JP4803765B2 - Method for producing extruded product of polyphenylene ether resin - Google Patents

Description

  The present invention relates to a method for producing a polyphenylene ether resin extruded product.

Polyphenylene ether resin is excellent in processability and productivity, and can efficiently produce products / parts of the desired shape by molding methods such as injection molding and extrusion molding, and the heat resistance, mechanical properties, Because of its excellent electrical characteristics, it is widely used as a material for products and parts in the electric / electronic field, automobile field, and other various industrial material fields (see, for example, Patent Documents 1 and 2).
However, in the conventional disclosed technology (for example, refer to Patent Document 3), quality such as productivity and surface smoothness when extrusion molding a polyphenylene ether-based resin composition to obtain a molded body such as a film or a sheet is obtained. Not necessarily good. Further, secondary workability such as large deflection when compression molding or vacuum molding was performed on the obtained molded body was not sufficiently satisfied. Furthermore, the obtained molded body may have a problem in the surface appearance and the like, and has not yet been widely deployed for use as an electric / electronic member, an automobile member, a building member, or other industrial member ( For example, refer to Patent Documents 3 to 5.)

Japanese Patent Publication No. 45-997 JP 2001-302911 A JP-A 63-277269 Japanese Patent Laid-Open No. 63-277270 JP-A-11-323122

  In view of the above-mentioned conventional problems, the present invention provides the productivity at the time of extrusion molding, the secondary workability at the time of compression molding and vacuum forming the obtained molded body, the heat resistance of the molded body, An object of the present invention is to provide a method for producing a polyphenylene ether-based resin molded article which has an excellent surface appearance and is suitable for use as an electric / electronic member, an automobile member, a building member, or other industrial member.

  The method for producing a polyphenylene ether-based resin molded article of the present invention comprises: (A) 5 to 95 parts by weight of a polyphenylene ether-based resin and (B) 5 to 95 parts by weight of a polyamide resin. Polyphenylene ether resin extrusion characterized by extruding a polyphenylene ether resin composition comprising 0.1 to 10 parts by weight of (C) ultrahigh molecular weight polymer having a molecular weight of 400,000 to 15 million using a heat insulating mold It is a manufacturing method of a molded object.

The polyphenylene ether-based resin composition of the present invention has the effect of being excellent in productivity at the time of extrusion molding, secondary workability at the time of compression molding and vacuum molding of the obtained molded body, and surface appearance of the molded product. Have.

Hereinafter, the present invention will be specifically described.
The polyphenylene ether-based resin composition of the present invention comprises (C) an ultra high molecular weight with respect to 100 parts by weight of a total amount of (A) 5 to 95 parts by weight of a polyphenylene ether resin and (B) 5 to 95 parts by weight of a polyamide resin. A polyphenylene ether-based resin composition comprising 0.1 to 10 parts by weight of a polymer.
The polyphenylene ether-based resin molded body of the present invention is a molded body obtained by extruding polyphenylene ether-based resin pellets obtained by melt-kneading the polyphenylene ether-based resin composition and then pelletizing.
<(A) Polyphenylene ether resin>
The (A) polyphenylene ether resin in the present invention is not particularly limited, but preferably comprises a mixture of (D) 5 to 100% by weight of polyphenylene ether and (E) 0 to 95% by weight of styrene resin.
The (D) polyphenylene ether of the present invention has a main chain structure of the following (formula 1), and can produce products / parts of a desired shape by a molding method such as a melt injection molding method or a melt extrusion molding method. It is a plastic material widely used as a material for products and parts in the electronic field, automobile field, and other various industrial material fields.

In the (D) polyphenylene ether represented by (Formula 1), R ₁ and R ₄ each independently represent hydrogen, primary or secondary lower alkyl, phenyl, aminoalkyl, or hydrocarbonoxy. R ₂ and R ₃ each independently represents hydrogen, primary or secondary lower alkyl, or phenyl.
The (D) polyphenylene ether of the present invention has a reduced viscosity measured at 30 ° C. using a 0.5 g / dl, chloroform solution, preferably in the range of 0.15-1.0 dl / g, more preferably 0.20-0. A polymer or copolymer in the range of 70 dl / g.
Specifically, the (D) polyphenylene ether of the present invention includes (F) poly (2,6-dimethyl-1,4-phenylene ether), poly (2-methyl-6-ethyl-1,4-phenylene ether). , Poly (2-methyl-6-phenyl-1,4-phenylene ether), poly (2,6-dichloro-1,4-phenylene ether) and the like.

As another specific example of the (D) polyphenylene ether of the present invention, a copolymer of 2,6-dimethylphenol and other phenols (for example, 2,3,6-trimethylphenol or 2-methyl-6-butylphenol) is used. Also included are polyphenylene ether copolymers such as polymers.
Among the above-mentioned (D) polyphenylene ethers of the present invention, (F) poly (2,6-dimethyl-1,4-phenylene ether), a copolymer of 2,6-dimethylphenol and 2,3,6-trimethylphenol. A polymer can be preferably used, and most preferred is poly (2,6-dimethyl-1,4-phenylene ether).

The manufacturing method of (D) polyphenylene ether used by this invention is not specifically limited.
As an example of the production method of (D) polyphenylene ether used in the present invention, there is a method of oxidative polymerization of 2,6-xylenol using a complex of cuprous salt and amine described in (Patent Document 6) as a catalyst.
US Pat. No. 3,306,874, US Pat. No. 3,306,875, US Pat. No. 3,257,357, US Pat. No. 3,257,358, Japanese Patent Publication No. 52-17880, Japanese Patent Laid-Open No. 50-51197, The method described in 63-152628 is also preferable as the method for producing the polyphenylene ether of the present invention.
The terminal structure of (D) polyphenylene ether of the present invention is preferably the following structure (Formula 2).

[Wherein, R ₁ , R ₂ , R ₃ and R ₄ are defined in the same manner as R ₁ , R ₂ , R ₃ and R ₄ in (Formula 1), respectively. ]
The terminal structure of (D) polyphenylene ether of the present invention is more preferably the following structure (Formula 3).

[Wherein R ₅ and R ₅ ′ represent hydrogen or an alkyl group. ]
As a method of obtaining (D) polyphenylene ether having a terminal structure of (Formula 3), a catalyst containing copper or manganese is used, and 2,6-dimethylphenol is obtained in the presence of a primary or secondary amine. An example is a method of oxidative coupling reaction.
As the primary or secondary amine, dialkylamine is preferable, and di-n-butylamine, dimethylamine, and diethylamine are more preferably used.
In the (D) polyphenylene ether of the present invention, a desired additive may be added in advance according to the purpose.

<(B) Polyamide resin>
Any (B) polyamide resin that can be used in the present invention can be used as long as it has an amide bond {—NH—C (═O) —} in the polymer main chain. .
In general, the (B) polyamide resin is obtained by ring-opening polymerization of lactams, polycondensation of diamine and dicarboxylic acid, polycondensation of aminocarboxylic acid, and the like, but is not limited thereto.
The diamines are roughly classified into aliphatic, alicyclic and aromatic diamines. Specific examples include tetramethylene diamine, hexamethylene diamine, undecamethylene diamine, dodecamethylene diamine, tridecamethylene diamine, 2, 2 , 4-trimethylhexamethylenediamine, 2,4,4-trimethylhexamethylenediamine, 5-methylnanomethylenediamine, 1,3-bisaminomethylcyclohexane, 1,4-bisaminomethylcyclohexane, m-phenylenediamine, p -Phenylenediamine, m-xylylenediamine, p-xylylenediamine.

Dicarboxylic acids are roughly classified into aliphatic, alicyclic and aromatic dicarboxylic acids. Specific examples include adipic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, 1,1,3-tridecane. Examples include diacid, 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-aminonanoic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid, and 13-aminotridecane. An acid etc. are mentioned.

In the present invention, any of these lactams, diamines, dicarboxylic acids, and ω-aminocarboxylic acids can be used alone or as a copolymerized polyamide obtained by polycondensation in a mixture of two or more.
Also, 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 resin 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.

  The polyamide resin (B) that can be preferably used in the present invention is 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, 12, polyamide 6, MXD (m-xylylenediamine), 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 / Polyamides such as 12/6, T, polyamide 6/12/6, I, polyamide 6, 6/12/6, I and the like, and a polyamide obtained by copolymerizing a plurality of polyamides with an extruder or the like It can be used.

More preferable (B) polyamide resin in the present invention is polyamide 6, polyamide 6,6, polyamide 6 / 6,6 and a mixture thereof, and most preferably polyamide 6, polyamide 6,6, or a mixture thereof. .
The (B) polyamide resin highly preferred in the present invention is a polyamide comprising a mixture of polyamide 6,6, 0 to 100% by weight and polyamide 6, 100 to 0% by weight.
The preferred viscosity range of the polyamide that can be used in the present invention is such that the viscosity number measured in 96% sulfuric acid according to ISO 307 is 50 to 300 ml / g. More preferably, it is the range of 80-180 ml / g.

In the present invention, even if the (B) polyamide resin is a polyamide mixture having a viscosity number outside the above range, it can be used without any problem as long as the viscosity number of the mixture is within the above range. . Examples thereof include a mixture of a polyamide having a viscosity number of 150 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.
Also in these cases, any mixture ratio may be used as long as the viscosity number of the mixture is within the above range. Whether or not the viscosity number of these mixtures is within the above range can be easily confirmed by dissolving in 96% sulfuric acid at a mixing weight ratio and measuring the viscosity number according to ISO307.

(B) A particularly preferable mixed form among the polyamide resins is a mixture of polyamides in which each polyamide is in the range of 90 to 150 ml / g in viscosity and different in viscosity number.
Polyamide generally has an amino group and a carboxyl group as terminal groups, but a preferable ratio of these is 9/1 to 1/9, more preferably 8/2 to 1 in terms of amino group / carboxyl group concentration ratio. / 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 concentration of the terminal carboxyl group is preferably at least 9 × 10 ⁵ mol / g or more. More preferably, it is 9 × 10 ⁵ or more and 13 × 10 ⁵ mol / g or less.

As a method for quantifying amino groups and carboxyl groups, which are polyamide end groups, J. Org. E. Waltz, Guy B. Taylor, “Determination of the Molecular Weight of Nylon”, Ind. Eng. Chem. Anal. Ed. 19,448 (1947) can be preferably used.
In addition to the above method, the amino group / carboxyl group concentration ratio can be determined from the intensity ratio of peaks derived from the respective terminal groups by the 1H-NMR method.
As a method for adjusting the end groups of these polyamides, a known method as will be apparent to those skilled in the art can be used. 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.

In the present invention, (B) a metal stabilizer as described in JP-A-1-163262, which has been publicly known for the purpose of improving the heat resistance stability of polyamide, should be used without any problem. Can do.
Among these metal stabilizers, those which can be particularly preferably used include CuI, CuCl ₂ , copper acetate, cerium stearate and the like. Further, halogenated salts of alkyl metals typified by potassium iodide, potassium bromide and the like can also be suitably used. Of course, these may be added together.
A preferred blending amount of the metal stabilizer and / or the alkyl metal halide salt is 0.001 to 1 part by weight with respect to 100 parts by weight of the polyamide as a total amount.

Moreover, in this invention, a well-known organic stabilizer other than the metal stabilizer mentioned above can be used without a problem. Examples of organic stabilizers include hindered phenol antioxidants typified by Irganox 1098, phosphorus processing heat stabilizers typified by Irgaphos 168, and lactone processing heat stability typified by HP-136. Agents, sulfur heat stabilizers, hindered amine light stabilizers, and the like.
Among these organic stabilizers, a hindered phenol antioxidant, a phosphorus processing heat stabilizer, or a combination thereof is more preferable.
A preferable blending amount of these organic stabilizers is 0.001 to 1 part by weight with respect to 100 parts by weight of (N) polyamide. In addition to the above, known additives that can be added to (N) polyamide may be added in an amount of less than 10 parts by weight with respect to 100 parts by weight of (N) polyamide.

<(C) Ultra high molecular weight polymer>
In the polyphenylene ether resin composition of the present invention, (C) the addition of the ultrahigh molecular weight polymer improves the productivity during extrusion molding, and a polyphenylene ether resin molded article with a smooth surface and good appearance is obtained. It is done.
(C) The ultrahigh molecular weight polymer has a viscosity average molecular weight measured by a viscosity method of 400,000 or more from the viewpoint of improving productivity, and 15 million or less from an appearance problem.
In the present invention, when the viscosity average molecular weight of the (C) ultrahigh molecular weight polymer is preferably 1.2 million to 10 million, more preferably 3 million to 9 million, the productivity at the time of extrusion molding is particularly good. Become.

(C) Ultra high molecular weight polymer preferable in the present invention is polyethylene, polystyrene, polymethyl methacrylate, styrene-butadiene block copolymer, hydrogenated styrene-butadiene block copolymer, polyalkyl methacrylate, alkyl acrylate copolymer. Ultra high molecular weight materials such as polytetrafluoroethylene can be used.
(C) Ultra high molecular weight polymer more preferable in the present invention includes ultra high molecular weight polyethylene, ultra high molecular weight polyalkyl methacrylate, and ultra high molecular weight alkyl methacrylate copolymer in view of productivity at the time of extrusion molding and appearance of the molded product. It is a combination or ultra high molecular weight polytetrafluoroethylene.
The most preferred (C) ultra high molecular weight polymer in the present invention is ultra high molecular weight polyethylene.

The addition amount of (C) the ultra high molecular weight polymer in the polyphenylene ether resin composition of the present invention is 100 weights comprising (A) 5 to 95 parts by weight of the polyphenylene ether resin and (B) 5 to 95 parts by weight of the polyamide resin. Part is 0.1 parts by weight or more from the point of smoothness of the surface of the molded body, 10 parts by weight or less from the point of rigidity and heat resistance, preferably 0.3 to 8 parts by weight, most preferably, 0.5 to 6 parts by weight.
The viscosity average molecular weight of ultrahigh molecular weight polyethylene is an average molecular weight measured by a viscosity method. Specifically, according to DIN 53 728 sheet 4, the viscosity number is measured using decahydronaphthalene, and the average molecular weight is calculated using the following equation.

Martin's equation log η = log [η] + K · [η] · c
η: Viscosity number [η]: Intrinsic viscosity (dl / g)
K: 0.139 (g)
c: 0.03 (g / dl)
Margolys's equation M = 5.37 · 10 ⁴ [η] ^1.49
M: Viscosity average molecular weight

<(E) Styrenic resin>
(E) Styrenic resin referred to in the present invention is homopolystyrene, rubber-modified polystyrene (HIPS), styrene-acrylonitrile copolymer (AS resin), styrene-rubber polymer-acrylonitrile copolymer (ABS resin), Examples thereof include styrene-containing block copolymers.
In the present invention, from the viewpoint of maintaining high heat resistance of the polyphenylene ether resin composition, a styrene-containing block copolymer can be preferably used as the (E) styrene resin.

<Styrene-containing block copolymer>
The styrene-containing block copolymer that can be used in the present invention is a block copolymer comprising a polymer block mainly composed of at least one styrene compound and a polymer block mainly composed of at least one conjugated diene compound. A polymer or a hydrogenated styrene-containing block copolymer hydrogenated to an unsaturated bond in a polymer block mainly composed of a conjugated diene compound in the block copolymer.

The “mainly” in the polymer block mainly composed of the styrene compound of the present invention refers to a block in which at least 50% by weight or more of the block is a styrene compound. More preferably, it is 70 weight% or more, More preferably, it is 80 weight% or more, Most preferably, it is 90 weight% or more. The same applies to “mainly” in a polymer block mainly composed of a conjugated diene compound, and indicates a block in which at least 50% by weight or more is a conjugated diene compound. More preferably, it is 70 weight% or more, More preferably, it is 80 weight% or more, Most preferably, it is 90 weight% 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 styrene compound block, if 50% by weight of the block is formed from the styrene compound, It is regarded as a block copolymer mainly composed of a styrene compound. The same applies to the case of a conjugated diene compound.

Specific examples of the styrene compound include styrene, α-methylstyrene, vinyltoluene and the like. One or more compounds selected from these are used, and styrene is particularly preferable among them.
Specific examples of the conjugated diene compound include butadiene, isoprene, piperylene, 1,3-pentadiene and the like, and one or more compounds selected from these are used. Of these, butadiene, isoprene and combinations thereof are preferable. .
As for the microstructure of the block part of the conjugated diene compound of the styrene-containing block copolymer, the 1,2-vinyl content or the total amount of the 1,2-vinyl content and the 3,4-vinyl content is preferably 5 to 80%, more preferably 10 to 50% is preferable, and 15 to 40% is most preferable.
In the styrene-containing block copolymer of the present invention, the polymer block a mainly composed of a styrene compound and the polymer block b mainly composed of a conjugated diene compound are ab type, aba type, ab type. A block copolymer having a bond type selected from the -ab type is preferred. Among these, the aba type is more preferable. Of course, these may be a mixture.

The styrene-containing block copolymer used in the present invention is preferably a hydrogenated styrene-containing block copolymer.
A hydrogenated styrene-containing block copolymer is an aliphatic double polymer block composed mainly of a conjugated diene compound by hydrogenating the above-mentioned block copolymer of a styrene compound and a conjugated diene compound. The bond is hydrogenated at least 50% or more. More preferably 80% or more, and most preferably 98% or more hydrogenated.
The number average molecular weight of the hydrogenated styrene-containing block copolymer that can be used in the present invention is desirably 200,000 or more and 300,000 or less. Although it is possible to use a hydrogenated block copolymer outside this molecular weight range, it is possible to use a hydrogenated block copolymer in this range even in a small amount in order to develop a high impact with a small amount of addition. desirable.

The number average molecular weight referred to in the present invention is measured with an ultraviolet spectroscopic detector [UV-41: Showa Denko KK] using a gel permeation chromatography measuring device [GPC SYSTEM21: Showa Denko KK]. And the number average molecular weight in terms of standard polystyrene. [Solvent: Chloroform, Temperature: 40 ° C., Column: Sample side (KG, K-800RL, K-800R), Reference side (K-805L × 2), Flow rate 10 ml / min, Measurement wavelength: 254 nm, Pressure 15-17 kg / cm < ² >]. At this time, a low molecular weight component due to catalyst deactivation during polymerization may be detected. In this case, the low molecular weight component is not included in the molecular weight calculation. Usually, the calculated correct molecular weight distribution (weight average molecular weight / number average molecular weight) is in the range of 1.0 to 1.2.

The styrene-containing block copolymer is generally produced by a living anion polymerization method, and a copolymer having a very narrow molecular weight distribution (Mw / Mn = about 1.0 to 1.2) is obtained.
Further, unless the styrene-containing block copolymer is contrary to the spirit of the present invention, those having different bonding types, those having different styrene compound types, those having different conjugated diene compound types, 1,2-bonded vinyl content or A mixture having a different 1,2-bonded vinyl content and a 3,4-bonded vinyl content, a different styrene compound component content, a different hydrogenation rate, or the like may be used in combination. Of course, there is no problem in adding a block copolymer other than the styrene-containing block copolymer defined in the present invention.
Further, the styrene-containing block copolymer used in the present invention may be a styrene-containing block copolymer that has been modified in whole or in part.

The modified styrene-containing block copolymer here refers to a styrene-containing block copolymer modified with (G) a modifier or (I) an acid modifier described in detail later.
As a method for producing a modified styrene-containing block copolymer, (1) in the presence or absence of a radical initiator, at a temperature not lower than the softening point temperature of the styrene-containing block copolymer and not higher than 250 ° C. A method of reacting by melting and kneading with a modifying compound, (2) a styrene-containing block copolymer and (G) a modification at a temperature below the softening point of the styrene-containing block copolymer in the presence or absence of a radical initiator. Or (I) a method of reacting an acid modifier in a solution; (3) a styrene-containing block copolymer at a temperature below the softening point of the styrene-containing block copolymer in the presence or absence of a radical initiator. Examples thereof include a method of reacting the coalescence with (G) the modifier or (I) the acid modifier without melting.

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.
Moreover, you may use for the styrene containing block copolymer of this invention what mixed beforehand the oil which has a paraffin as a main component. The processability of the resin composition can be improved by preliminarily mixing oil mainly composed of paraffin.

<(G) Denaturant>
The modifier (G) used in the present invention has at least one carbon-carbon double bond or triple bond and at least one acyl oxide group, imino group, imide group, or glycidyl group in the molecular structure. It is.
The compound used as the modifier (G) of the present invention includes, for example, maleimide, N-alkylmaleimide, N-arylmaleimide, N-alkylmaleamic acid, N-arylmaleamic acid, maleic anhydride, maleic acid, fumaric acid. Acids, phenylmaleimide, itaconic acid, glycidyl methacrylate, glycidyl acrylate, and the like.
The (G) modifier of the present invention is very preferably maleic anhydride, maleic acid, fumaric acid, phenylmaleimide, or itaconic acid.
The modified polyphenylene ether of the present invention comprises (F) 100 parts by weight of poly (2,6-dimethyl-phenylene oxide), at least one carbon-carbon double bond or triple bond in the molecular structure, and at least one It is obtained by subjecting 0.1 to 10 parts by weight of at least one (G) modifier selected from those having an acyl oxide group, an imino group, an imide group, or a glycidyl group to a heat reaction in advance.

The production method of the modified polyphenylene ether of the present invention is 0.1 parts by weight or more from the viewpoint of the effect with respect to 100 parts by weight of the polyphenylene ether (A), and 10 parts by weight or less from the viewpoint of occurrence of silver streak during molding. Yes, it is necessary to mix the above-mentioned amount of the (G) modifier and react by heating.
As (D) polyphenylene ether of the present invention, (F) 100 parts by weight of poly (2,6-dimethyl-phenylene oxide), at least one carbon-carbon double bond or triple bond in the molecular structure, and at least 1 It is obtained by subjecting 0.1 to 10 parts by weight of at least one (G) modifier selected from those having one acyl oxide group, imino group, imide group, or glycidyl group to heat reaction (H). When a modified polyphenylene ether is used, the compatibility of the (A) polyphenylene ether resin is improved, so that it can be preferably used.

  As a method for producing the (A) polyphenylene ether-based resin of the present invention, a more preferable method is (F) 100 parts by weight of poly (2,6-dimethyl-phenylene oxide) and at least one carbon-carbon diene in the molecular structure. 0.1 to 10 parts by weight of at least one (G) modifier selected from those having a heavy bond or a triple bond and at least one acyl oxide group, imino group, imide group, or glycidyl group in advance. This is a method obtained by reacting to obtain a modified polyphenylene ether and subsequently adding (B) a polyamide resin.

<(I) Acid modifier>
The (I) acid modifier used in the present invention is a compound selected from polycarboxylic acids and / or modified products of polycarboxylic acids.
The acid modifying agent (I) used in the present invention is preferably a polycarboxylic acid such as citric acid or malic acid, or a derivative of citric acid or malic acid.
In the method for producing the acid-modified polyphenylene ether of the present invention, 0.1 to 10 parts by weight of the above-mentioned (I) acid modifier is mixed with 100 parts by weight of the polyphenylene ether (A), and the reaction is performed by heating. To do.

The acid-modified polyphenylene ether of the present invention is (F) 100 parts by weight of poly (2,6-dimethyl-phenylene oxide), at least one selected from polycarboxylic acid and / or a modified product of polycarboxylic acid ( I) It is obtained by heat-reacting 0.1 to 10 parts by weight of the acid modifier in advance.
As (D) polyphenylene ether of the present invention, (F) 100 parts by weight of poly (2,6-dimethyl-phenylene oxide), at least one selected from polycarboxylic acid and / or a modified product of polycarboxylic acid ( I) When an acid-modified polyphenylene ether obtained by heat-reacting 0.1 to 10 parts by weight of an acid modifier in advance is used, the compatibility of the (A) polyphenylene ether resin is improved, so that it can be preferably used.

As a method for producing the (A) polyphenylene ether resin of the present invention, a more preferred method is (F) poly (2,6-dimethyl-phenylene oxide) 100 parts by weight, polycarboxylic acid, and / or modification of polycarboxylic acid. First, 0.1 to 10 parts by weight of (I) acid modifier selected from products is first heated and reacted to obtain (J) acid-modified polyphenylene ether, and then (B) polyamide resin is added. It is a way to get.
In this invention, the polyphenylene ether-type resin composition which contains 0.1-5 weight part of (G) modifier | denaturant with respect to 100 weight part of (A) polyphenylene ether resin can also be used preferably.
In the present invention, a polyphenylene ether-based resin composition containing 0.1 to 5 parts by weight of (I) an acid modifier with respect to 100 parts by weight of (A) polyphenylene ether resin fat can also be preferably used.

<Carbon>
In the present invention, carbon may be added to the polyphenylene ether resin composition.
Examples of carbon that can be used in the present invention include ketjen black (EC, EC-600JD) available from Ketjen Black International and carbon fibrils (BN fibril) available from Hyperion Catalysis International. Can do. Among the carbon fibrils, carbon fibrils as disclosed in International Publication No. WO94 / 23433 are particularly preferable.
Although there is no restriction | limiting in particular regarding the addition method of carbon, The method of adding in the form of the masterbatch by which carbon was previously mix | blended with polyamide is preferable. In this case, when the polyamide master batch is 100% by weight, the amount of carbon is preferably 5 to 15% by weight.

<Other additives>
Additives used in the polyphenylene ether-based resin composition of the present invention include heat stabilizers, antioxidants, UV absorbers, surfactants, lubricants, fillers, polymer additives, dialkyl peroxides, diacyl peroxides, peroxys. , Peroxycarbonate, hydroperoxide, peroxyketal, inorganic filler (talc, kaolin, zonotlite, wollastonite, titanium oxide, potassium titanate, carbon fiber, glass fiber, etc.), inorganic filler and resin Known silane coupling agents, flame retardants (halogenated resins, silicone flame retardants, magnesium hydroxide, aluminum hydroxide, organic phosphate compounds, ammonium polyphosphate, red phosphorus, etc.) for dropping affinity Fluoropolymers and plasticizers (oil, low molecular weight Fins, polyethylene glycols, fatty acid esters, etc.) and flame retardant aids such as antimony trioxide, colorants such as carbon black, antistatic agents, various peroxides, zinc oxide, zinc sulfide, antioxidants, UV absorption Agents, light stabilizers and the like.

The specific addition amount of these components is in a range not exceeding 100 parts by weight (as a total of additional components) when the total of polyamide and polyphenylene ether is 100 parts by weight.
Furthermore, various stabilizers known for stabilizing polyphenylene ether can also be suitably used. Examples of stabilizers are metal stabilizers such as zinc oxide and zinc sulfide, organic stabilizers such as hindered phenol stabilizers, phosphorus stabilizers, and hindered amine stabilizers. The amount is less than 5 parts by weight based on 100 parts by weight of polyphenylene ether.

<Polyphenylene ether resin pellet>
A preferred form for applying the polyphenylene ether resin composition of the present invention to various molding methods is polyphenylene ether resin pellets obtained by melt-kneading the polyphenylene ether resin composition of the present invention and then pelletizing. .
Specific processing machines for melt-kneading the polyphenylene ether-based resin 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. However, among these, a twin screw extruder can be preferably used.
The above processing machine that can be preferably used in the present invention is a twin screw extruder.
A processing machine that can be particularly preferably used in the present invention is a twin screw extruder having an upstream supply port and one or more downstream supply ports and having a screw diameter of 40 mm or more and an L / D of 30 or more.
At this time, the processing set temperature of the cylinder or the like of the processing machine is not particularly limited, and the conditions under which a suitable composition is obtained can be arbitrarily selected from 240 to 360 ° C.

<Polyphenylene ether resin extrusion molding method and molded article>
From the polyphenylene ether-based resin composition of the present invention, in order to give the shapes of parts and the like required in various industries, usually, an injection molding method, a melt molding method such as an extrusion molding method, a press molding method, a vacuum molding method, etc. A known processing method such as a heat molding method can be employed.
The polyphenylene ether resin composition of the present invention and / or the above polyphenylene ether resin pellets can be suitably used particularly for a processing method of an extrusion molding method.
The polyphenylene ether-based resin composition of the present invention and / or the polyphenylene ether-based resin extruded product obtained by extruding the above-mentioned polyphenylene ether-based resin pellet is superior in productivity and product to the conventional extruded product. Excellent surface smoothness. The mold used in the extrusion molding of the present invention is not particularly limited, but preferably a heat insulating mold, and more preferably a fluororesin-coated mold is preferable because productivity and product quality can be further improved.

Especially when extruding.
Polyphenylene ether resin extrusion molded products molded using a heat-insulating mold have a stable extrusion speed because the molding speed of the molded product is stable, and the product surface smoothness is particularly excellent, and the product thickness is stable. Therefore, it is very preferable.
The heat insulating mold of the present invention has a heat insulating layer on the inner surface of a metallic mold.
Although it does not specifically limit as a material of the said heat insulation layer in this invention, Ceramics, a high heat resistant thermoplastic resin, and a thermosetting resin can be used preferably.
In the present invention, it is preferable to use a thermosetting resin as the heat insulating layer, and it is very preferable to use a fluororesin.
When a fluororesin-coated mold is used as the heat insulating mold, a molded article having a good surface can be obtained, and the deterioration of the heat insulating layer is small, which is extremely preferable as a polyphenylene ether-based resin extrusion molding method.

The shape of the molded product obtained by the polyphenylene ether resin extrusion molding method of the present invention is not particularly limited.
The polyphenylene ether-based resin extrusion molding method of the present invention can be preferably used as a film or sheet molding method having a thickness of 1 μm to 5 mm.
The polyphenylene ether resin extruded film formed by the polyphenylene ether resin extrusion molding method of the present invention is particularly excellent in surface smoothness and thickness uniformity.
Furthermore, this polyphenylene ether-based resin extrusion-molded film has low productivity when pre-heated during secondary processing by a molding method such as press molding or vacuum molding, and is excellent in productivity.
The masking material formed by press-molding or vacuum-molding the polyphenylene ether-based resin extruded film of the present invention is excellent in surface smoothness and dimensional accuracy, and can be suitably used for various applications in the electronic / electric field and automobile field. It is.
Hereinafter, the present invention will be described in more detail with reference to examples and comparative examples.

Hereinafter, the present invention will be described in more detail based on examples. In the examples, “part” represents “part by weight”.
<Raw material>
The raw materials used in the examples are as follows.
<(A) Polyphenylene ether resin>
In the examples of the present invention, the (A) polyphenylene ether resin has a reduced viscosity of 0.42 dl / g (0.5 g / dl, chloroform solution, measured at 30 ° C. using an Ubbelohde viscometer) (F ) Set a cylinder temperature of 320 ° C. with 0.1 parts by weight of a radical initiator and 1.5 parts by weight of maleic anhydride added to 100 parts by weight of poly (2,6-dimethyl-phenylene oxide) Modified polyphenylene ether (hereinafter referred to as MPPE) obtained by melt kneading using the twin screw extruder was used.

<(B) Polyamide resin>
In Examples of the present invention, Leona 1200 (trade name) (hereinafter referred to as PA), which is polyamide-6,6 manufactured by Asahi Kasei Chemicals Corporation, was used as the polyamide resin (B).
<(C) Ultra high molecular weight polymer>
In the examples of the present invention, (C) ultrahigh molecular weight polymers manufactured by TICONA GmbH, GUR (registered trademark) 4113 (viscosity average molecular weight: 3.2 million) (hereinafter, HMWPE-1) and GHR8110 (GHR8110) Viscosity average molecular weight: 490,000) (hereinafter, HMWPE-2) was used.

<(E) Styrenic resin>
In an example of the present invention, Kraton G1651 (SEB) is a kind of polystyrene-polyethylenebutylene-polystyrene block copolymer (SEBS) of (K) styrene-containing block copolymer manufactured by Kraton Polymer Japan Co., Ltd. (Trade name) (number average molecular weight: about 250,000) (hereinafter referred to as SEBS) was used.
<Twin screw extruder>
In the examples of the present invention, a ZSK40MC [manufactured by Coperion (Germany)] having an L / D of 44 was used. All cylinder temperatures were set to 300 ° C and the die temperature was set to 280 ° C. In addition, when the total length of the screw was 1.0, vent ports were installed at two locations, a position of about 0.35 and a position of about 0.90 when viewed from the upstream side, and vacuum suction was performed.

[Example 1]
Each raw material was quantitatively supplied to the twin screw extruder from a hopper type supply port using a weight type feeder. The feed amount of the polyphenylene ether resin composition is as follows: MPPE: 38 parts by weight, SEBS: 10 parts by weight, PA: 47 parts by weight, HMWPE-1 : 5 parts by weight.
The screw rotation speed of the twin screw extruder was set to 240 rpm (discharge amount / screw rotation speed ratio = 0.25), and melt kneading was performed at a total raw material supply amount per hour of 60 kg / h.
The string-like strand melt-kneaded and discharged from the die was cut with a strand cutter to obtain a polyphenylene ether resin pellet.

The obtained pellets were melted at a molten resin temperature using a sheet molding machine (Technobel: KZW15 twin screw extruder) with a heat insulating mold formed by applying Teflon (registered trademark) of about 200 μm to the inner surface of the mold. It was set at 280 ° C. and a mold temperature of 90 ° C., and molded into a sheet shape having a thickness of 3 mm and a width of 15 cm to obtain a polyphenylene ether-based resin sheet. The molding speed was gradually increased until a defect on the sheet surface occurred, and a defective discharge amount at which a crust-like defect occurred on the sheet end face was determined.
The surface smoothness was evaluated by measuring the gloss of the obtained sheet at 60 ° oblique angle by the method of JIS K 7105.
Further, vacuum forming was performed on the obtained sheet. Prior to vacuum forming, preheating is carried out. The preheating temperature was gradually increased, and the bending temperature at which the polyphenylene ether resin sheet was bent was measured.
A box-shaped molded product was molded from the above pellets by vacuum molding, and the surface of the molded product was observed.

[Example 2]
HMWPE-1 in the raw material in the polyphenylene ether resin composition used in Example 1 was replaced with HMWPE-2, and the others were carried out in the same manner as in Example 1.

[Comparative Example 1]
The supply amount of each raw material of the polyphenylene ether resin composition in Example 1 is MPPE: 40 parts by weight, SEBS: 10 parts by weight, PA: 50 parts by weight with respect to a total of 100 parts by weight of the total raw material supply amount per hour. The others were carried out in the same manner as in Example 1 in place of the parts.

[Comparative Example 2]
HMWPE-1 in the raw material in the polyphenylene ether-based resin composition used in Example 1 was replaced with high density polyethylene having a viscosity average molecular weight of 80,000, and the others were carried out in the same manner as in Example 1.
(result)
The amount of defective discharge, 60 degree glossiness, and rupture temperature were corrected to values obtained when the result of Example 1 was set to 100, and compared with Example 2 and Comparative Example. The results are shown in Table 1 together with the observation results of the press-formed product.

By using the polyphenylene ether-based resin composition of the present invention, the productivity at the time of extrusion molding, the secondary workability at the time of compression molding and vacuum molding of the obtained molded body, and the surface appearance of the molded product It has become possible to stably form a polyphenylene ether-based resin molded article that is excellent and suitable for use as an electric / electronic member, an automobile member, a building member, and other industrial members.
Furthermore, the polyphenylene ether resin molded product obtained by molding this polyphenylene ether resin composition has good quality.

Claims (2)

  Ultra high molecular weight polymer (C) having a viscosity average molecular weight of 400,000 to 15 million with respect to a total amount of 100 parts by weight of 5 to 95 parts by weight of polyphenylene ether resin (A) and 5 to 95 parts by weight of polyamide resin (B) A method for producing a polyphenylene ether-based resin extruded product, comprising extruding a polyphenylene ether-based resin composition comprising 0.1 to 10 parts by weight using a heat insulating mold.   The method for producing a polyphenylene ether-based resin extruded product according to claim 1, wherein the heat insulating mold is a fluororesin-coated mold.