JP4236006B2 - Polyamide-polyphenylene ether resin composition - Google Patents

Description

  The present invention relates to a resin composition containing polyamide and polyphenylene ether, and a resin composition having little change in fluidity during molding even when the moisture content contained in the resin composition fluctuates in a wide range, and a resin composition obtained therefrom. It relates to a molded article. Furthermore, the present invention relates to a resin composition in which the residence stability during molding and the thermal stability of the molded article, particularly the paint adhesion after heat exposure, are remarkably improved, and a molded article comprising the resin composition.

Polyphenylene ether has excellent mechanical properties, electrical properties, and heat resistance, and is excellent in dimensional stability, so it is used in a wide range of applications. Polyphenylene ether alone is inferior in moldability, and a technique for blending polyamide has been proposed to improve this. Polyphenylene ether is now a material used in a very wide variety of applications.
Recently, polyamide-polyphenylene ether alloy has been rapidly used for exterior parts (fenders, door panels, etc.) of automobiles, etc. Molding is often performed at the upper limit of the capacity of the molding or molding machine. In particular, in a large molded product such as an automobile fender, retention stability at the time of molding is indispensable in order to ensure the quality of the molded body appearance. In particular, if the retention stability at the time of molding is poor, the appearance of the molded product is deteriorated, resulting in a decrease in coating adhesion and a deterioration in the sharpness of the appearance after coating. In order to improve the retention stability, a technique of blending an acetal and a polyphosphate into a polyamide-polyphenylene ether alloy (Patent Document 1), an organophosphorus stabilizer and zinc oxide and / or zinc sulfide are added to the polyamide-polyphenylene ether alloy. Techniques for blending (Patent Document 2), techniques for blending a phosphorus-based heat stabilizer (Patent Document 3), and the like are disclosed.

Also disclosed is a production method in which a primary condensate of polyamide and polyphenylene ether are alloyed while a polymerization reaction is advanced so as to increase the relative viscosity of the primary condensate, and a composition obtained thereby (Patent Document 4). , 5). These documents describe that sodium hypophosphite is effective in promoting the increase in the degree of polymerization of polyamide and effective in improving the color tone of the composition.
In general, when a polyamide-polyphenylene ether alloy is molded, a polymer containing a large amount of moisture has a problem such as the occurrence of silver streak, and therefore it is necessary to reduce the moisture. On the other hand, if the water content is reduced more than necessary, the fluidity is lowered, and there arises a problem that a molding defect occurs such that the mold cannot be completely filled. Thus, it is essential to manage moisture within a certain range. Even within that range, when a normal amount of sodium hypophosphite, which is a polymerization catalyst for polyamide, is present, the viscosity of the polyamide changes during molding due to the moisture content in the polymer, making it difficult to control fluidity.

Therefore, in order to ensure the quality of the molded body appearance and improve the processing stability at the time of molding, there has been a demand for a resin composition with little change in fluidity even in a wide moisture range and excellent in retention stability. .
Furthermore, in applications that require electrostatic coating properties, it is important to ensure the quality of the molded body appearance in order to ensure the coating adhesion and the sharpness of the appearance after coating. In particular, in automobile fenders, a resin molded body is also subjected to a heat treatment step together with the metal panel in order to cure the rust-preventing paint applied to the metal panel after online electrostatic coating. These heat treatment steps are typically exposed at a temperature of about 170 ° C. to 200 ° C. or higher for about 10 to 50 minutes. Therefore, the resin moldings used are currently required to have improved thermal stability, especially coating adhesion after exposure to heat.
JP-A-8-73730 JP-A-7-26134 JP 7-41658 A JP 7-331063 A Japanese Patent Laid-Open No. 7-166053

  The object of the present invention is suitable for large molded articles such as automobile exterior parts, has little change in fluidity in a wide moisture content range, which could not be achieved by the above-described technology, and has excellent residence stability in a molding machine. It is intended to provide a polyamide-polyphenylene ether alloy resin composition and a molded body comprising the resin composition. It is another object of the present invention to provide a polyamide-polyphenylene ether alloy resin composition and a molded body that improve the quality of the molded body appearance and remarkably improve the coating adhesion after heat exposure.

As a result of intensive studies in order to solve the above-mentioned problems, the present inventors have included phosphorous compounds such as phosphoric acid, phosphorous acid, metal salts of hypophosphorous acid, phosphoric acid esters, polyamides, polyphenylene ethers, elastomers And it discovered that the resin composition which contains 1-335 ppm as a phosphorus element with respect to a total of 100 mass% of a phosphorus compound was effective in order to obtain the resin composition and molded object which were excellent in the said characteristic. The present invention has been completed based on the above findings.
These and other solutions, features and benefits of the present invention will become apparent from the following detailed description and claims.
The present invention relates to (A) polyamide, (B) polyphenylene ether, (C) elastomer and (D) phosphoric acid, phosphorous acid, hypophosphorous acid, metal phosphate, metal phosphite, metal hypophosphite A method for producing a resin composition by melt-kneading one or more phosphorus compounds selected from salts and phosphate esters, wherein (A) component is a component when (D) component is polymerized with (A) component (A-1) a polyamide containing 35 ppm or more and 250 ppm or less of phosphorus element and (A-2) a polyamide containing 0 ppm or more and less than 35 ppm of phosphorus element, (A) to (D ) the method for producing a resin composition the ratio of phosphorus element against the total 100 wt%, characterized in that to obtain a resin composition which is 2~20ppm component.

Next, in order to facilitate understanding of the present invention, basic features and preferred embodiments of the present invention will be listed.
1. (A) Polyamide, (B) Polyphenylene ether, (C) Elastomer and (D) Phosphoric acid, phosphorous acid, hypophosphorous acid, phosphoric acid metal salt, phosphorous acid metal salt, hypophosphorous acid metal salt and phosphorus A method for producing a resin composition by melt-kneading one or more phosphorus compounds selected from acid esters,
The component (A) is a component in which the component (D) is added during the polymerization of the component (A), and (A-1) a polyamide containing 35 ppm to 250 ppm of phosphorus element and (A-2) phosphorus element A polyamide containing 0 ppm or more and less than 35 ppm,
(A)-(D) The manufacturing method of the resin composition characterized by obtaining the resin composition whose ratio of the phosphorus element with respect to 100 mass% of the sum total is 2-20 ppm.
2. (D) The method for producing a resin composition according to 1 above, wherein the component is one or more phosphorus compounds selected from metal phosphates, metal phosphites, and metal hypophosphites. .
3. (D) 1 or more types as which a component is 1 or more types of phosphorus compounds chosen from phosphoric acid, phosphorous acid, and hypophosphorous acid, periodic table 1st group and 2nd group, manganese, zinc, and aluminum 2. The method for producing a resin composition as described in 1 above, which is a salt with a metal.
4). Difference in melt flow rate per 100 ppm moisture content in the resin composition (MFR; measured at 280 ° C. under 5 kg load in accordance with ASTM D1238) (ΔMFR; moisture content in the resin composition in the range of 200 ppm to 1200 ppm) MFR was measured for pellets having at least three different moisture contents, and the measured MFR values were plotted on a graph showing the relationship between MFR and moisture content, and the moisture content was 100 ppm from the slope of the straight line approximating the least squares. 4. The method for producing a resin composition according to any one of the above items 1 to 3, wherein (determined by obtaining a difference in per unit MFR) is 0.65 g / 10 min or less.
5 . (F) further comprising a soluble metal aluminate represented by the general formula (M ₂ O) _X (Al ₂ O ₃ ) _Y (X + Y = 1, and M is a metal element of Group 1 of the Periodic Table). The manufacturing method of the resin composition in any one of said 1-4 to do.
6 . (F) Sodium aluminate represented by a general formula (Na ₂ O) _X (Al ₂ O ₃ ) _Y (X + Y = 1 and 0.35 ≦ Y / X ≦ 1.25) 6. The resin composition as described in 5 above, which is
7 . The method for producing a resin composition as described in 5 or 6 above, wherein the component (F) is added to the component (A) and blended in advance.
8 . The method for producing a resin composition according to any one of 1 to 7 , wherein the resin composition further contains an alkali metal halide compound and / or a copper compound.
9 . 9. The method for producing a resin composition as described in 8 above, comprising 1 to 100 ppm of copper element with respect to 100% by mass of the total amount of the resin composition.
10 . (A) polyamide, method for producing a resin composition according to any one of the above 1 to 9, characterized in that the aliphatic polyamide.
11 . Any one of 1 to 9 above, wherein the polyphenylene ether is a polymer of 2,6-dimethylphenol and / or a copolymer of 2,6-dimethylphenol and 2,3,6-trimethylphenol. The manufacturing method of the resin composition as described in any one of.
12 . (G) The resin composition as described in any one of 1 to 11 above, further comprising a styrene polymer.
13 . (H) The method for producing a resin composition according to any one of the above 1 to 12 , further comprising an inorganic filler.
14 . (H) The method for producing a resin composition as described in ( 13 ) above, wherein the inorganic filler is at least one selected from glass fiber, talc, clay, wollastonite, and titanium oxide.
15 . (C) The resin according to any one of 1 to 14 above, wherein the elastomer is a hydrogenated product of a block copolymer comprising a polymer block of an aromatic vinyl compound and a polymer block of a conjugated diene compound. A method for producing the composition.
16 . (I) The resin composition as described in any one of 1 to 15 above, further comprising a conductive carbon-based filler, wherein the conductive carbon-based filler is at least one selected from carbon fibrils and carbon black. Manufacturing method.

  The resin composition of the present invention comprises a polyamide-polyphenylene ether alloy resin composition having little change in MFR over a wide range of moisture content in the resin composition and excellent in residence stability in a molding machine, and the resin composition. A molded body can be provided. The fact that the change in MFR of the resin composition is reduced in a wide moisture content range can simplify the strict moisture content management for the resin composition at the time of production or before molding. This means that production efficiency can be improved and defective filling of the mold during molding can be reduced. Since the resin composition has remarkably improved residence stability during molding, a good appearance of the molded product can be achieved within a very wide range of molding conditions. Furthermore, it is possible to provide a polyamide-polyphenylene ether alloy resin composition and a molded article that have significantly improved coating adhesion after heat exposure.

Below, each component which comprises the resin composition of this invention is described in detail.
As the kind of polyamide that can be used as the component (A) in the present invention, any polyamide having an amide bond {—NH—C (═O) —} in the repeating structural unit of the polymer main chain may be used. Can be used without limitation.
In general, polyamides are obtained by ring-opening polymerization of lactams, polycondensation of diamine and dicarboxylic acid, polycondensation of aminocarboxylic acid, and the like, but are not limited thereto.
Examples of the diamine include aliphatic, alicyclic and aromatic diamines, and specific examples include tetramethylene diamine, hexamethylene diamine, undecamethylene diamine, dodecamethylene diamine, tridecamethylene diamine, and 1,9-nonane diamine. 2-methyl-1,8-octanediamine, 2,2,4-trimethylhexamethylenediamine, 2,4,4-trimethylhexamethylenediamine, 5-methylnonamethylenediamine, 1,3-bisaminomethylcyclohexane, Examples include 1,4-bisaminomethylcyclohexane, m-phenylenediamine, p-phenylenediamine, m-xylylenediamine, p-xylylenediamine and the like.

Dicarboxylic acids include aliphatic, alicyclic and aromatic dicarboxylic acids, and specific examples include adipic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, 1,1,3-tridecanedioic acid. 1,3-cyclohexanedicarboxylic acid, terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, dimer acid and the like.
Specific examples of lactams include ε-caprolactam, enantolactam, and ω laurolactam.
Specific examples of aminocarboxylic acids include ε-aminocaproic acid, 7-aminoheptanoic acid, 8-aminooctanoic acid, 9-aminononanoic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid, and 13-aminotriic acid. Examples include decanoic acid.

In the present invention, these lactams, diamines, dicarboxylic acids, and ω-aminocarboxylic acids are either polyamides obtained by polymerizing alone or copolymerized polyamides obtained by polycondensation of two or more mixtures. Can be used.
Further, those obtained by polymerizing these lactams, diamines, dicarboxylic acids, and ω-aminocarboxylic acids up to a low molecular weight oligomer stage in a polymerization reactor and increasing the molecular weight in an extruder or the like can be suitably used.
The method for polymerizing the polyamide used in the present invention is not particularly limited, and any of melt polymerization, interfacial polymerization, solution polymerization, bulk polymerization, solid phase polymerization, and a combination thereof may be used. Among these, melt polymerization is more preferably used.

  Particularly, polyamides that can be usefully used in the present invention include polyamide 6, polyamide 6,6, polyamide 4,6, polyamide 11, polyamide 12, polyamide 6,10, polyamide 6,12, polyamide 6 / 6,6, Polyamide 6/6, Polyamide MXD (m-xylylenediamine), 6, Polyamide 6, T, Polyamide 6, I, Polyamide 6/6, T, Polyamide 6/6, I, Polyamide 6, 6/6 T, polyamide 6,6 / 6, I, polyamide 6/6, T / 6, I, polyamide 6,6 / 6, T / 6, I, polyamide 6/12/6, T, polyamide 6,6 / 12 / 6, T, polyamide 6/12/6, I, polyamide 6, 6/12/6, I, polyamide 9, T, and the like. Polyamide obtained by copolymerizing a plurality of polyamides with an extruder or the like Earth can also be used.

Preferred polyamides are aliphatic polyamides, more preferably polyamide 6, polyamide 6,6, polyamide 6 / 6,6 and mixtures thereof, most preferably polyamide 6, polyamide 6,6, and their It is a mixture.
The preferred viscosity range of the polyamide that can be used in the various resin compositions of the present invention is such that the viscosity number measured in 96% sulfuric acid according to ISO 307 is 90 to 160 ml / g. More preferably, it is the range of 100-150 ml / g.
In the present invention, even a mixture of polyamides can be used. Examples thereof include a mixture of a polyamide having a viscosity number of 170 ml / g and a polyamide having a viscosity number of 80 ml / g, a mixture of a polyamide having a viscosity number of 120 ml / g and a polyamide having a viscosity number of 115 ml / g.

A particularly preferable mixing form among the polyamide mixtures is a mixture of polyamides having a viscosity number of 90 to 160 ml / g and different viscosity numbers.
The viscosity number of these mixtures can be confirmed by dissolving in 96% sulfuric acid at a mixing mass ratio and measuring the viscosity number according to ISO307.
The polyamide generally has an amino group and a carboxyl group as terminal groups, but these preferred ratios in the present invention are amino group / carboxyl group concentration ratios of 9/1 to 1/9, more preferably 8 / 2 to 1/9, more preferably 6/4 to 1/9.
The concentration of the terminal amino group is preferably at least 1 × 10 ⁻⁵ mol / g or more. More preferably, it is 1 × 10 ⁻⁵ or more and 4 × 10 ⁻⁵ mol / g or less.

The terminal carboxyl group concentration is preferably at least 5 × 10 ⁻⁵ mol / g or more. More preferably, it is 7 × 10 ⁻⁵ or more and 13 × 10 ⁻⁵ mol / g or less.
A known method can be used as a method for adjusting the end groups of these polyamide resins. For example, there may be mentioned a method of adding one or more selected from diamine compounds, monoamine compounds, dicarboxylic acid compounds, monocarboxylic acid compounds and the like so that a predetermined terminal concentration is obtained during polymerization of the polyamide resin.
Furthermore, in addition to the above, known additives that can be added to the polyamide may be added in an amount of less than 10 parts by mass with respect to 100 parts by mass of the polyamide.
The polyphenylene ether that can be used as the component (B) in the present invention is a homopolymer and / or copolymer composed of a structural unit represented by the following formula (1).

[Wherein, O is an oxygen atom, and each R is independently hydrogen, halogen, primary or secondary C1-C7 alkyl group, phenyl group, C1-C7 haloalkyl group, C1-C7 aminoalkyl. A group, a C1-C7 hydrocarbyloxy group, or a halohydrocarbyloxy group, provided that at least two carbon atoms separate the halogen atom from the oxygen atom. ]
Specific examples of the polyphenylene ether of the present invention include, for example, poly (2,6-dimethyl-1,4-phenylene ether), poly (2-methyl-6-ethyl-1,4-phenylene ether), and poly (2-methyl-6-phenyl-1,4-phenylene ether), poly (2,6-dichloro-1,4-phenylene ether) and the like, and 2,6-dimethylphenol and other phenols (For example, a copolymer with 2,3,6-trimethylphenol or a copolymer with 2-methyl-6-butylphenol as described in JP-B-52-17880) Polyphenylene ether copolymers such as

Among these, particularly preferred polyphenylene ethers include poly (2,6-dimethyl-1,4-phenylene ether), 2,6-dimethyl-1,4-phenol and 2,3,6-trimethyl-1,4- A copolymer with phenol, or a mixture thereof.
In addition, when using a copolymer of 2,6-dimethyl-1,4-phenol and 2,3,6-trimethyl-1,4-phenol, the ratio of each monomer unit is the same as that of polyphenylene ether copolymer. When the total amount is 100% by mass, about 80 to about 90% by mass of 2,6-dimethyl-1,4-phenol and about 10 to about 20% by mass of 2,3,6-trimethyl-1, More preferred is a copolymer comprising 4-phenol.

The method for producing the polyphenylene ether used in the present invention is not particularly limited as long as it can be obtained by a known method. For example, U.S. Pat. Nos. 3,306,874, 3,306,875, 3,257,357, and 3,257,358, JP-A-50-51197, JP-B-52-17880, and 63. And the production method described in JP-A No.-152628.
The reduced viscosity of the polyphenylene ether that can be used in the present invention (ηsp / c: 0.5 g / dl, chloroform solution, measured at 30 ° C.) is preferably in the range of 0.15 to 0.70 dl / g, More preferably, it is the range of 0.20-0.60 dl / g, More preferably, it is the range of 0.40-0.55 dl / g.

In the present invention, a blend of two or more polyphenylene ethers having different reduced viscosities can be used without any problem. For example, a mixture of a polyphenylene ether having a reduced viscosity of 0.45 dl / g or less and a polyphenylene ether having a reduced viscosity of 0.50 dl / g or more, a low molecular weight polyphenylene ether having a reduced viscosity of 0.40 dl / g or less, and a reduced viscosity of 0.50 dl / g or more. A mixture of polyphenylene ethers, etc., of course, is, of course, not limited to these.
The polyphenylene ether that can be used in the present invention may be a completely modified polyphenylene ether or a mixture of an unmodified polyphenylene ether and a modified polyphenylene ether.

The modified polyphenylene ether here means at least one carbon-carbon double bond or triple bond and at least one carboxylic acid group, acid anhydride group, amino group, hydroxyl group, or glycidyl in the molecular structure. The polyphenylene ether modified with at least one modifying compound having a group.
The method for producing the modified polyphenylene ether includes: (1) a modified compound without melting the polyphenylene ether in the temperature range of 100 ° C. or higher and lower than the glass transition temperature of the polyphenylene ether in the presence or absence of a radical initiator. A method of reacting, (2) a method of reacting by melting and kneading with a modifying compound in the temperature range of the glass transition temperature of polyphenylene ether to 360 ° C. in the presence or absence of a radical initiator, and (3) presence of a radical initiator. Examples thereof include a method of reacting polyphenylene ether with a modifying compound in a solution at a temperature lower than or below the glass transition temperature of polyphenylene ether. Any of these methods may be used, but the methods (1) and (2) are preferable.

Next, at least one modified compound having at least one carbon-carbon double bond or triple bond and at least one carboxylic acid group, acid anhydride group, amino group, hydroxyl group, or glycidyl group in the molecular structure Will be described in detail.
Examples of modified compounds having a carbon-carbon double bond and a carboxylic acid group and / or an acid anhydride group in the molecule include maleic acid, fumaric acid, chloromaleic acid, cis-4-cyclohexene-1,2-dicarboxylic acid And acid anhydrides thereof. Of these, fumaric acid, maleic acid and maleic anhydride are preferred, and fumaric acid and maleic anhydride are particularly preferred.
In addition, compounds in which one or two of the carboxyl groups of the unsaturated dicarboxylic acid are esterified can also be used.

Examples of the modified compound having a carbon-carbon double bond and a glycidyl group in the molecule include allyl glycidyl ether, glycidyl acrylate, glycidyl methacrylate, and epoxidized natural fats and oils.
Among these, glycidyl acrylate and glycidyl methacrylate are particularly preferable.
Examples of the modified compound having a carbon-carbon double bond and a hydroxyl group in the molecule include general formula C _n H _2n-3 OH such as allyl alcohol, 4-penten-1-ol, and 1,4-pentadien-3-ol. (n is a positive integer) of unsaturated alcohols of the general formula _{C n H 2n-5 OH,} ( n is a positive integer) _{C n H 2n-7} OH include unsaturated alcohols such as.

The above-described modifying compounds may be used alone or in combination of two or more.
The amount of the modifying compound added when producing the modified polyphenylene ether is preferably 0.1 to 10 parts by mass, more preferably 0.3 to 5 parts by mass with respect to 100 parts by mass of the polyphenylene ether.
Examples of the radical initiator include known organic oxides and diazo compounds. Specific examples include benzoyl peroxide, dicumyl peroxide, di-tert-butyl peroxide, tert-butyl cumyl peroxide, tert-butyl hydroperoxide, cumene hydroperoxide, azobisisobutyronitrile, and the like. It is done.

A preferable amount of the radical initiator when producing the modified polyphenylene ether using the radical initiator is 0.001 to 1 part by mass with respect to 100 parts by mass of the polyphenylene ether.
Further, the addition rate of the modifying compound in the modified polyphenylene ether is preferably 0.01 to 5% by mass. More preferably, it is 0.1-3 mass%.
In the modified polyphenylene ether, an unreacted modified compound and / or a polymer of the modified compound may remain.
Also, various stabilizers known for stabilizing the polyphenylene ether can be suitably used. Examples of the stabilizer include organic stabilizers such as metal stabilizers such as zinc oxide and zinc sulfide, hindered phenol stabilizers, phosphate ester stabilizers, and hindered amine stabilizers. These preferable compounding quantities are less than 5 mass parts with respect to 100 mass parts of polyphenylene ether.

Furthermore, you may add the well-known additive etc. which can be added to polyphenylene ether in the quantity of less than 10 mass parts with respect to 100 mass parts of polyphenylene ether.
Although there is no restriction | limiting in particular in the compounding ratio of the polyamide and polyphenylene ether in this invention, 30 / 70-80 / 20 is preferable for polyamide / polyphenylene ether, More preferably, 40 / 60-75 / 25, More preferably, 45/55 70/30.
As an elastomer that can be used as the component (C) in the present invention, a block copolymer comprising a polymer block mainly composed of at least one aromatic vinyl compound and a polymer block mainly composed of at least one conjugated diene compound. And a hydrogenated product thereof, ethylene-α-olefin copolymer, rubber-modified polystyrene (HIPS), and one or more selected from the group consisting of styrene-rubber polymer-acrylonitrile copolymer (ABS resin).

The “mainly” in the polymer block mainly composed of the aromatic vinyl compound of the present invention refers to a block in which at least 50% by mass or more of the block is an aromatic vinyl compound. More preferably, it is 70 mass% or more, More preferably, it is 80 mass% or more, Most preferably, it is 90 mass% or more. The same applies to “mainly” in a polymer block mainly composed of a conjugated diene compound, and refers to a block in which at least 50% by mass or more is a conjugated diene compound. More preferably, it is 70 mass% or more, More preferably, it is 80 mass% or more, Most preferably, it is 90 mass% or more.
In this case, for example, even in the case of a block in which a small amount of a conjugated diene compound or other compound is randomly bonded in the aromatic vinyl compound block, 50% by mass of the block is formed from the aromatic vinyl compound. Thus, it is regarded as a block copolymer mainly composed of an aromatic vinyl compound. The same applies to the case of a conjugated diene compound.

Specific examples of the aromatic vinyl compound include styrene, α-methylstyrene, vinyltoluene and the like, and one or more compounds selected from these are used, and among them, styrene is particularly preferable.
Specific examples of the conjugated diene compound include butadiene, isoprene, piperylene, 1,3-pentadiene and the like. One or more compounds selected from these are used, but butadiene, isoprene and combinations thereof are particularly preferable.
The microstructure of the block part of the conjugated diene compound block of the block copolymer is preferably 1,2-vinyl content or the total amount of 1,2-vinyl content and 3,4-vinyl content of 5-80%, more preferably 10-50 % Is preferable, and 15 to 40% is most preferable.

In the block copolymer of the present invention, the polymer block [A] mainly composed of an aromatic vinyl compound and the polymer block [B] mainly composed of a conjugated diene compound are AB type and ABA type. A block copolymer having a bond type selected from A-B-A-B type is preferable, and a mixture thereof may be used. Among these, the AB type, the ABA type, or a mixture thereof is more preferable, and the ABA type is most preferable.
The block copolymer of an aromatic vinyl compound and a conjugated diene compound that can be used in the present invention is more preferably a hydrogenated block copolymer. The hydrogenated block copolymer is an aliphatic double bond of a polymer block mainly composed of a conjugated diene compound by subjecting the block copolymer of the aromatic vinyl compound and the conjugated diene compound to a hydrogenation treatment. Is controlled in the range of more than 0 and 100%. A preferable hydrogenation rate of the hydrogenated block copolymer is 80% or more, and most preferably 98% or more.

These block copolymers can be used without any problem as a mixture of a non-hydrogenated block copolymer and a hydrogenated block copolymer.
In addition, these aromatic vinyl compound-conjugated diene compound block copolymers are different in bond type, different in aromatic vinyl compound type, different in conjugated diene compound type, unless contrary to the spirit of the present invention, A mixture of 1,2-bonded vinyl content, 1,2-bonded vinyl content and 3,4-bonded vinyl content, or different aromatic vinyl compound component content may be used. .
The block copolymer used in the present invention is preferably a mixture of a low molecular weight block copolymer and a high molecular weight block copolymer. Specifically, it is a mixture of a low molecular weight block copolymer having a number average molecular weight of less than 120,000 and a high molecular weight block copolymer having a number average molecular weight of 120,000 or more. More preferably, it is a mixture of a low molecular weight block copolymer having a number average molecular weight of less than 120,000 and a high molecular weight block copolymer having a number average molecular weight of 170,000 or more.

The mass ratio of these low molecular weight block copolymer and high molecular weight block copolymer is low molecular weight block copolymer / high molecular weight block copolymer = 95/5 to 5/95. Preferably it is 90/10-10/90.
In the present invention, the preferred range of the content of the polymer block mainly comprising an aromatic vinyl compound in the low molecular weight block copolymer is 55% by mass or more and less than 90% by mass. Since the heat resistance can be improved by using a block copolymer having an aromatic vinyl polymer block within this range as the low molecular weight block copolymer, it can be used more suitably.

Furthermore, a block copolymer containing a low molecular weight block copolymer in a quantity of 55% by weight or more and less than 90% by weight of a polymer block mainly composed of an aromatic vinyl compound, and a heavy polymer composed mainly of an aromatic vinyl compound. It may be a mixture with a block copolymer containing a combined block in an amount of 20% by mass or more and less than 55% by mass.
Further, the block copolymer used in the present invention may be a completely modified block copolymer or a mixture of an unmodified block copolymer and a modified block copolymer. Absent.
The modified block copolymer as used herein refers to at least one carbon-carbon double bond or triple bond and at least one carboxylic acid group, acid anhydride group, amino group, hydroxyl group in the molecular structure. Alternatively, it refers to a block copolymer modified with at least one modifying compound having a glycidyl group.

  The method for producing the modified block copolymer is as follows: (1) Reaction by melting and kneading with the modifying compound in the temperature range of the softening point temperature of the block copolymer to 250 ° C. in the presence or absence of a radical initiator. (2) a method in which the block copolymer and the modifying compound are reacted in a solution at a temperature below the softening point of the block copolymer in the presence or absence of a radical initiator, and (3) a radical initiator. And a method of reacting the block copolymer and the modifying compound without melting at a temperature below the softening point of the block copolymer in the presence or absence of. Any of these methods may be used, but the method (1) is preferable, and the method (1) performed in the presence of a radical initiator is most preferable.

At least one modification having at least one carbon-carbon double bond or triple bond and at least one carboxylic acid group, acid anhydride group, amino group, hydroxyl group, or glycidyl group in the molecular structure referred to herein. As the compound, the same modified compounds as described in the modified polyphenylene ether can be used.
The blending amount of the elastomer in the present invention is preferably less than 50 parts by mass with respect to 100 parts by mass of the total amount of polyamide and polyphenylene ether.
In the present invention, it is possible to add a known compatibilizer of polyamide and polyphenylene ether.

The main purpose of using the compatibilizer is to improve the physical properties of the polyamide-polyphenylene ether mixture. The compatibilizing agent that can be used in the present invention refers to a polyfunctional compound that interacts with polyphenylene ether, polyamide, or both. This interaction may be chemical (eg, grafting) or physical (eg, changing the surface properties of the dispersed phase).
In any case, the resulting polyamide-polyphenylene ether mixture exhibits improved compatibility.
Examples of compatibilizers that can be used in the present invention are described in detail in WO 01/81473, and all of these known compatibilizers can be used, and can be used in combination. .

Among these various compatibilizers, examples of particularly suitable compatibilizers include maleic acid, maleic anhydride, and citric acid.
The preferred amount of the compatibilizing agent in the present invention is 0.01 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, and most preferably 0.1 to 100 parts by mass of the mixture of polyamide and polyphenylene ether. ˜1% by mass.
The phosphorus compounds that can be used as component (D) in the present invention are 1) phosphoric acids, phosphorous acids and hypophosphorous acids, 2) metal phosphates, metal phosphites and metal hypophosphites And 3) one or more selected from phosphoric acid compounds such as phosphoric acid esters and phosphorous acid esters, phosphorous acid compounds, and hypophosphorous acid compounds.

Examples of 1) phosphoric acid, phosphorous acid and hypophosphorous acid include phosphoric acid, phosphorous acid, hypophosphorous acid, pyrophosphorous acid, diphosphorous acid and the like.
The metal phosphate, metal phosphite, and metal hypophosphite of 2) above are the phosphorus compound of 1) and Groups 1 and 2 of the periodic table, manganese, zinc, aluminum, ammonia, Mention may be made of salts with alkylamines, cycloalkylamines and diamines.
The phosphoric acid esters and phosphites of 3) are represented by the following general formula.
Phosphate ester; (OR) _n PO (OH) _3-n
Phosphite; (OR) _n P (OH) _3-n
Here, n represents 1, 2 or 3, and R represents an alkyl group, a phenyl group, or an alkyl group in which a part of these groups is substituted with a hydrocarbon group or the like. When n is 2 or more, a plurality of (RO) groups in the general formula may be the same or different.

As R, methyl group, ethyl group, n-propyl group, n-butyl group, t-butyl group, n-hexyl group, cyclohexyl group, n-octyl group, nonyl group, decyl group, stearyl group, oleyl group And an aliphatic group such as an aliphatic group such as phenyl group and biphenyl group, or an aromatic group having a substituent such as hydroxyl group, methyl group, ethyl group, propyl group, methoxy group and ethoxy group. .
The preferred phosphorus compound of the present invention is at least one selected from metal phosphates, metal phosphites or metal hypophosphites. Among these, a salt of a phosphorus compound selected from phosphoric acid, phosphorous acid, and hypophosphorous acid and a metal selected from Groups 1 and 2 of the periodic table, manganese, zinc, and aluminum is preferable. More preferably, it is a metal salt consisting of a phosphorus compound selected from phosphoric acid, phosphorous acid and hypophosphorous acid and a metal of Group 1 of the periodic table, and more preferably phosphorous acid or hypophosphorous acid and the periodic rule. It is a metal salt composed of a group 1 metal, and most preferably sodium hypophosphite (NaH ₂ PO ₂ ) or a hydrate thereof (NaH ₂ PO ₂ .nH ₂ O).

As a compounding quantity of (D) component in this invention, it is necessary to mix | blend so that a phosphorus element may be 1-35 ppm with respect to a total of 100 mass% of (A)-(D) component in this resin composition. is there. If the phosphorus element is less than 1 ppm, silver streak is likely to occur during high temperature molding. On the other hand, if the amount of phosphorus element exceeds 35 ppm, the fluidity greatly varies under the influence of moisture. More preferably, it is 1-30 ppm, More preferably, it is 2-25 ppm, Most preferably, it is 2-20 ppm.
The phosphorus element in the resin composition can be quantified, for example, at a wavelength of 213.618 (nm) by high-frequency inductively coupled plasma (ICP) emission analysis using IRIS / IP manufactured by Thermo Jarrel Ash.

  Although there is no restriction | limiting in particular as a method of mix | blending the (D) component of this invention in a resin composition, For example, (1) Before superposing | polymerizing polyamide, (D) component is previously mix | blended and polymerized in a polyamide formation component. A method, or (2) a method of blending the component (D) into the polyamide in a molten state at any time during the polymerization of the polyamide, (3) a method of blending the component (D) in the polyamide using an extruder or the like, Or (4) The method of mix | blending (D) component, etc. are mentioned when melt-kneading polyamide and polyphenylene ether with an extruder. Among them, it is preferable to blend the component (D) in the polyamide in advance before melt-kneading the polyamide and polyphenylene ether. Examples of the method include the methods (1) to (3) described above. Among them, the method (1) is particularly preferable. A more preferred method is a method in which the component (D) is made into an aqueous solution and blended with the polyamide-forming component to carry out polymerization. Thereby, the subject of this invention can be achieved more notably.

In the present invention, it is preferable that the polyamide previously blended with the component (D) as described above is a mixture of two or more kinds of polyamides having different phosphorus element concentrations. Moreover, it is more preferable to be a mixture of polyamide containing 35 ppm or more as a phosphorus element and polyamide containing less than 35 ppm as a phosphorus element. More preferably, it is a mixture of polyamide containing 35 ppm or more and less than 250 ppm as phosphorus element and polyamide containing 0 ppm or more and less than 35 ppm as phosphorus element. Thereby, the subject of this invention can be achieved more notably.
In the present invention, the difference (ΔMFR) in MFR (measured under a load of 5 kg at 280 ° C. according to ASTM D1238) per 100 ppm of water content in the resin composition is preferably 0.80 g / 10 min or less. More preferably, ΔMFR is 0.70 g / 10 min or less, and more preferably ΔMFR is 0.65 g / 10 min or less.

In the present invention, (E1) a periodic table group IA base selected from oxides, carbonates, alkoxides, bicarbonates and hydroxides and / or (E2) group IIA, zinc and aluminum 1 It is preferable to further include a polyvalent metal compound selected from a carboxylate of at least one metal and a water-soluble compound of at least one metal selected from Group IIA, zinc and aluminum.
The (E1) Periodic Table Group IA base of the present invention is preferably selected from oxides, carbonates, alkoxides, bicarbonates and hydroxides. In particular, sodium bicarbonate, potassium bicarbonate, potassium hydroxide or sodium hydroxide is more preferred, and sodium bicarbonate and potassium bicarbonate are more preferred.

The (E2) polyvalent metal compound of the present invention comprises one or more metal carboxylates selected from Group IIA, zinc and aluminum and one or more metal water-soluble compounds selected from Group IIA, zinc and aluminum. It is preferable to be selected. In particular, one or more metal carboxylates (acetate, propionate, benzoate, stearate, etc.) selected from group IIA, zinc and aluminum, one or more selected from group IIA, zinc and aluminum More preferred is a metal nitrate of at least one metal selected from Group IIA, zinc, and aluminum, and more preferably calcium acetate and aluminum distearate.
In the present invention, it is preferable to contain 0.10 to 50 mol of the total concentration of Group IA base and / or polyvalent metal compound in the periodic table per 1,000,000 g of resin composition, and 0.10 to 10 mol. It is more preferable to contain, and it is more preferable to contain 0.10-3 mol.

The resin composition of the present invention has a ratio of the sum of the number of moles of polyvalent metal and monovalent metal to the number of moles of phosphorus (P) element, that is, (number of moles of polyvalent metal + number of moles of monovalent metal). / (Number of moles of P) is preferably more than 1 and 8 or less, more preferably 2 to 7.5, and most preferably 2 to 7. By setting each concentration within the above range, the melt viscosity, which is the object of the present invention, is stabilized, and the residence stability and the paintability after heat exposure tend to be further improved.
The addition method of (D) phosphorus compound and (E1) periodic table group IA base and / or (E2) polyvalent metal compound used in the present invention is a method of adding in advance to a polyamide-forming component before polymerization of polyamide. Or a method of adding to a polyamide in a molten state at any time during polymerization of polyamide, a method of blending in a polyamide using an extruder, or a method of adding polyamide and polyphenylene ether when melt-kneading with an extruder, etc. Is mentioned. Although these methods are not particularly limited, it is preferable to preliminarily blend the polyamide and polyphenylene ether in the polyamide before melt-kneading. Particularly preferable methods are (D) a phosphorus compound, (E1) a group IA base of the periodic table and / or (E2) a polyvalent metal compound which is previously blended with a polyamide-forming component and polymerized. ) Phosphorus compound is pre-blended with polyamide-forming component and polymerized, then in the middle of the polymerization process or after completion of polymerization (E1) Periodic Table Group IA base and / or (E2) polyvalent metal compound in molten state It is the method of mix | blending in the polyamide of this.

In addition, the (D) phosphorus compound and (E1) periodic table group IA base and / or (E2) polyvalent metal compound previously blended in the polyamide are solid or in the form of an aqueous solution in the polyamide-forming component or melted. It can be added to the polyamide.
In the present invention, (F) further includes a soluble metal aluminate represented by the general formula (M ₂ O) _X (Al ₂ O ₃ ) _Y (X + Y = 1, and M is a metal element of Group 1 of the periodic table). It is preferable.
A more preferable component (F) of the present invention is sodium aluminate in which the main component of M in the above general formula is sodium.

The value of the molar ratio Y / X between aluminum (Al) and group 1 metal M of the periodic table in the above general formula is preferably 0.35 ≦ Y / X ≦ 1.25, more preferably 0.8. 35 ≦ Y / X ≦ 1.00, and more preferably 0.5 ≦ Y / X ≦ 0.90.
In the present invention, the molar ratio of Al metal to monovalent metal (number of moles of Al metal / number of moles of monovalent metal) in the resin composition is 0.10 to 1.0, preferably 0.8. It is 25-0.9, More preferably, it is 0.30-0.75. By setting each concentration within the above range, the melt viscosity, which is the object of the present invention, is stabilized, and the residence stability and the paintability after heat exposure tend to be further improved.

In the present invention, it is preferable to contain 0.10 to 10 mol of Al metal and 0.10 to 10 mol of monovalent metal per 1,000,000 g of resin composition, and 0.20 to 7.5 mol of Al metal and More preferably, it contains 0.20 to 7.5 mol of a monovalent metal.
The resin composition of the present invention has a ratio between the sum of the number of moles of Al metal and monovalent metal and the number of moles of phosphorus (P) element, that is, (number of moles of Al metal + number of moles of monovalent metal) / ( The value of the number of moles of P is preferably more than 1 and 8 or less, more preferably 2 to 7.5, and most preferably 3 to 7.5.
(D) Phosphorus compound and (F) soluble metal aluminate used in the present invention may be added to a polyamide-forming component before polyamide polymerization, or in a molten state at any point during polyamide polymerization. The method of adding to the polyamide, the method of blending in the polyamide using an extruder or the like, or the method of adding the polyamide and polyphenylene ether when melt-kneading with an extruder are included. Although not particularly limited to these methods, it is preferable that the polyamide and polyphenylene ether are preliminarily blended in the polyamide before being melt-kneaded. Particularly preferable methods are (D) a method in which both the phosphorus compound and the (F) soluble metal aluminate salt are blended in the polyamide-forming component for polymerization, and (D) a phosphorus compound is blended in the polyamide-forming component. This is a method in which polymerization is performed, and then (F) a soluble metal aluminate salt is blended with a molten polyamide during or after the polymerization step.

  A more preferred method is that (D) a phosphorus compound and (F) a soluble metal aluminate are mixed in an aqueous solution. In particular, the (F) soluble aluminates are more preferably added as an aqueous solution having a pH exceeding 9. When added as an aqueous solution, the (F) soluble aluminates tend to be more uniformly mixed with the polyamide-forming component, the polyamide in the polymerization step and the molten polyamide than when added as a powder. Thereby, the subject of this invention can be achieved more notably. In order to prepare an aqueous solution having a pH exceeding 9, soluble aluminates may be directly dissolved in water, or an aqueous solution containing an alkali component, preferably an alkali component such as diamine or monoamine, which is a polyamide-forming component in advance. And then the aluminates may be dissolved.

In the present invention, a metal stabilizer as described in JP-A-1-163262, which is known for the purpose of improving the heat resistance stability of the polyamide resin, can also be used without any problem. .
Among these metal stabilizers, those that can be particularly preferably used include CuI, CuCl ₂ , copper acetate, cerium stearate and the like, and copper compounds represented by CuI, copper acetate and the like are more preferable. More preferably, it is CuI. As a preferable compounding amount of these copper compounds, an amount of 1 to 100 ppm, more preferably 1 to 30 ppm, still more preferably 1 to 100 ppm with respect to 100% by mass of the total amount of the resin composition in the resin composition as a copper element. An amount containing 10 ppm.

The quantification of the copper element in the resin composition can be quantified by high-frequency inductively coupled plasma (ICP) emission analysis using, for example, an IRIS / IP manufactured by Thermo Jarrel Ash, similarly to the quantification of the phosphorus element.
Moreover, the halogenated alkyl metal compound represented by potassium iodide, potassium bromide, etc. can also be used conveniently, It is preferable to add together a copper compound and a halogenated alkyl metal compound.
Furthermore, in the present invention, (G) a styrenic polymer may be included. Examples of the styrenic polymer in the present invention include homopolystyrene, rubber-modified polystyrene (HIPS), styrene-acrylonitrile copolymer (AS resin), styrene-rubber polymer-acrylonitrile copolymer (ABS resin), and the like. It is done. By including the styrenic polymer, the weather resistance can be improved in addition to achieving the object of the present invention. A preferable blending amount of the styrenic polymer is an amount of less than 50 parts by mass with respect to 100 parts by mass in total of polyamide and polyphenylene ether.

In the present invention, (H) an inorganic filler may be added. Examples of the inorganic filler that can be used in the present invention include glass fiber, wollastonite, talc, kaolin, zonotlite, titanium oxide, potassium titanate, zinc oxide and the like. Of these, glass fiber, wollastonite, talc, clay, titanium oxide, and zinc oxide are preferable, and glass fiber, wollastonite, talc, and titanium oxide are more preferable.
There is no restriction | limiting in particular in the glass fiber which can be used by this invention, It can select and use from long fiber type roving, a short fiber type chopped strand, a milled fiber, etc. Among these, those having an average fiber diameter of 5 to 20 μm are preferable, and those having an average fiber diameter of 8 to 17 μm are more preferable.

These glass fibers may be surface-treated with a coupling agent (eg, silane, titanate, aluminum, zirconium, etc.). Further, a sizing agent may be applied, and an epoxy-based, urethane-based, urethane / maleic acid-modified compound, or urethane / amine-modified compound can be preferably used. These surface treatment agents and sizing agents may be used in combination. The preferable compounding amount of these glass fibers is 2 to 80 parts by mass with respect to 100 parts by mass in total of polyamide and polyphenylene ether. More preferably, it is 2-70 mass parts, More preferably, it is 5-60 mass parts.
The wollastonite that can be used in the present invention is a product obtained by purifying, grinding and classifying a natural mineral containing calcium silicate as a component. Artificially synthesized materials can also be used. The size of wollastonite is preferably one having an average particle diameter of 2 to 9 μm and an aspect ratio of 5 or more, more preferably an average particle diameter of 3 to 7 μm and an aspect ratio of 5 or more, and further preferably an average particle diameter of 3 to 3. 7 μm, aspect ratio 8 to 30.

In addition, these wollastonites have higher fatty acids or their derivatives and derivatives such as salts (eg, stearic acid, oleic acid, palmitic acid, magnesium stearate, calcium stearate, aluminum stearate, stearic acid) as surface treatment agents. Amide, stearic acid ethyl ester, etc.) and coupling agents (for example, silane, titanate, aluminum, zirconium, etc.) can be used if necessary. The amount used is preferably 0.05 to 5% by mass with respect to wollastonite.
The preferable compounding amount of these wollastonites is 2 to 80 parts by mass with respect to 100 parts by mass in total of polyamide and polyphenylene ether. More preferably, it is 2-70 mass parts, More preferably, it is 5-60 mass parts.

Talc that can be used in the present invention is a refined, ground and classified natural mineral containing magnesium silicate as a component.
In addition, these talcs have, as surface treatment agents, higher fatty acids or derivatives thereof such as esters and salts thereof (for example, stearic acid, oleic acid, palmitic acid, magnesium stearate, calcium stearate, aluminum stearate, stearamide, Stearic acid ethyl ester and the like) and coupling agents (for example, silane-based, titanate-based, aluminum-based, zirconium-based, etc.) can be used as necessary. The amount used is preferably 0.05 to 5% by mass with respect to talc.
A preferable blending amount of these talcs is 2 to 80 parts by mass with respect to 100 parts by mass in total of polyamide and polyphenylene ether. More preferably, it is 2-70 mass parts, More preferably, it is 5-60 mass parts.

In the present invention, (I) conductive carbon-based filler may be added.
Specific examples of the conductive carbon filler that can be used in the present invention include conductive carbon black, carbon fibril (also referred to as carbon nanotube), carbon fiber, and the like.
The conductive carbon black usable in the present invention preferably has a dibutyl phthalate (DBP) oil absorption of 250 ml / 100 g or more, more preferably a carbon having a DBP oil absorption of 300 ml / 100 g or more, more preferably 350 ml / 100 g or more. Black. The DBP oil absorption referred to here is a value measured by a method defined in ASTM D2414.

The conductive carbon black that can be used in the present invention preferably has a BET specific surface area (JIS K6221-1982) of 200 m ² / g or more, and more preferably 400 m ² / g or more. Examples of commercially available products include Ketjen Black International Ketjen Black EC and Ketjen Black EC-600JD.
Examples of carbon fibrils that can be used in the present invention include US Pat. No. 4,663,230, US Pat. No. 5,165,909, US Pat. No. 5,171,560, US Pat. No. 5,578,543, US Pat. No. 5,589,152, US Pat. No. 5,650,370, This refers to a carbon fiber with few branches having a hollow structure with a fiber diameter of less than 75 nm described in US Pat. No. 6,235,674. Moreover, the thing of the coil shape which a helix makes a round with the pitch of 1 micrometer or less is also contained. Examples of commercially available products include carbon fibrils (BN fibrils) available from Hyperion Catalysis International.

Examples of the carbon fiber that can be used in the present invention include polyacrylonitrile-based carbon fiber, rayon-based carbon fiber, lignin-based carbon fiber, and pitch-based carbon fiber. These may be used alone or in combination of two or more.
The preferable compounding amount of the conductive carbon-based filler in the present invention is in the range of 0.3 to 3% by mass with respect to 100% by mass of the total amount of polyamide and polyphenylene ether. More preferably, it is 0.3-2 mass%.
There are no particular restrictions on the method of adding these conductive carbon fillers, but a method of adding the filler to a molten mixture of polyamide and polyphenylene ether and melt-kneading, or a form of a masterbatch in which the filler is pre-blended with polyamide And the like. In particular, it is preferable to add in the form of a master batch in which the filler is blended in polyamide.

When the filler is carbon fibril, a polyamide 66 / carbon fibril masterbatch (trade name: Polyamide 66 with Fibril ™ Nanotubes RMB4620-00: carbon fibril amount 20%) available from Hyperion Catalyst International Co., Ltd. is used as a master batch. Can be used.
The amount of the conductive carbon-based filler in these master batches is preferably 5 to 25% by mass when the master batch is 100% by mass.
As an example of a manufacturing method of these master batches, a polyamide is supplied from the upstream side using a twin screw extruder having one supply port on the upstream side and one or more supply ports on the downstream side, and conductive from the downstream side. Examples include a production method in which a carbon-based filler is added and melt-kneaded, and a production method in which a part of the polyamide is supplied from the upstream side and the remaining polyamide and the conductive carbon-based filler are simultaneously added from the downstream side and melt-kneaded.

Moreover, although there is no restriction | limiting in particular as a preset temperature of the processing machine at the time of manufacturing these master batches, it is preferable that it is the range of 240-350 degreeC. More preferably, it is the range of 240-300 degreeC, More preferably, it is the range of 240-280 degreeC.
In the present invention, in addition to the above-described components, additional components may be added as necessary within a range not impairing the effects of the present invention.
Examples of additional components are listed below.
Known adhesion improvers and flame retardants to increase the affinity between the inorganic filler and the resin (halogenated resin, silicone flame retardant, magnesium hydroxide, aluminum hydroxide, organophosphate compound, ammonium polyphosphate , Red phosphorus, etc.), fluorine-based polymers showing anti-dripping effect, plasticizers (oil, low molecular weight polyolefin, polyethylene glycol, fatty acid esters, etc.), flame retardant aids such as antimony trioxide, antistatic agents, Oxides, zinc sulfide, antioxidants, ultraviolet absorbers, light stabilizers, and the like.

Specific processing machines for obtaining the composition of the present invention include, for example, a single screw extruder, a twin screw extruder, a roll, a kneader, a Brabender plastograph, a Banbury mixer, and the like. Among these, a twin screw extruder is preferable, and a twin screw extruder having an upstream supply port and one or more downstream supply ports having a screw diameter of 25 mm or more and an L / D of 30 or more is preferable, and a screw diameter of 45 mm or more. A twin screw extruder having an L / D of 30 or more is most preferable.
The cylinder set temperature of the processing machine at this time is not particularly limited, and the conditions under which a suitable composition can be obtained can be arbitrarily selected from 240 to 360 ° C.
The composition of the present invention obtained as described above can be molded as a molded body of various parts by various conventionally known methods such as injection molding.

  These various parts include, for example, motorcycle / car electrical parts typified by relay block materials, IC tray materials, chassis of various disk players, electrical / electronic parts such as cabinets, various computers, and OA such as peripheral equipment. Parts and machine parts, as well as motorcycle cowls, automobile bumpers, fenders, door panels, various moldings, emblems, outer door handles, door mirror housings, wheel caps, roof rails and their stays and spoilers. In addition, it can be suitably used for interior parts represented by instrument panels, console boxes, trims, and the like.

EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention further in detail, this invention is not limited to what was shown by this Example.
(Raw materials used)
(1) Polyamide 6, 6 (hereinafter abbreviated as PA)
(1-1) Polyamide 6,6 (hereinafter abbreviated as PA-1)
Into a 50 wt% aqueous solution containing 1600 kg of a polyamide 66 forming component (equimolar salt of hexamethylene diamine and adipic acid), 828 g of acetic acid and 828 g of hexamethylene diamine are blended as end-capping agents, and sodium hypophosphite ( A mixed liquid containing 394 g of a 10 wt% aqueous solution of NaH ₂ PO ₂ ) and 55 g of a silicone-based antifoaming agent was prepared. The mixed solution was charged into a concentration tank, mixed under a temperature condition of about 50 ° C., and replaced with nitrogen. Next, the temperature of the mixed solution was raised from about 50 ° C. to about 150 ° C.
At this time, in order to keep the pressure in the concentration tank at a gauge pressure of about 0.05 to 0.15 MPa, heating was continued while removing water out of the system, and the concentration of the mixed solution was concentrated to about 80%. The obtained concentrated solution was transferred to an autoclave, and the temperature of the concentrated solution was increased from 150 ° C. to about 220 ° C., and the pressure in the autoclave was increased to about 1.77 MPa using the gauge pressure. Thereafter, the temperature was raised from about 220 ° C. to about 260 ° C., and heating was performed while removing water from the system so as to keep the pressure at about 1.77 MPa. Finally, the pressure was slowly reduced to atmospheric pressure while raising the temperature to about 280 ° C. The inside of the autoclave was pressurized with nitrogen, the produced polymer was discharged from the lower nozzle in a strand shape, water-cooled and cut to obtain pellets. The obtained pellets were dried in a nitrogen stream at 150 ° C. for 60 minutes to obtain a polyamide having the following viscosity number, phosphorus element concentration, and copper element concentration.
Viscosity number: 141 (measured in 96% sulfuric acid according to ISO 307)
Phosphorus element: 10ppm
Copper element: 0ppm

(1-2) Polyamide 6,6 (hereinafter abbreviated as PA-2)
The following polyamide was obtained in the same manner as in Example 1 except that the amount of 10% by weight aqueous solution of sodium hypophosphite (NaH ₂ PO ₂ ) was changed to 2957 g.
Viscosity number: 141 (measured in 96% sulfuric acid according to ISO 307)
Phosphorus element: 75ppm
Copper element: 0ppm
(1-3) Polyamide 6,6 (hereinafter abbreviated as PA-3)
It implemented by the method similar to Example 1, and the following polyamide was obtained. However, the blending amount of a 10% by weight aqueous solution of sodium hypophosphite (NaH ₂ PO ₂ ) was 5914 g. Moreover, it added at the time of superposition | polymerization so that the density | concentration of the copper iodide in polyamide might be 270 ppm.
Viscosity number: 141 (measured in 96% sulfuric acid according to ISO 307)
Phosphorus element: 150ppm
Copper element: 90ppm

(1-4) Polyamide 6,6 (hereinafter abbreviated as PA-4)
The following polyamide was obtained in the same manner as in Example 1 except that no sodium hypophosphite (NaH ₂ PO ₂ ) aqueous solution was added.
Viscosity number: 141 (measured in 96% sulfuric acid according to ISO 307)
Phosphorus element: 0ppm
Copper element: 0ppm
(1-5) Polyamide 6,6 (hereinafter abbreviated as PA-5)
828 g of acetic acid and 828 g of hexamethylene diamine are blended as end-capping agents in a 50 wt% aqueous solution containing 1600 kg of polyamide 66-forming component (equimolar salt of hexamethylene diamine and adipic acid). A mixed liquid containing 138 g of sodium acid, 345 g of potassium bicarbonate, and 55 g of a silicone-based antifoaming agent was prepared. The mixed solution was charged into a concentration tank, mixed under a temperature condition of about 50 ° C., and replaced with nitrogen. Subsequent operations were carried out in the same manner as in Example 1, and the following polyamide was obtained.
Viscosity number: 141 (measured in 96% sulfuric acid according to ISO 307)
Phosphorus element: 35ppm
Copper element: 0ppm

(1-6) Polyamide 6,6 (hereinafter abbreviated as PA-6)
A 50 wt% aqueous solution containing a polyamide 66 forming component (an equimolar salt of hexamethylenediamine and adipic acid) was preheated from 40 ° C to 100 ° C. Next, it is injected into a concentration / reaction apparatus for continuous polymerization at a rate of about 3000 kg / hr, and water is removed from the system in order to keep the pressure in the apparatus at a gauge pressure of about 0.1 to 0.5 MPa. However, the concentration of the solution was concentrated to about 90% at a temperature of 200 ° C. to 270 ° C.
Next, the concentrated liquid was discharged to a flasher, and the pressure was slowly reduced to atmospheric pressure. It transferred to the following superposition | polymerization container and superposition | polymerization process was performed by hold | maintaining on the conditions of about 280 degreeC temperature and the atmospheric pressure or less. Next, the produced polymer was extruded from a nozzle to form a strand, cooled and cut into pellets, and the following polyamide was obtained. However, in the continuous polymerization, a sodium hypophosphite aqueous solution was blended with the polyamide-forming component aqueous solution, and calcium acetate was blended with the polyamide in the polymerization step. The blending amounts of sodium hypophosphite and calcium acetate were adjusted so that the concentrations in the polyamide were 100 ppm and 500 ppm, respectively.
Viscosity number: 141 (measured in 96% sulfuric acid according to ISO 307)
Phosphorus element: 35ppm
Copper element: 0ppm

(1-7) Polyamide 6,6 (hereinafter abbreviated as PA-7)
828 g of acetic acid and 828 g of hexamethylene diamine are blended as end-capping agents in a 50 wt% aqueous solution containing 1600 kg of polyamide 66 forming component (equimolar salt of hexamethylene diamine and adipic acid), and sodium aluminate ((Na _{2 O) X (Al 3 O} 2) Y (X + Y = 1 and Y / X = 0.59)) of 38 wt% aqueous solution 726 g, 10 wt% aqueous solution of sodium hypophosphite _{(NaH 2} PO 2) 1380g A mixed liquid containing 55 g of a silicone-based antifoaming agent was prepared. The mixed solution was charged into a concentration tank, mixed under a temperature condition of about 50 ° C., and replaced with nitrogen. Subsequent operations were performed in the same manner as in Example 1, and the following polyamide was obtained.
Viscosity number: 141 (measured in 96% sulfuric acid according to ISO 307)
Phosphorus element: 35ppm
Copper element: 0ppm

(1-8) Polyamide 6,6 (hereinafter abbreviated as PA-8)
726 g of a 38 wt% aqueous solution of sodium aluminate ((Na ₂ O) _X (Al ₃ O ₂ ) _Y (X + Y = 1 and Y / X = 0.59)) was added to powdered sodium aluminate ((Na ₂ O) _X (Al ₂ O ₃ ) _Y (X + Y = 1 and Y / X = 0.81)) The same polyamide was obtained as in (1-7) except that 550 g was obtained.
Viscosity number: 141 (measured in 96% sulfuric acid according to ISO 307)
Phosphorus element: 35ppm
Copper element: 0ppm

(2) Polyphenylene ether (hereinafter abbreviated as PPE)
Poly (2,6-dimethyl-1,4-phenylene ether)
Reduced viscosity: 0.52 dl / g, (0.5 g / dl, chloroform solution, measured at 30 ° C.)
(3) Elastomer Polystyrene-hydrogenated polybutadiene-polystyrene block copolymer (hereinafter abbreviated as SEBS)
Product name: Kraton G1651 (manufactured by Kraton Polymer)
(4) Polystyrene (hereinafter abbreviated as GPPS)
Product name: Polystyrene 685 (manufactured by PS Japan)
(5) Inorganic filler (5-1) Glass fiber (hereinafter abbreviated as GF)
Product name: CS-03-MA-FT2A (Asahi Fiber Glass Co., Ltd.)
(6) Conductive carbon filler Product name: Ketjen Black EC-600JD (Ketjen Black International) (hereinafter abbreviated as CB)
Using a twin-screw extruder having one supply port on each of the upstream side and the downstream side, 90 parts by mass of polyamide 66 (PA-4) was added from the upstream supply port under the conditions set at a cylinder temperature of 270 ° C. After supplying and melting, 10 parts by mass of conductive carbon-based filler was added from the downstream supply port, and melt-kneaded to prepare a master batch. (Hereafter abbreviated as PA / CB-MB)
(7) Maleic anhydride (hereinafter abbreviated as MAH)
Product name: CRYSTALMAN-AB (manufactured by NOF Corporation)

(Evaluation methods)
The evaluation method is described below.
<Metal analysis>
Phosphorus in the composition and polyamide was quantified at a wavelength of 213.618 (nm) by high frequency inductively coupled plasma (ICP) emission analysis using an IRIS / IP manufactured by Thermo Jarrel Ash. Other metal elements were similarly quantified at the respective characteristic wavelengths.
<Adjustment of moisture content of pellet>
The resin composition pellets obtained in the examples and comparative examples were dried at 80 ° C. for 24 hours under a nitrogen atmosphere using a dryer. The dried resin pellet was sealed in an aluminum moisture-proof bag and allowed to stand at 23 ° C. for 24 hours. The moisture content of the resin pellet at this time was about 200 ppm. The pellets were left in a constant temperature and humidity room at 23 ° C. and 50 RH%, and after 20 minutes and 45 minutes, they were sealed again in aluminum moisture-proof bags and left at 23 ° C. for 24 hours. The moisture content of the resin pellets at this time was about 500 ppm and about 1,200 ppm, respectively.

<Melt flow rate (MFR)>
About the pellet which adjusted the moisture content, MFR under 280 degreeC and a 5-kg load was measured according to ASTMD1238.
<ΔMFR>
MFR was measured for pellets having at least three different moisture percentages in the resin composition in the range of about 200 ppm to about 1200 ppm, and the measured MFR values were plotted on a graph showing the relationship between MFR and moisture percentage. Then, ΔMFR was determined by obtaining the difference in MFR per 100 ppm of moisture content from the slope of a straight line obtained by approximating the plot to the least square.
<Silver Streak>
Using pellet 2 (water content of about 500 ppm), using a Toshiba IS-80EPN molding machine (melting resin temperature 280 ° C, mold temperature set to 80 ° C), molding a flat molded piece of 90 x 50 x 2.5 mm did. The molding conditions were an injection speed of 700 mm / second, a holding pressure of 40 MPa, an injection time + pressure holding time of 10 seconds in total, and a cooling time of 15 seconds. First, after forming 10 shots, the molding machine was stopped for 20 minutes, and then the molding was restarted. The first 5 shots of flat plate molded pieces were visually confirmed, and the number of molded pieces in which silver streaks were observed was counted. .

<Coating adhesion test>
The test piece was prepared using an injection molding machine (manufactured by Nissei Plastic Industry Co., Ltd .: FS80S), and a flat plate of 10 cm × 10 cm (thickness 2 mm) was created with a cylinder temperature of 305 ° C., a mold temperature of 80 ° C., and a filling time of 1 second. did.
The coating adhesion was measured on a flat plate after heat exposure at 204 ° C. for 40 minutes. Using an automatic spray coating apparatus, the coating thickness was adjusted to 20 μm and coating was performed. The paint used was an acrylic urethane paint (Origin Electric Co., Ltd., OP-Z-NY). After spray coating, baking was performed at a temperature of 150 ° C. for 20 minutes.
After painting, leave it in an environment with a temperature of 23 ° C and a humidity of 50%, and after 24 hours, scratch it in a grid pattern with a cutter knife so that the glance is 2mm square in the range of 2cm x 2cm (total 100), a coating film peeling test was performed in which an adhesive tape was applied and peeled off at once. The number of grids remaining without peeling after 100 peel tests was measured.

[Example 1-8, Comparative Example 1 to 7
It has an upstream supply port in the first barrel from the upstream side of the extruder, and a downstream supply port in the sixth barrel, and L / D (extruder cylinder length / extruder cylinder diameter) = 44 (barrel Number: 11) using a twin screw extruder [ZSK-40: manufactured by Coperion (Germany)], 320 ° C. from the upstream supply port to the downstream supply port, and 280 from the downstream supply port to the die. Set to ℃, screw rotation speed 300rpm, discharge rate 60kg / h, supply PPE, SEBS, GPPS, MAH from the upstream supply port so that the rate shown in Table 1 is melt kneaded, then supply downstream PA and NaH ₂ PO ₂ were supplied from the mouth to produce resin composition pellets. After adjusting the moisture of the obtained resin composition, MFR and silver streak were evaluated. The physical property values are shown in Table 1 and Table 2 together with the composition.

[Examples 9 to 16, Comparative Examples 8 to 11 ]
It has an upstream supply port in the first barrel from the upstream side of the extruder, a downstream first supply port in the sixth barrel, and a downstream second supply port in the eighth barrel. Length / cylinder diameter of the extruder) = 44 (number of barrels: 11) using a twin screw extruder [ZSK-40: manufactured by Coperion (Germany)], from the upstream supply port to the downstream first supply port Set to 320 ° C up to 280 ° C, and 280 ° C from the downstream first supply port to the die, and supply PPE, SEBS, MAH from the upstream supply port at a screw speed of 300 rpm and a discharge rate of 60 kg / h. After that, PA and PA / CB-MB were supplied from the downstream first supply port. Furthermore, GF was supplied from the downstream second supply port. Resin composition pellets were prepared so as to have the ratios shown in Table 2. After adjusting the moisture of the obtained resin composition, MFR and silver streak were evaluated. Moreover, about the resin composition which mix | blended the conductive carbon type filler, the coating adhesiveness was evaluated after shaping | molding. The physical property values are shown together with the composition in Table 3.

  According to the present invention, it is possible to obtain a polyamide-polyphenylene ether alloy resin composition having a small change in melt flow rate in a wide moisture content range and having excellent residence stability in a molding machine, and a molded body comprising the resin composition. It can be used in a wide range of fields such as electric / electronic parts, OA parts, vehicle parts, and machine parts. In particular, it can be suitably used for exterior parts such as automobiles that require large molded products.

Claims (16)

(A) Polyamide, (B) Polyphenylene ether, (C) Elastomer and (D) Phosphoric acid, phosphorous acid, hypophosphorous acid, phosphoric acid metal salt, phosphorous acid metal salt, hypophosphorous acid metal salt and phosphorus A method for producing a resin composition by melt-kneading one or more phosphorus compounds selected from acid esters,
The component (A) is a component in which the component (D) is added during the polymerization of the component (A), and (A-1) a polyamide containing 35 ppm to 250 ppm of phosphorus element and (A-2) phosphorus element A polyamide containing 0 ppm or more and less than 35 ppm,
(A)-(D) The manufacturing method of the resin composition characterized by obtaining the resin composition whose ratio of the phosphorus element with respect to 100 mass% of the sum total is 2-20 ppm.   2. The resin composition according to claim 1, wherein the component (D) is one or more phosphorus compounds selected from metal phosphates, metal phosphites, and metal hypophosphites. Method.   (D) 1 or more types as which a component is 1 or more types of phosphorus compounds chosen from phosphoric acid, phosphorous acid, and hypophosphorous acid, periodic table 1st group and 2nd group, manganese, zinc, and aluminum The method for producing a resin composition according to claim 1, wherein the salt is a metal salt.   Difference in melt flow rate per 100 ppm moisture content in the resin composition (MFR; measured at 280 ° C. under 5 kg load in accordance with ASTM D1238) (ΔMFR; moisture content in the resin composition in the range of 200 ppm to 1200 ppm) MFR was measured for pellets having at least three different moisture contents, and the measured MFR values were plotted on a graph showing the relationship between MFR and moisture content, and the moisture content was 100 ppm from the slope of the straight line approximating the least squares. The method for producing a resin composition according to any one of claims 1 to 3, wherein (determined by obtaining a difference in per unit MFR) is 0.65 g / 10 min or less. (F) further comprising a soluble metal aluminate represented by the general formula (M ₂ O) _X (Al ₂ O ₃ ) _Y (X + Y = 1, and M is a metal element of Group 1 of the Periodic Table). The manufacturing method of the resin composition in any one of Claims 1-4. (F) The aluminate in which the soluble metal aluminate is represented by the general formula (Na ₂ O) _X (Al ₂ O ₃ ) _Y (X + Y = 1 and 0.35 ≦ Y / X ≦ 1.25). It is sodium, The manufacturing method of the resin composition of Claim 5 characterized by the above-mentioned. The method for producing a resin composition according to claim 5 or 6 , wherein the component (F) is added in advance to the component (A) and blended. The method for producing a resin composition according to any one of claims 1 to 7 , wherein the resin composition further contains an alkali metal halide compound and / or a copper compound. The method for producing a resin composition according to claim 8 , comprising 1 to 100 ppm of copper element with respect to 100% by mass of the total amount of the resin composition. (A) polyamide, method for producing a resin composition according to any one of claims 1 to 9, characterized in that the aliphatic polyamide. (B) The polyphenylene ether is a polymer of 2,6-dimethylphenol and / or a copolymer of 2,6-dimethylphenol and 2,3,6-trimethylphenol. The method for producing a resin composition according to any one of 9 . (G) The method for producing a resin composition according to any one of claims 1 to 11 , further comprising a styrene-based polymer. (H) The method for producing a resin composition according to any one of claims 1 to 12 , further comprising an inorganic filler. The method for producing a resin composition according to claim 13 , wherein the inorganic filler (H) is at least one selected from glass fiber, talc, clay, wollastonite, and titanium oxide. The elastomer (C) is a hydrogenated product of a block copolymer composed of a polymer block of an aromatic vinyl compound and a polymer block of a conjugated diene compound, according to any one of claims 1 to 14 . A method for producing a resin composition. The resin according to any one of claims 1 to 15 , further comprising (I) a conductive carbon-based filler, wherein the conductive carbon-based filler is at least one selected from carbon fibrils and carbon black. A method for producing the composition.