanese Patent Publication No. 61-29984 discloses a composition prepared by blending a polyphenylene ether with a copolymer of olefins and glycidyl methacrylate or glycidyl acrylate. However, in each case, the physical properties of the composition were not always sufficient.

[0006]

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. To provide a composition.

[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,
(A') alkenyl aromatic resin and/or rubber-modified alkenyl aromatic resin, (B) (a) ethylene unit is 5
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) Regarding the ratio with the component (A′), the component (A) is 1 to 99% by weight, the component (A′) is 99 to 1% by weight, and the weight sum of the component (A) and the component (B) is 100. Component (C) is 0.1 to 70 parts by weight with respect to parts by weight, and component (A) and component (A′)
As for the ratio of the weight sum of the component (B) and the component (C), the weight sum of the component (A), the component (A′) and the component (B) is 1 to 99% by weight, and the component (C) is The thermoplastic resin composition is 99 to 1% by weight. [2] Polyphenylene ether in which the component (A) is 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.
The thermoplastic resin composition according to [1], wherein the ratio of 02/X to 1/X is a modified polyphenylene ether modified with an aminomethyl group.

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 ₃ , R ₄ , R ₅ , R ₆ and R ₇ 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 polyphenylene ether obtained by oxidative polymerization with gas.

In the phenol compound represented by the above general formula (2), specific examples of R ₃ , R ₄ , R ₅ , R ₆ and R ₇ 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-
t-Butylphenol, thymol, 2-methyl-6-allylphenol and the like can be mentioned.

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

Component (A) of the thermoplastic resin composition of the present invention
The polymer of 2,6-dimethylphenol or 2,6-diphenylphenol, as well as a large amount of 2,6-dimethylphenol and a small amount of 3-methyl-6-t-butylphenol, or 2,3, as the polyphenylene ether of
A copolymer with 6-trimethylphenol is preferred. A polymer of 2,6-dimethylphenol is particularly preferable.

Further, as the polyphenylene ether of the component (A), a small amount of a phenol compound other than the above general formula (2), such as bisphenol-A, tetrabromobisphenol-A, resorcin, hydroquinone,
A copolymer of a polyhydroxy aromatic compound such as a 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. A modified polyphenylene ether having a structural unit in which a part of the methyl group at the position is modified to an aminomethyl group (—CH ₂ NH ₂ ) is preferable. 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.

Next, as a method for producing the polyphenylene ether of the component (A), the following general formula (3) is used.

[Chemical 4] (In the formula, R ₈ , R ₉ , and R ₁₀ 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 (4)

[0019]

[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 by forming a ring).
It is preferable to carry out the polymerization in an amount of 001 to 0.2 mol, preferably 0.005 to 0.05 mol.

If the amount used is less than 0.001 mol per mol of the nuclear-substituted phenols, polyphenylene ether of excellent quality cannot be obtained, and if it exceeds 0.2 mol, a practical molecular weight is obtained. This is not preferable because the polyphenylene ether can not be obtained. In this way, a polyphenylene ether having the amine in the side chain can be obtained. The nuclear-substituted phenols can be used alone or in combination of two or more.

Next, as the amines represented by the general formula (4), specifically, n-propylamine, iso-propylamine, n-butylamine, iso-butylamine, sec-butylamine, n-hexylamine, n-
1 such as octylamine, 2-ethylhexylamine, cyclohexylamine, laurylamine, benzylamine, etc.
Examples include secondary amines 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 (4)
Is also equivalent to the amine represented by the general formula (4), 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 (4) 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 consisting 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 hydroxides, alkoxides or phenoxides of Group IA metals, hydroxides of Group IIA metals, oxides, alkanolamines, and catalyst systems containing amines are used. There is a method of doing.

In this way, the following general formula (5)

[Chemical 6] (In the formula, the definitions of Q ₁ and Q ₂ are the same as the definition in the general formula (3).) A structure in which the methyl group at the 2-position and/or the 6-position of the phenylene group is modified by the group represented by A polyphenylene ether having units 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.

Component (A) of the thermoplastic resin composition of the present invention
As a modified polyphenylene obtained by melting and kneading the polyphenylene ether having a secondary or tertiary amine bonded to the 2-position and/or 6-position methyl groups of the phenylene group thus obtained while devolatilizing. Ether can be used. The melt kneading is performed at a cylinder set temperature of 200 to 300° C., preferably 230 to 280.
It is better to carry out at ℃. If the cylinder set temperature is lower than 200°C, 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.

The modified polyphenylene ether has a number average degree of polymerization of X, preferably 0.02/X to 1/ of the methyl group at the 2-position and/or the 6-position of the phenylene group.
X, more preferably 0.05/X to 1/X modified with an aminomethyl group, is preferable because it is more excellent in heat resistance and mechanical properties when used as a component of the resin composition.

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 component (B).
Rich in reactivity with epoxy group-containing ethylene copolymer of
It is preferable because it gives a thermoplastic resin composition having good properties.

It is also possible to blend a radical initiator at the time of melt-kneading and melt-knead. Further, the polyphenylene ether may be previously blended with a radical initiator 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
The reduced viscosity η _{SP /} c (value measured at 25° C. for a chloroform solution of 0.5 g/dl) of the polyphenylene ether and the modified polyphenylene ether is 0.30.
The range of ˜0.65 dl/g is preferred. η _SP /c is 0.
If it is less than 30 dl/g, the heat resistance of the composition is significantly lowered,
Further, when η _SP /c exceeds 0.65 dl/g, the moldability of the composition is deteriorated, which is not preferable.

The alkenyl aromatic resin as the component (A') in the present invention is represented by the general formula

[Chemical 7] (In the formula, R represents hydrogen, a lower alkyl group (for example, an alkyl group having 1 to 4 carbon atoms) or halogen, Z represents hydrogen, a vinyl group, a halogen, a hydroxyl group or a lower alkyl group, and p is 0 or 1 Represents an integer of 5) and has at least 25% by weight of polymer units derived from monomers having Specific examples of the alkenyl aromatic resin include homopolymers of polystyrene, polychlorostyrene, poly-α-methylstyrene and the like, and copolymers thereof, styrene-containing copolymers such as styrene-acrylonitrile copolymer, styrene-divinyl. Benzene copolymer, styrene-acrylonitrile-α-
Methyl styrene copolymer etc. are mentioned. Of these, preferred are homopolystyrene and styrene-α-
They are a methylstyrene copolymer, a styrene-acrylonitrile copolymer, a styrene-α-chlorostyrene copolymer, and a styrene-methylmethacrylate copolymer. Especially preferred is homopolystyrene.

The rubber-modified alkenyl aromatic resin in the present invention refers to one having a two-phase system in which rubber particles are dispersed in an alkenyl aromatic resin matrix. Examples of this production method include mechanical mixing of a rubber and an alkenyl aromatic resin, which will be described later, or a method of dissolving the rubber in the alkenyl aromatic monomer and then polymerizing the alkenyl aromatic monomer. The latter method is industrially produced as so-called high impact polystyrene. Further, a mixture obtained by mixing the rubber obtained by the latter method with a rubber and/or an alkenyl aromatic resin is also included in the rubber-modified alkenyl aromatic resin in the present invention.

The rubber in the present invention means natural and synthetic polymers which are elastic at room temperature, for example, 20 to 25°C. Specific examples thereof include natural rubber, diene rubber (for example, polybutadiene, polyisoprene, polychloroprene) and a copolymer of a diene and a vinyl monomer (for example, styrene-butadiene random copolymer, styrene-butadiene block copolymer, Styrene-Butadiene-Styrene block copolymer, polybutadiene graft-copolymerized with styrene, butadiene-
Acrylonitrile copolymer), polyisobutylene and copolymers of isobutylene and butadiene or isoprene, ethylene-propylene copolymer and ethylene-propylene-diene copolymer, thiochol rubber, polysulfide rubber, acrylic rubber, polyurethane rubber, polyether Examples thereof include rubber and epichlorohydrin rubber. Further, various modified products of these rubbers are also included. (For example, hydroxy- or carboxy-terminated polybutadiene, partially hydrogenated styrene-butadiene-styrene block copolymers) or diene rubbers and copolymers of dienes and vinyl compounds, double bond microstructures (vinyl groups, cis- 1.4-bond, trans1.4-bond)
Different rubbers are also used as the rubber of the present invention. Preferred rubbers include polybutadiene and butadiene 40
To 100 wt% and styrene 60 to 0 wt%, butadiene 65 to 82 wt% and acrylonitrile 35 to 18 wt%, styrene-butadiene, and styrene-butadiene-styrene block copolymer (All linear block copolymers, radial block copolymers, etc. are included.), styrene graft polybutadiene (polybutadiene or butadiene-styrene copolymer latex to which styrene is added and emulsion-polymerized by a radical initiator), There are ethylene-propylene copolymers and ethylene-propylene-diene copolymers.

Component (B) of the thermoplastic resin composition of the present invention
The epoxy group-containing ethylene copolymer is (a) ethylene unit of 50 to 99% by weight, (b) unsaturated carboxylic acid glycidyl ester unit or 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 (6) and (7), respectively.

[0034]

[Chemical 8] (R is a C2-C13 hydrocarbon group having an ethylenically unsaturated bond.)

[0035]

[Chemical 9] (The definition of R is the same as the definition in the general formula (6),
X is -CH ₂ -O- or

[Chemical 10] Is. Specific examples thereof include glycidyl acrylate, glycidyl methacrylate, itaconic acid glycidyl ester, allyl glycidyl ether, 2-methylallyl glycidyl ether, and styrene-p-glycidyl ether.

Further, the epoxy group-containing ethylene copolymer used in the present invention includes a ternary or more ternary copolymer of unsaturated carboxylic acid glycidyl ester or unsaturated glycidyl ether and ethylene and (c) ethylenic unsaturated ester compound. Polymers can also be used. Examples of the ethylenic unsaturated ester compound (c) include vinyl acetate, vinyl propionate, methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate, carboxylic acid vinyl esters such as butyl methacrylate, Examples include α,β-unsaturated carboxylic acid alkyl esters and the like. Especially vinyl acetate, methyl acrylate,
Ethyl acrylate is preferred.

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. Further, the melt index of the epoxy group-containing ethylene copolymer (JIS K6760, 190
C.) is preferably 0.5 to 100 g/10 minutes, more preferably 2 to 50 g/10 minutes. The melt index may be out of this range, but if the melt index exceeds 100 g/10 minutes, it is not preferable in terms of mechanical properties when the composition is formed, and if it is less than 0.5 g/10 minutes, the component (A) is The compatibility with the modified polyphenylene ether 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 atm and 100 to 300° C. in the presence or absence of a suitable solvent or chain transfer agent. It is produced by the method of copolymerizing below. It can also be produced by a method in which an unsaturated epoxy compound and a radical generator are mixed with polyethylene and melt graft copolymerization is performed 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 (8) obtained by reacting a dihydric phenol with a carbonate precursor such as phosgene, haloformate, and carbonic acid ester.

[Chemical 11] (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. These specific polymerization methods 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 exemplified by the polycarbonate-styrene block copolymers disclosed in JP-B-48-25076 can also be used.

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

The ratio of the component (A) to the component (A') in the thermoplastic resin composition of the present invention is such that the component (A) is 1-9.
9% by weight, the component (A′) is 99 to 1% by weight, and the component (C) is 0.1 to 70 relative to 100 parts by weight of the total weight of the component (A) and the component (A′). The weight ratio is preferably 1 to 40 parts by weight, and the weight ratio of the component (A), the component (A′) and the component (B) to the component (C) is the same as that of the component (A) and the component (A). ') and component (B) are in a weight sum of 1 to 99% by weight, and component (C) is in a range of 99 to 1% by weight.

Regarding the ratio of the component (A) to the component (A'), when the component (A) exceeds 99% by weight, the resin composition obtained has little effect of improving molding processability and impact resistance. If (A) is less than 1% by weight, the heat resistance of the resin composition is insufficient, which is not preferable. Further, when the amount of the component (B) is less than 0.1 part by weight based on 100 parts by weight of the total weight of the component (A) and the component (A'), the impact resistance improving effect of the resin composition is not recognized. Further, if the amount of the component (B) exceeds 70 parts by weight, the heat resistance and rigidity of the resin composition decrease, which is not preferable. Further, regarding the weight ratio of the component (A), the component (A′) and the component (B) and the ratio of the component (C), the weight sum of the component (A), the component (A′) and the component (B) is 1 If it is less than wt% or exceeds 99 wt%, the heat resistance and molding processability of the obtained resin composition may become insufficient, which is not preferable.

As a method for producing the thermoplastic resin composition of the present invention, for example, polyphenylene ether is melted and kneaded while devolatilizing using a kneader, and then the component (A') is added thereto.
The alkenyl aromatic resin and/or the rubber-modified alkenyl aromatic resin, component (B), the epoxy group-containing ethylene copolymer, and component (C), the aromatic polycarbonate are blended and kneaded together to produce the composition. Method, or modified polyphenylene ether of component (A), alkenyl aromatic resin and/or rubber modified alkenyl aromatic resin of component (A'), epoxy group-containing ethylene copolymer of component (B) and component (C) Examples include a method of dissolving each aromatic polycarbonate in a solvent and mixing the components in a solution state, and evaporating the solvent, or charging the aromatic polycarbonate into a solvent in which the resin component is not dissolved to precipitate the resin composition.

As a preferred manufacturing method, polyphenylene ether is charged from the first feed port of the kneading extruder,
After producing the modified polyphenylene ether by melt-kneading the polyphenylene ether in the kneading extruder between the first feed port and the second feed port, the alkenyl of the component (A′) is fed from the second feed port of the extrusion kneading machine. Aromatic resin and/or rubber-modified alkenyl aromatic resin, epoxy group-containing ethylene copolymer of component (B), component (C)
And the modified phenyl aromatic ether and/or rubber modified alkenyl aromatic resin of component (A′), the epoxy group-containing ethylene copolymer and the aromatic polycarbonate. A method for producing the thermoplastic resin composition of the present invention by melt-kneading in a kneading extruder is also included.

The melt-kneading is carried out at a cylinder set temperature of 210.
˜340° C., preferably 260 to 300° C. When the cylinder set temperature is lower than 210°C, the raw material polyphenylene ether has poor moldability, and when the cylinder set temperature exceeds 300°C, the polyphenylene ether and the epoxy group-containing ethylene copolymer may be 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.

A radical initiator can be used in the melt-kneading. The radical initiator is not particularly limited, and a desired one can be appropriately selected and used. For example, various radical initiators such as those described in JP-A-2-160856 can be mentioned, including azo compounds such as 2,2′-azobisisobutyronitonyl.

In the thermoplastic resin composition of the present invention,
Inorganic fillers are used if desired. Such inorganic fillers include calcium carbonate, talc, clay, silica, magnesium carbonate, barium sulfate, titanium oxide, alumina, gypsum, glass fiber, carbon fiber, alumina fiber,
Examples thereof include aluminum borate whiskers and potassium titanate fibers.

If necessary, the thermoplastic resin composition of the present invention may further contain an antioxidant, a heat stabilizer, a light stabilizer, a flame retardant, a lubricant, an antistatic agent, an inorganic or organic colorant, and a rust inhibitor. 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.

[0051]

[Determination of amine in raw material polyphenylene ether and modified polyphenylene ether]

-Nitrogen content in total amine: Approximately 1 g of a sample was weighed and dissolved in 50 cc of chloroform, and after adding 5 cc of acetic acid,
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 the 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 replaced with a solution of 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. The polyphenylene ether peaks are mainly attributed to Macromolecules (Macromoles).
, 23, 1318-1329 (1990)
Year) paper.

[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, a molding temperature of 270°C to 30
The molding was performed at 0° C. and a mold temperature of 80 to 110° C. by injection molding. Melt index (MI) 10 kg load and 28 temperature according to JIS K6760
It was measured at 0°C. The unit is g/10 min. -Tensile test ASTM No. 4 tensile dumbbell is molded and ASTM D63
Tensile strength was measured according to 8.

Bending Elastic Modulus A 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 and -30°C.

[Polyphenylene ether of component (A),
Modified Polyphenylene Ether] The abbreviations and contents of the polyphenylene ether and modified polyphenylene ether used in the thermoplastic resin composition of the present invention are as follows. Abbreviations: Content AA-1: Polyphenylene ether manufactured by Nippon Polyether Co., Ltd., η _sp /C=0.42 AA-2: PCM-30 manufactured by Ikegai Tekko KK, and the inside of the hopper was under a nitrogen atmosphere. Then, add polyphenylene ether AA-1 and set the cylinder temperature to 27.
Melt kneading was performed while devolatilization was performed at 3° C. and a screw rotation speed of 80 rpm. The modified polyphenylene ether thus obtained is abbreviated as AA-2.

Table 1 shows the nitrogen contents of various amines of AA-2. Compared with polyphenylene ether AA-1,
It can be seen that a modified polyphenylene ether in which the tertiary amine was significantly reduced and the primary amine was significantly increased was obtained.

[0061]

[Table 1]

Two-dimensional HMQC of AA-1 and AA-2
The NMR 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.

The attributions of the main peaks are as follows.
In the two-dimensional HMQC NMR spectrum of AA-1, the signals having chemical shifts of ¹³ C:58.1 ppm and ¹ H:3.62 ppm indicated by arrows are shown in the literature Macromol.
ecules, 23 , 1318 (1990), the carbon and hydrogen of the methylene group at the 2-position or 6-position of the phenylene group of the polyphenylene ether having dibutylamine bonded thereto, respectively. The intensity of this signal is AA-
2 markedly decreased and was newly shown by the arrow ¹³ C: 36.3
A signal having a chemical shift of ppm, ¹ H:3.89 ppm is observed. Reference Phytochem. , 1
8 , 1547 (1979), the chemical shift of the carbon of the methylene group of the benzyl group to which the primary amine is bound is 39.
Showing 4 ppm, and reference Aldrich Li
blurry of NMR Spectra, II , 1
066 (1983), the chemical shift of hydrogen of the methylene group of the benzyl group to which the primary amine is bonded is 3.9 pp.
It is known to indicate m. Therefore, the signals having the chemical shifts of ¹³ C: 36.3 ppm and ¹ H: 3.89 ppm observed in AA-2 are the methylenes at the 2- or 6-position of the phenylene group of the polyphenylene ether to which the primary amine is bound. Assigned to the carbon and hydrogen of the radical. 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. AA-3: Polyphenylene ether manufactured by Nippon Polyether Co., Ltd., η _SP /C=0.3 Here, the reduced viscosity η _SP /C is a value measured at 25° C. for a chloroform solution of polyphenylene ether of 0.5 g/dl. Is.

[Alkenyl aromatic resin and/or rubber-modified alkenyl aromatic resin of component (A')] The abbreviations and contents of the alkenyl aromatic resin and/or rubber-modified alkenyl aromatic resin used are as follows. Abbreviation: Content A'-1: High-impact polystyrene S-Bright 500
HS [Sumitomo Chemical Co., Ltd.] A'-2: Polystyrene Esbright 7M [Sumitomo Chemical Co., Ltd.] A'-3: Ikegai Tekko Co., Ltd. twin-screw extruder PCM-2 type Cylinder setting temperature 190 ℃, screw rotation speed 90 rpm, A'-2 100 parts by weight, styrene-
Butadiene-styrene copolymer Kraton TR110
6.7 parts by weight of 2 (manufactured by Shell Kagaku Co., Ltd.) were mixed and melt-kneaded. The obtained resin is abbreviated as A'-3.

[Epoxy Group-Containing Ethylene Copolymer of Component (B)] The 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
L, E/GMA/MA=67/3/30 weight ratio, MFR
=9 B-2: Sumitomo Chemical Co., Ltd. Bond First 2
C, E/GMA=94/6, MFR=3 Here, E is ethylene, GMA is glycidyl methacrylate, and MA is methyl acrylate. Also, MFR
Was measured at a load of 2.16 kg and a temperature of 190° C. according to JIS K6760. 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. CC-1: Polycarbonate CA manufactured by Sumitomo Dow Co., Ltd.
LIBRE 200-15, MFR=15 CC-2: Sumitomo Dow Co., Ltd. Polycarbonate CA
LIBRE 200-3, MFR=3 MFR is 1.2 kg load according to JIS K6760,
It was measured at a temperature of 190°C. The unit is g/10 min.

Examples 1 to 6 and Comparative Examples 1 to 3 The components shown in Table 2 were mixed together with a stabilizer in a Henschel mixer, and PCM-30 manufactured by Ikegai Tekko KK
Cylinder set temperature 257 using a mold (twin screw extruder)
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. It can be seen that the thermoplastic resin composition of the present invention is excellent in molding processability and is inexpensive, with well-balanced heat resistance and mechanical properties.

[0069]

[Table 2]

[0070]

INDUSTRIAL APPLICABILITY The thermoplastic resin composition of the present invention is an inexpensive thermoplastic resin which utilizes the excellent properties of polyphenylene ether such as mechanical properties and heat resistance, and has improved molding processability and impact resistance. The composition is used for molded articles, sheets, tubes, films, fibers, laminates, coating materials and the like by injection molding or extrusion molding by making use of such characteristics.

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 shows a two-dimensional HMQC NMR spectrum of polyphenylene ether (AA-1).

FIG. 2: Modified polyphenylene ether (AA-2)-2
Fig. 3 shows a dimensional HMQC NMR spectrum diagram.

Claims (2)

[Claims] 1. A polyphenylene ether (A), (A')
Alkenyl aromatic resin and/or rubber-modified alkenyl aromatic resin, (B) (a) ethylene unit of 50 to 99
% By weight, (b) 0.1 to 30 unsaturated carboxylic acid glycidyl ester units or unsaturated glycidyl ether units.
Wt%, (c) an ethylenically unsaturated ester compound unit is an epoxy group-containing ethylene copolymer consisting of 0 to 50 wt%, and (C) an aromatic polycarbonate as a main component, and the component (A) and the component (A The ratio of the component (A) is 1 to 99% by weight, and the ratio of the component (A') is 9).
9 to 1% by weight, and the component (C) is 0.1 to 70 parts by weight with respect to 100 parts by weight of the total weight of the components (A) and (B). ') and ingredients (B)
For the ratio of the weight sum of the component (C) to the component (C),
A thermoplastic resin composition in which 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. 2. A polyphenylene ether whose component (A) is 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.
The thermoplastic resin composition according to claim 1, wherein the ratio of 02/X to 1/X is a modified polyphenylene ether modified with an aminomethyl group.