JP2985903B2 - Thermoplastic resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermoplastic resin composition having improved heat processing rigidity, comprising a polyphenylene ether mixture and a polyamide as main components, having improved moldability.

[0002]

2. Description of the Related Art By filling glass fibers into a thermoplastic resin, the rigidity and heat resistance of the thermoplastic resin can be improved. In the field of so-called engineering plastics, for example, when polyamide is filled with glass fibers, the above effects can be expected. However, when a polyamide alone is filled with glass fibers, there remains a problem that water absorption is large. In addition, when glass fiber is filled into a typical engineering plastic, polyphenylene ether,
Defects such as poor fluidity and moldability remain.

On the other hand, when glass fibers are filled in a resin composition composed of polyphenylene ether and polyamide, the advantages of each of polyphenylene ether, polyamide, and glass fibers are utilized, that is, high rigidity, high heat resistance, and solvent resistance Is excellent, it is expected to be a material with good moldability, however, also in this case, the moldability, ie, fluidity, has not been greatly improved in the past, and particularly, the wall thickness is less than 0.4 mm. It has been found that a thin molded product is likely to be actually short shot in the injection molding process.

[0004]

Although the conventional thermoplastic resin has excellent rigidity at high temperatures, it has a problem in that the moldability is inferior as described above. An object of the present invention is to improve the above and provide a thermoplastic resin composition having excellent heat resistance rigidity and markedly improved moldability.

[0005]

Means for Solving the Problems The present invention has been found to improve the moldability of a resin composition by combining high-viscosity and low-viscosity polyphenylene ethers and polyamides, and have reached the present invention.

That is, the present invention relates to a high-viscosity polyphenylene ether (A) having an intrinsic viscosity (η _A ) of 0.4 dl / g to 1.0 dl / g and an intrinsic viscosity (η _B ) of 0.25 dl / g.
The low-viscosity polyphenylene ether (B) having a weight ratio (A) / (B) of less than 0.4 dl / g is 10 / 90-9.
A polyphenylene ether, which is a mixture having a ratio of 0/10, is mixed with 30 to 60 parts by weight based on 100 parts by weight of the total of (A), (B) and (C), and has a relative viscosity (η _r ) of 1.0.
To 8.0 parts by weight of the polyamide (C), based on a total of 100 parts by weight of (A), (B) and (C), 40 to 70 parts by weight,
Compound (F) having both an unsaturated group and a polar group in the same molecule
With 0.1 to 10 parts by weight and mineral filler and / or glass fiber (G) based on 100 parts by weight of the total of (A), (B) and (C), with (A), (B) and 0.1 to 10 parts by weight based on 100 parts by weight of (C) in total
Melt flow rate (MF) measured at 80 ° C and 5 kg load
R5) and the flow ratio (FR = MFR5 / MFR2) represented by the ratio of the melt flow rate (MFR2) measured at 280 ° C. under a load of 2.16 kg (FR = MFR5 / MFR2) is 2.5 or more, and the MFR
5 is a thermoplastic resin composition having 30 or more.

<Constituent Components> The polyphenylene ether used in the present invention has the following formula (I):

[0008]

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Wherein n is at least 50, and R ¹ , R ² , R ³ and R ⁴ do not contain a hydrogen atom, a halogen atom and a tertiary α-carbon atom, respectively. A group consisting of a hydrocarbon group, a halohydrocarbon group in which a halogen atom is substituted through at least two carbon atoms, a hydrocarbonoxy group, and a halohydrocarbon oxy group in which a halogen atom is substituted through at least two carbon atoms Represents a monovalent substituent selected from the above.

Examples of the hydrocarbon group containing no tertiary α-carbon atom include lower alkyl groups such as methyl, ethyl, propyl, isopropyl and butyl: alkenyl groups such as vinyl, allyl, butenyl and cyclobutenyl; Aryl groups such as tolyl, xylyl and 2,4,6-trimethylphenyl; aralkyl groups such as benzyl, phenylethyl and phenylpropyl. Examples of the halohydrocarbon group in which a halogen atom is substituted through at least two carbon atoms include, for example, 2-chloroethyl, 2
-Bromoethyl, 2-fluoroethyl, 2,2-dichloroethyl, 2- or 3-bromopropyl, 2,2-difluoro-3-iodopropyl, 2-, 3-, 4- or 5
-Fluoroamyl, 2-chlorovinyl, chloroethylphenyl, ethyl (chloro) phenyl, fluoroxylyl, chloronaphthyl, bromobenzyl and the like.

The hydrocarbon oxy group includes, for example, methoxy, ethoxy, propoxy, butoxy, phenoxy, ethylphenoxy, naphthoxy, methylnaphthoxy, benzyloxy, phenylethoxy, tolylethoxy and the like. Examples of the halohydrocarbon oxy group in which a halogen atom is substituted through at least two carbon atoms include 2-chloroethoxy, 2-bromoethoxy, 2-fluoroethoxy, 2,2-dibromoethoxy, 2- or 3 -Bromopropoxy, chloroethylphenoxy, ethyl (chloro) phenoxy, iodoxylyloxy, chloronaphthoxy, bromobenzyloxy, chlorotolylethoxy and the like.

The polyphenyl ether (I) used in the present invention comprises 2,6-dimethylphenol and 2,3,6
Copolymer of trimethylphenol, copolymer of 2,6-dimethylphenol and 2,3,5,6-tetramethylphenol, copolymer of 2,6-diethylphenol and 2,3,6
-Copolymers such as trimethylphenol copolymers are also included. In addition, styrene-based monomers (for example, styrene, p-methylstyrene,
Modified polyphenylene ethers such as those obtained by graft polymerization of α-methylstyrene or the like may be used.

The method for producing the above-mentioned polyphenylene ether (I) is known, and is described, for example, in US Pat. No. 3,306,687.
No. 4, No. 3,306,875, No. 3,257,357 and No. 3,257,358, and JP-B-52-1.
No. 7,880 and JP-A-50-51197.

Preferred polyphenylene ethers (I) for the purposes of the present invention are poly (2,6-dimethyl-1,1
(4-phenylene ether) and a copolymer of 2,6-dialkylphenol and 2,3,6-trialkylphenol having an alkyl substituent at two ortho positions to the ether oxygen atom.

The polyphenylene ether (I) used in the present invention has an intrinsic viscosity of 0.25 to 1.0 dl / g measured in chloroform at 30.degree. Among them, polyphenylene ether (A) has an intrinsic viscosity of 0.4 to 1.0 dl / g,
The intrinsic viscosity of (B) is 0.25 dl / g or more and 0.4 dl / g.
And preferably the intrinsic viscosity of (A) is from 0.45 to
0.70 dl / g, particularly preferably 0.46 to 0.56 dl / g
The intrinsic viscosity of (B) is preferably from 0.25 to 0.35 dl / g, particularly preferably from 0.30 to 0.35 dl / g. Here, when the intrinsic viscosity of (A) exceeds 1.0 dl / g, the fluidity is extremely deteriorated, and the polyphenylene ether dispersion in the polyamide becomes coarse, leading to a decrease in mechanical strength. Further, if the intrinsic viscosity of (B) is less than 0.25 dl / g, the polyphenylene ether dispersion in the polyamide becomes coarse, and the mechanical strength is extremely low, which is of no practical value.

Next, the polyamide of component (C) has a --CONH-- bond in the polymer main chain and can be heated and melted. Typical examples thereof include nylon-4, nylon-6, nylon-6,6, nylon-4,6, nylon-12, nylon-6,10, and other known aromatic diamines and aromatic dicarboxylic acids. A crystalline or amorphous polyamide containing a monomer component such as the above can be used. Here, the amorphous polyamide refers to a differential scanning calorimeter (D
SC) means substantially no crystallinity measured by SC).

Preferred polyamide (C) is nylon-
6, 6, nylon-6 and amorphous polyamide.

The polyamide (C) used in the present invention has a relative viscosity of 1.0 to 8.0 (measured at 25 ° C. in 98% concentrated sulfuric acid, JIS K 6810), and preferably 1.7.
３3.2. When the relative viscosity is less than 1.0, in addition to low mechanical strength, low-molecular polyamide is volatilized during molding to cause mold contamination, thereby lowering the commercial value of the molded product surface. Further, it is not preferable to use a polyamide having a relative viscosity of more than 8.0, because the molecular weight is reversibly reduced during kneading or molding and the appearance of the product is reduced due to moisture and degradation products generated by decomposition. The polyamide (C) is preferably a combination of a high viscosity polyamide and a low viscosity polyamide.

Those having relative viscosities exceeding 4.0 as high viscosity polyamides and those having a relative viscosity of 4.0 or less as low viscosity polyamides are used in combination. The mixing ratio of the high-viscosity polyamide and the low-viscosity polyamide is 90:10 to 10:90 by weight, preferably 80:20 to 20:80, and particularly preferably 70:30 to 70:80.
The ratio is 30:70. Next, the alkenyl aromatic compound polymer of the component (D) has the following formula (II):

[0020]

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(Wherein, Y represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, Z represents a halogen atom or an alkyl group having 1 to 4 carbon atoms, and r represents O or an integer of 1 to 3). A homopolymer composed of 50% by weight or more of an alkenyl aromatic compound monomer unit or a copolymer with another copolymerizable vinyl monomer, having improved moldability and appearance,
Specific examples of such an alkenyl aromatic compound polymer include polystyrene, polychlorostyrene, polybromostyrene, poly (α-methylstyrene), styrene-acrylonitrile copolymer, styrene-methyl methacrylate copolymer, and the like. Polystyrene is particularly preferred.

The impact modifier of component (E) used in the present invention is a rubbery substance for the purpose of improving impact resistance, and comprises a polyolefin copolymer or an alkenyl aromatic compound and a conjugated diene as a main monomer. Random, graft,
It is a copolymer having a bonding mode such as a block, and may be a copolymer partially containing a crosslinked structure, or a copolymer obtained by partially hydrogenating an aliphatic unsaturated bond derived from a conjugated diene. If the tensile modulus of these elastomers is too high, they will be insufficient as impact modifiers, so the tensile modulus of the elastomers is 5000 kg / cm ² (ASTM D8
82) The following is preferred.

The alkenyl aromatic compound is preferably styrene, but α-methylstyrene, vinyltoluene, lower alkyl-substituted styrene, vinylnaphthalene and the like are also used.

The conjugated diene is particularly preferably butadiene, but may be isoprene or one containing both butadiene and isoprene. Further, as the conjugated diene component, in addition to butadiene and isoprene, cyclopentadiene and other derivatives, lower alkyl-substituted butadiene such as 2,3-dimethylbutadiene, and the like may be contained.

Further, in addition to the above-mentioned diene component, olefinic hydrocarbons such as ethylene, propylene and 1-butene and non-conjugated dienes may be contained as long as the elastomeric properties of the copolymer are not significantly impaired.

The preferred component (E) is a copolymer containing alkenyl aromatic and conjugated diene as main monomer components.
It is a copolymer containing a partially crosslinked structure or a partially hydrogenated aliphatic unsaturated bond derived from a conjugated diene.

A particularly preferred copolymer is a styrene-butadiene-styrene triblock copolymer having a styrene content of 10% by weight or more or a hydride thereof, and one or a combination of two or more of these is used. Can be

Further, maleic acid, maleic acid monomethyl ester, maleic anhydride,
Itaconic acid, itaconic acid monomethyl ester, itaconic anhydride. Α, β-unsaturated dicarboxylic acids such as fumaric acid,
Or endo-bicyclo [2.2.1] -5-heptene-
An alicyclic carboxylic acid such as 2,3-carboxylic acid or a derivative thereof may be graft-polymerized using peroxide, ionizing radiation, ultraviolet light, or the like.

For example, α, β-unsaturated carboxylic acid-modified ethylene-propylene copolymer, same-modified ethylene-butene copolymer, same-modified ethylene-propylene-tertiary component terpolymer, same-modified ethylene-butene A third component terpolymer, the same modified acrylonitrile-butadiene elastomer, the same modified hydrogenated acrylonitrile-butadiene elastomer, the same modified partially crosslinked hydrogenated acrylonitrile elastomer, an alkenyl aromatic compound-isobrene copolymer or / and hydrogenation thereof Things can be used.

Further, core-shell elastomers having a crosslinked acrylic rubber as a core and an alkenyl aromatic polymer as a shell, and / or an α, β-unsaturated carboxylic acid-modified rubber thereof, and the like are listed. -10 ° C
An elastomer having the following applies: Preferably-
Elastomers having a glass transition point between 30 and -100C are selected.

Next, the compound having both an unsaturated group and a polar group in the same molecule of the component (F) may be an unsaturated group, ie, a carbon-carbon double bond or a carbon-carbon triple bond, and a polar group, ie, a polyamide. Is a compound having a carboxyl group or an amino group present at the amide bond or the chain terminal and a functional group exhibiting affinity or chemical reactivity in the same molecule. Examples of such a functional group include a carboxyl group of a carboxylic acid, a group derived from the carboxylic acid, that is, various salts, esters, acid amides, acid anhydrides, imides, acid azides substituted with a hydrogen atom or a hydroxyl group of the carboxyl group. Oxazoline, nitrile, epoxy group, amino group, hydroxyl group or isocyanate ester.

Compounds having both an unsaturated group and a polar group include unsaturated carboxylic acids, unsaturated carboxylic acid derivatives, unsaturated epoxy compounds, unsaturated alcohols, unsaturated amines,
Unsaturated isocyanates are mainly used. Specifically, maleic anhydride, maleic acid, fumaric acid, maleimide, maleic hydrazide, a reaction product of maleic anhydride and a diamine, for example, the following formula (III) and (IV)
Compound represented by

[0033]

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[0034]

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(Wherein R represents an aliphatic group or an aromatic group), such as methylnadic anhydride, dichloromalenic anhydride, maleic amide, itaconic acid and itaconic anhydride; Saturated dicarboxylic acids or derivatives thereof; soybean oil, tung oil, castor oil, linseed oil, hemp seed oil, cottonseed oil, sesame oil, rapeseed oil, peanut oil, camellia oil, olive oil, coconut oil, sardine oil, and other natural oils and fats; epoxidized soybean oil Epoxidized natural fats and oils;

Acrylic acid, butenoic acid, crotonic acid, vinyl acetic acid, methacrylic acid, pentenoic acid, angelic acid, tibric acid, 2-pentenoic acid, 3-pentenoic acid, α-ethylacrylic acid, β-methylcrotonic acid, -Pentenoic acid, 2-hexenoic acid, 2-methyl-2-pentenoic acid, 3
-Methyl-2-pentenoic acid, α-ethylcrotonic acid,
2,2-dimethyl-3-butenoic acid, 2-heptenoic acid, 2
-Octenoic acid, 4-decenoic acid, 9-undenoic acid, 10-
Undecenoic acid, 4-dodecenoic acid, 5-dodeceneic acid, 4-
Tetradecenoic acid, 9-tetradecenoic acid, 9-hexadecenoic acid, 2-octadecenoic acid, 9-octadecenoic acid, eicosenoic acid, docosenoic acid, erucic acid, tetracosenoic acid, mycolipene acid,

2,4-pentadienoic acid, 2,4-hexadienoic acid, diallylacetic acid, geranic acid, 2,4-decadienoic acid, 2,4-dodecadienoic acid, 9,12-hexadecadienoic acid, 9,12- Octadecadienoic acid, hexadecatrienoic acid, linoleic acid, linolenic acid, octadecatrienoic acid, eicosadienoic acid, eicosatrienoic acid,
Eicosatetraenoic acid, ricinoleic acid, eleostearic acid, oleic acid, eicosapentaenoic acid, erucic acid, docosadienoic acid, docosatrienoic acid, docosatetraenoic acid, docosapentaenoic acid, tetracosenoic acid, hexacosenoic acid, hexacodienoic acid, octacocene Unsaturated carboxylic acids such as acids and traacontenic acid; or esters, acid amides and anhydrides of these unsaturated carboxylic acids;

Alternatively, allyl alcohol, crotyl alcohol, methyl vinyl carbinol, allyl carbinol, methyl propenyl carbinol, 4-pentene-1
-Ol, 10-undecene-1-ol, propargyl alcohol, 1,4-pentadien-3-ol,
1,4-hexadiene-3-ol, 3,5-hexadiene-2-ol, _{2,4-hexadiene-1-ol, C n H 2n-5 OH} , C n H 2n-7 OH, C n H 2n _-9 OH
(Where n is a positive integer),
Butene-1,2-diol, 2,5-dimethyl-3-hexene-2,5-diol, 1,5-hexadiene-
Unsaturated alcohols such as 3,4-diol and 2,6-octadiene-4,5-diol;

Alternatively, the unsaturated alcohol such as O
An unsaturated amine in which the H group is replaced by an NH ₂ group; or a low molecular weight substance such as butadiene or isoprene (for example, having an average molecular weight of about 500 to 10,000); or a high molecular weight substance (for example, having an average molecular weight of 10, 000 or more) to which maleic anhydride or phenols are added, or an amino group, a carboxyl group, a hydroxyl group, an epoxy group, or the like is introduced; or allyl isocyanate.

The definition of a compound having both an unsaturated group and a polar group includes, of course, a compound containing two or more unsaturated groups and two or more (same or different) polar groups. It is also possible to use two or more compounds as component (F). Of these, more preferred are maleic anhydride, maleic acid, itaconic anhydride, unsaturated dicarboxylic acids such as itaconic acid and anhydrides thereof, unsaturated alcohols such as oleic alcohol, and epoxidized natural fats and oils, and still more preferably. Are maleic anhydride, maleic acid, oleyl alcohol, epoxidized soybean oil, epoxidized linseed oil, particularly preferably maleic anhydride or a mixture of maleic anhydride and maleic acid.

Next, as the mineral filler of the component (G), an inorganic powder known as an inorganic filler can be used. The shape of the inorganic filler is various such as spherical, cubic, granular, needle-like, plate-like, and fibrous, and any of them can be used.

As such an inorganic filler, a metal element (for example, Fe, Na, or the like) in Groups I to VIII of the periodic table is used.
K, Cu, Mg, Ca, Zn, Ba, Al, Ti) or simple substance of silicon element, oxide, hydroxide, carbonate, sulfate, silicate, sulfite or various clay minerals composed of these compounds There are specifically, for example, titanium oxide,
Zinc oxide, barium sulfate, silica, calcium carbonate, iron oxide, alumina, calcium titanate, aluminum hydroxide, magnesium hydroxide, calcium hydroxide, magnesium carbonate, calcium sulfate, sodium sulfate, calcium sulfite, calcium silicate, Kurewo Last night, glass beads, glass powder, silica sand, silica stone,
Quartz powder, whitebait, diatomaceous earth, white carbon, iron powder, aluminum powder and the like can be mentioned, and these may be used in combination.

These inorganic fillers may be used without any treatment, but for the purpose of increasing the affinity or interfacial bonding force with the resin, an inorganic surface treating agent, a higher fatty acid or an ester thereof,
Derivatives such as salts (eg, stearic acid, oleic acid, palmitic acid, calcium stearate, magnesium stearate, aluminum stearate, stearic acid amide, ethyl stearate, methyl stearate, calcium oleate, oleic amide, oleic acid Ethyl ester, calcium palmitate, palmitic acid amide, palmitic acid ethyl ester, or a coupling agent (eg, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane, γ-chloropropyltrimethoxysilane, γ-amino) Propyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, β- (3,4
-Epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, or the like; or a titanium coupling agent (for example, isopropyltriisostyaroyl titanate, isopropyltrilauryl myristyl titanate, isopropylisostearoyl dimethacryl titanate, isopropyl) Tridiisooctyl phosphate titanate).

Among the components (G) used in the present invention, glass fibers having an average diameter of 3 to 20 μm further improve the balance of physical properties (heat stiffness, impact strength), and warp and reheat during molding. It is preferable in that the warpage is further reduced. The method for producing the glass fiber is, for example, as follows. First, the melted glass is formed into glass balls of a predetermined size called marble, which are softened by heating in a spinning furnace called pushing, and are allowed to flow down from a number of nozzles of the furnace table. While stretching, the sizing agent is adhered by immersion in a sizing agent coating device provided in the middle of the sizing agent, bundled, dried and wound up by a rotating drum. At this time, the average diameter of the glass fibers is adjusted to a predetermined size by adjusting the nozzle diameter, the take-up speed, the take-off atmosphere temperature, and the like.

Although the length of the glass fiber is not specified, roving supply, chopped strand of about 1 to 8 mm, and the like are preferable. In this case, the number of convergence is usually 1
00-5000 are preferable. Also, after kneading to polyamide, if the average length in the polyamide is 0.1 mm or more, so-called milled fiber,
A crushed product of a strand called glass powder may be used, or a sliver of a continuous single fiber type may be used. The composition of the raw glass is preferably non-alkali, and one example is E glass.

If the average diameter of the glass fibers exceeds 20 μm, the degree of improvement in the mechanical strength of the composition becomes small, and the amount of warpage in the molding becomes large, which is not preferable. Here, the average diameter is observed by an electron microscope or the like, and “average” indicates a number average.

Here, the sizing agent usually comprises a film forming agent, a surfactant, a softening agent, an antistatic agent or a lubricant, but may be a surface treating agent alone.

When these glass fibers are used, various coupling agents can be used for the purpose of increasing the affinity with the resin, that is, the interfacial bonding force. Usually, a silane-based, chrome-based, or titanium-based coupling agent is used. Among them, epoxy silanes such as γ-glycidoxypropyltrimethoxysilane; vinyl silanes such as vinyl trichlorosilane; γ-aminopropyl triethoxy silane It is preferable to include a silane coupling agent such as aminosilane. At this time, it is possible to improve the mechanical strength and kneadability by combining the treatment with various surfactants such as nonionic, cationic and anionic types and dispersants such as fatty acids, metal soaps and various resins. Is preferred.

<Composition Ratio of Constituent Components> Regarding the blending ratio of each component in the thermoplastic resin composition of the present invention, the component (A), (B) and (C) were added to 100 parts by weight in total. The total amount of components (A) and (B) is from 30 to 6
0 parts by weight, preferably 35 to 55 parts by weight, particularly preferably 35 to 50 parts by weight. The weight ratio of (A) / (B) is 10/90 to 90/10, preferably 20/90.
/ 80-80 / 20, particularly preferably 30 / 70-60
/ 40.

The intrinsic viscosities η _A and η _{B of the} components (A) and (B) and the respective contents [P _A =
(A) / {(A) + (B)}] and [P _B = (B) /
{(A) + (B)}] is the expression 0.1 ≦ η _A −η _B ≦ 0.8
It is preferable to satisfy the condition of 0.1 ≦ P _B −P _A ≦ 0.8. Component (C) comprises components (A), (B) and (C)
40 to 70 parts by weight for a total of 100 parts by weight of
Preferably 45 to 65 parts by weight, particularly preferably 50 to 6 parts by weight.
5 parts by weight.

When the component (D) is added, the component (A)
0.1 to 100 parts by weight of the total of (B) and (C)
20 parts, preferably 0.5 to 10 parts. When the component (E) is added, 0.1 parts by weight of the total (100 parts by weight) is added.
It is 1 to 50 parts by weight, preferably 0.5 to 30 parts. Component (F) is added in an amount of 0.1 to 100 parts by weight in total.
10 parts by weight, preferably 0.5 to 1.5 parts by weight, particularly preferably 0.9 to 1.1 parts by weight. Component (G) is 5 to 100 parts by weight, preferably 15 to 80 parts by weight, particularly preferably 2 to 100 parts by weight.
0 to 80 parts by weight.

The total amount of the components (A) and (B) was 3 parts per 100 parts by weight of the total of the components (A), (B) and (C).
If the amount is less than 0 parts by weight, the heat resistance of the final composition is unsatisfactory,
If it exceeds 60 parts by weight, the moldability and impact strength of the final composition will be unsatisfactory. Component (C) is composed of components (A) and (B)
If it is less than 40 parts by weight with respect to the total of 100 parts by weight of (C) and (C), the moldability will be insufficient, and if it exceeds 70 parts by weight, the heat resistance will be insufficient. Further, component (D) is composed of components (A) and (B)
When the amount exceeds 20 parts by weight with respect to the total of 100 parts by weight of (C) and (C), the heat resistance of the final composition becomes unsatisfactory. When the component (E) exceeds 50 parts by weight based on 100 parts by weight of the total of the components (A), (B) and (C), heat resistance and rigidity are insufficient. If the component (F) is less than 0.1 part by weight based on 100 parts by weight, the impact resistance of the final composition is insufficient, and if it exceeds 10 parts by weight, there is a problem in appearance of a molded article of the final composition. If the component (G) is less than 5 parts by weight with respect to the total of 100 parts by weight of the components (A), (B) and (C), rigidity and heat resistance are insufficient, and if it exceeds 100 parts by weight, moldability is deteriorated. The manufacture of the product itself becomes difficult.

[0053] The thermoplastic resin composition of the present invention comprises 280
° C, melt flow rate (MFR) measured at 5 kg load
5) The flow ratio (FR = MFR5 / MFR2) represented by the ratio of the melt flow rate (MFR2) measured at 280 ° C. under a load of 2.16 kg is 2.5 or more, and the MFR
5 needs to be 30 or more, and when FR is less than 2.5 or MFR5 is less than 30, the moldability is unsatisfactory. The composition according to the present invention is, as long as the object of the present invention is not impaired, a thermoplastic or thermosetting resin other than the above-mentioned polymer component, a rubber component antioxidant, a weather resistance improver, and a nucleating agent, if necessary. And components such as slip agents, inorganic or organic fillers or reinforcing agents, flame retardants, various colorants, antistatic agents, and release agents.

<Blending Method> The composition of the present invention can be produced by using a usual kneading machine such as a single screw extruder, a twin screw extruder, a Banbury mixer, a roll, a Brabender plastograph, a kneader and the like. Usually, it is kneaded with an extruder to form a pellet-shaped compound and then subjected to processing. In a special case, however, it is also possible to directly supply all the components to various molding machines and perform molding while kneading with the molding machine. In addition, the filler and other components are kneaded at a high concentration (with various additives, if necessary) to form a masterbatch, which is separately diluted with another polymer or the like, blended, and compounded. Or molded.

The blending of the filler component is particularly preferably carried out by a method in which the other polymer component is melt-kneaded and subsequently the filler component is added, or a glass fiber roving is supplied. A kneaded composition can also be used.

In kneading, the compound (F) having both an unsaturated group and a polar group in the same molecule as the polymer is melt-kneaded in the presence or absence of a peroxide, or heated in an organic solvent. The method of mixing or partially graft-bonding may be used.

<Application of the Thermoplastic Resin Composition of the Present Invention> The molding method of the composition of the present invention is not particularly limited, and molding methods generally applied to thermoplastic resins, namely, extrusion molding, hollow molding, Although molding can be easily performed by a molding method such as injection molding, sheet molding, thermoforming, rotational molding, lamination molding, etc., injection molding is most preferable. It is suitable for electronic and electric parts because of its good mechanical properties, good dimensional stability and good fluidity.

[0058]

The present invention will be described below with reference to examples.
The invention is not intended to limit its scope. The components used are as follows. (A) Polyphenylene ether (A) manufactured by Mitsubishi Yuka Co., Ltd., intrinsic viscosity (η _A ) 0.56 dl / g (30
C, in chloroform) of poly (2,6-dimethyl-1,
4-phenylene ether) (b) polyphenylene ether (B) manufactured by Mitsubishi Yuka Co., Ltd., intrinsic viscosity (η _B ) 0.3 dl / g (30 ° C.,
Poly (2,6-dimethyl-1,4-) in chloroform
Phenylene ether)

(C) Polyamide (C) Crystalline nylon High viscosity (Nylon-6: MC161 manufactured by Kanebo) η _r = 6.8 Medium viscosity (Nylon-6: MC112L manufactured by Kanebo) η _r = 2.5 Low Viscosity (Nylon-6: MC100L manufactured by Kanebo) η _r = 2.1 Amorphous nylon (Novamid × 21 SO7 manufactured by Mitsubishi Kasei) η _r = 2.1 (d) Alkenyl aromatic polymer (D) polystyrene (Dialex HH200 manufactured by Mitsubishi Kasei Polytech Co., Ltd.) (e) Alkenyl aromatic compound-conjugated diene copolymer (E) Styrene-butadiene block copolymer (SBS: TR2400 manufactured by Nippon Synthetic Rubber Co., Ltd.) (f) Compound (F) having both an unsaturated group and a polar group in the same molecule, commercially available maleic anhydride (reagent grade) was used. (G) Filler (G) Glass fiber with an average diameter of 10 μm and a length of 3 mm

Examples 1 to 6 and Comparative Examples 2 and 3 Among the components shown in Table 1, (A), (B), (F) and amorphous nylon were first added to the same table using a Henschel mixer. After thoroughly mixing the indicated blending amount, the mixture was pelletized using a TEX44 twin-screw extractor manufactured by Nippon Steel Works, and the pellets and the amounts shown in the same table of components (C), (D) and (E) were added. Then, the chopped strand is fed halfway while being melt-kneaded by the same extractor, extruded into a strand, and pelletized by a cutter, and each of Examples 1 to 6 and Comparative Examples 2,
Thus, a thermoplastic resin composition of No. 3 was obtained.

Next, using these pellets, a wall thickness of 0.3
Using a comb mold shown in FIG. 1 having 30 bars of 5 mm and a length of 50 mm, weighing was constant (3 mm with Nikko J100SSIIA).
7), injection cylinder temperature 285 ° C, injection pressure 1200
When the resin was molded at a filling rate of 0.55 seconds at kg / cm ² , the state of resin filling was observed, and the filling rate was determined. Here, the filling ratio = (bar length / 50 mm) × 100% The filling ratio was obtained by averaging the five bars on the gate side and the average on the terminal side and shown in Table 1. Further, MFR5 and FR of the obtained thermoplastic material were measured and are shown in Table 1.

[0062]

[Table 1]

Comparative Example 1 The component (G) was fed in the middle, but pelletizing and evaluation tests were carried out in the same manner as in Examples 1 to 6 except that the other components shown in Table 1 were kneaded together. The results are shown in Table 1.

[0064]

From the results of the above evaluation tests, it can be seen that the thermoplastic resin composition of the present invention, in which high-viscosity and low-viscosity polyphenylene ethers and polyamides are combined, has significantly improved moldability. The composition of the present invention is reinforced with an inorganic filler, has excellent heat resistance rigidity, and has a remarkably improved processability as described above. It is a useful material.

[Brief description of the drawings]

FIG. 1 is a plan view of a comb mold used for a test of moldability.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI // (C08L 71/12 77:06 25:00 9:00) (72) Inventor Shoji Yoshino 1 Tohocho, Yokkaichi-shi, Mie (56) References JP-A-2-158661 (JP, A) JP-A-2-28248 (JP, A) JP-A 1-299868 (JP, A) JP 63-225655 (JP, A) JP-A-63-101452 (JP, A) JP-A-63-501580 (JP, A) (58) Fields investigated (Int. Cl. ⁶ , DB name) C08L 71/00 -71/14 C08L 77/00-77/12 C08L 25/00-25/18 C08L 9/00-9/01

Claims (2)

(57) [Claims] An intrinsic viscosity (η _A ) of 0.4 dl / g or more and 1.0
dl / g or less of high viscosity polyphenylene ether (A) and intrinsic viscosity (η _B ) of 0.25 dl / g or more and less than 0.4 dl / g, low viscosity polyphenylene ether (B), weight ratio (A) / (B) is a mixture of polyphenylene ether in a ratio of 10/90 to 90/10, 30 to 60 parts by weight relative to a total of 100 parts by weight of (A), (B) and the following (C), relative viscosity The polyamide (C) having (η _r ) of 1.0 to 8.0 is unsaturated in the same molecule in an amount of 40 to 70 parts by weight based on 100 parts by weight of the total of (A), (B) and (C). 0.1 to 10 parts by weight of a compound (F) having both a group and a polar group with respect to a total of 100 parts by weight of (A), (B) and (C), and a mineral filler and / or glass fiber (G) To
The melt flow rate (MFR5) measured at 280 ° C and 5 kg load is 5 to 100 parts by weight based on 100 parts by weight of the total of (A), (B) and (C).
Melt flow rate measured at 16 kg load (MFR2)
Flow ratio (FR = MFR5 / MF)
A thermoplastic resin composition wherein R2) is 2.5 or more and MFR5 is 30 or more. 2. The thermoplastic resin composition according to claim 1,
0.1 to 20 parts by weight of alkenyl aromatic compound polymer (D) based on 100 parts by weight of high viscosity polyphenylene ether (A), low viscosity polyphenylene ether (B) and polyamide (C) in the composition. And / or a thermoplastic resin composition containing 0.1 to 50 parts by weight of an impact modifier (E).