JP6231452B2 - Flame retardant resin composition and method for producing the same - Google Patents

Description

  The present invention relates to a flame retardant resin composition and a method for producing the same.

  Conventionally, polyphenylene ether-based resins have been used in home appliances, OA equipment, automobile parts, etc. because they have excellent electrical insulation properties, as well as good heat resistance, flame retardancy, hydrolysis resistance, and the like. Yes.

  In recent years, there has been a strong demand for resin compositions with excellent processability (particularly fluidity) in order to increase the size and precision of resin parts. On the other hand, resin compositions have impact resistance and flame resistance. Sex etc. are also demanded.

  In order to meet such requirements, by adding low molecular weight polystyrene resin, mineral oil, styrene elastomer, flame retardant, etc. to polyphenylene ether resin, the resin composition has high heat resistance inherently possessed by polyphenylene ether resin. In addition to the properties, attempts have been made to impart processability, impact resistance, flame retardancy, and the like.

  However, when a low molecular weight polystyrene resin or mineral oil is added, the resulting resin composition has excellent processability, but has a problem that it is difficult to provide sufficient heat resistance, impact resistance, and flame retardancy. (For example, refer to Patent Document 1).

  In addition, when a phosphate ester flame retardant is added, the resulting resin composition has excellent processability and flame retardancy, but it is difficult to provide sufficient heat resistance and impact resistance (see, for example, Patent Document 2). ).

  When a cyclic phosphazene compound, which is a flame retardant, is added instead of a phosphate ester flame retardant, the flame retardancy and heat resistance of the resulting resin composition are improved, but there are problems in terms of processability and cost. (For example, see Patent Document 3).

  Attempts have been made to use a cyclic phosphazene compound in combination with another phosphorus compound, but information on mechanical properties and the like necessary for practical use of the resin composition has not been sufficiently disclosed (for example, see Patent Document 4). ).

JP 2000-154289 A JP-A-9-31321 JP 2004-107374 A JP 2005-154762 A

  In these conventional techniques, when a cyclic phosphazene compound or a phosphate ester flame retardant is added to a polyphenylene ether resin, any of the processability, heat resistance, impact resistance and flame resistance of the resin composition is Although it is improved, there is a problem that any of the above characteristics is deteriorated, and it has not been possible to obtain a resin composition that sufficiently satisfies the level required in the market.

  Therefore, an object of the present invention is to provide a polyphenylene ether-based flame retardant resin composition having a good balance of workability, heat resistance, impact resistance, and flame retardancy, and a method for producing the same.

  As a result of intensive studies in order to solve the above problems, the present inventor, in a resin composition containing a polyphenylene ether resin, a cyclic phosphazene compound, and a condensed phosphate ester flame retardant, In addition, a polyphenylene ether-based flame retardant resin composition having a good balance of workability, heat resistance, impact resistance and flame resistance by containing a cyclic phosphazene compound and a condensed phosphate ester flame retardant as a specific mass ratio It has been found that the product can be obtained, and further, by using a specific production method, the productivity of the flame retardant resin composition can be improved, and the present invention has been completed.

［式中、ｎは３〜２５の整数である］
前記（ｃ）成分が下記式（２）で表される縮合リン酸エステル系難燃剤である、

［式中、ｍは１〜５の整数であり；Ｒ _１ 、Ｒ _２ 、Ｒ _３ 、Ｒ _４ は、それぞれ独立して、水素原子、ハロゲン原子、アルキル基、シクロアルキル基、アリール置換アルキル基、アリール基、ハロゲン置換アリール基、アルキル置換アリール基からなる群から選択される置換基であり；Ｒ _１ 、Ｒ _２ 、Ｒ _３ 、Ｒ _４ は、互いに同一でも異なっていてもよく；Ｘはアリーレン基である］
ことを特徴とする、難燃性樹脂組成物。 The gist of the present invention is as follows.
[1] (a) 60 to 94% by mass of a polyphenylene ether resin, (b) 0.6 to 36.0% by mass of a cyclic phosphazene compound, (c) 0.6 to 36.0% by mass of a condensed phosphate ester flame retardant % hints, weight ratio to the sum of the component (b) wherein the component (b) wherein the component (c) Ri der 0.10 to 0.90,
The component (b) is a cyclic phosphazene compound represented by the following formula (1):

[Wherein n is an integer of 3 to 25]
The component (c) is a condensed phosphate ester flame retardant represented by the following formula (2):

[Wherein, m is an integer of 1 to 5; R ₁ , R ₂ , R ₃ and R ₄ are each independently a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an aryl-substituted alkyl group, A substituent selected from the group consisting of an aryl group, a halogen-substituted aryl group and an alkyl-substituted aryl group; R ₁ , R ₂ , R ₃ and R ₄ may be the same or different from each other; X is an arylene group Is]
A flame retardant resin composition characterized by that.

[2] The flame-retardant resin composition according to [1], wherein a mass ratio of the component (b) to the sum of the component (b) and the component (c) is 0.15 to 0.85.

[3] A method for producing a flame retardant resin composition according to [1] or [2] ,
Part of the component (a) and the component (b) are premixed to prepare a premix, then the premix and the rest of the component (a) are melt-kneaded, and then the component (c) A method for producing a flame retardant resin composition, characterized by further adding melt kneading.

[4] A step in which the mass ratio of the component (a) to the sum of the components (a) and (b) in the preliminary mixture is 0.6 to 0.9, and the component (a) is melt-kneaded. The method for producing a flame retardant resin composition according to [3] , wherein

  According to the present invention, it is possible to provide a polyphenylene ether-based flame-retardant resin composition having a good balance of processability, heat resistance, impact resistance, and flame retardancy. According to the present invention, a polyphenylene ether-based flame retardant resin composition having a good balance of workability, heat resistance, impact resistance, and flame retardancy can be produced with high productivity.

  Hereinafter, a mode for carrying out the present invention (hereinafter also referred to as “the present embodiment”) will be described in detail. The present invention is not limited to the following description, and various modifications can be made within the scope of the gist thereof.

(Flame retardant resin composition)
The flame-retardant resin composition of the present embodiment comprises (a) 60 to 94% by mass of a polyphenylene ether resin, (b) 0.6 to 36.0% by mass of a cyclic phosphazene compound, and (c) a condensed phosphate ester-based difficulty. It contains 0.6 to 36.0% by mass of a flame retardant. And in this flame-retardant resin composition, the mass ratio with respect to the sum of (b) component of (b) component and (c) component is 0.10-0.90.

Hereinafter, the component of the flame retardant resin composition of this embodiment is demonstrated.
-(A) Polyphenylene ether resin-
The flame retardant resin composition of the present embodiment contains a polyphenylene ether resin (hereinafter also referred to as “PPE resin”) as the component (a). Since the flame retardant resin composition of this embodiment contains a polyphenylene ether resin, it can have excellent flame retardancy and heat resistance.

［式中、Ｒ₁₁、Ｒ₁₂、Ｒ₁₃、Ｒ₁₄は、それぞれ独立して、水素、ハロゲン、１〜７個の炭素原子を有する第一級又は第二級アルキル基、フェニル基、ハロアルキル基、アミノアルキル基、炭化水素オキシ基、ハロゲン原子と酸素原子との間に少なくとも２個の炭素原子を有するハロ炭化水素オキシ基からなる群から選択される置換基であり；Ｒ₁₁、Ｒ₁₂、Ｒ₁₃、Ｒ₁₄は、互いに同一でも異なっていてもよい。］ Examples of the PPE resin used in the present invention include those containing a PPE component composed of a bond unit represented by the following formula (3).

[Wherein R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ are each independently hydrogen, halogen, primary or secondary alkyl group having 1 to 7 carbon atoms, phenyl group, haloalkyl group. , An aminoalkyl group, a hydrocarbonoxy group, a substituent selected from the group consisting of a halohydrocarbonoxy group having at least two carbon atoms between a halogen atom and an oxygen atom; R ₁₁ , R ₁₂ , R ₁₃ and R ₁₄ may be the same as or different from each other. ]

  The PPE resin has a reduced viscosity of 0.15 dl / g measured from 30 ° C. using a chloroform solution having a concentration of 0.5 g / dl from the viewpoint of fluidity, toughness and chemical resistance during processing. Preferably, it is 0.20 dl / g or more, more preferably 0.3 dl / g or more, and preferably 2.0 dl / g or less, 1.0 dl / g or more. / G or less is more preferable, and 0.7 dl / g or less is particularly preferable.

The PPE resin may be a homopolymer (homopolymer) or a copolymer (copolymer).
The homopolymer is not particularly limited, and examples thereof include poly (2,6-dimethyl-1,4-phenylene ether), poly (2-methyl-6-ethyl-1,4-phenylene ether), Examples include poly (2-methyl-6-phenyl-1,4-phenylene ether) and poly (2,6-dichloro-1,4-phenylene ether).
The copolymer is not particularly limited. For example, 2,6-dimethylphenol and other phenols (for example, 2,3,6-trimethylphenol, 2-methyl-6-butylphenol, etc.) A copolymer etc. are mentioned.

  As the PPE-based resin, in particular, from the viewpoint of the balance between toughness and rigidity as a composition and easy availability, poly (2,6-dimethyl-1,4-phenylene ether), 2,6- A copolymer of dimethylphenol and 2,3,6-trimethylphenol is preferred, and poly (2,6-dimethyl-1,4-phenylene ether) is particularly preferred.

  The PPE resins may be used alone or in combination of two or more.

  The PPE resin can be produced by a known method. The method for producing the PPE resin is not particularly limited. For example, a mixture of cuprous salt and amine described in US Pat. No. 3,306,874 by Hay is used as a catalyst, and 2,6-xylenol is used. Oxidative polymerization method, U.S. Pat. No. 3,306,875, U.S. Pat. No. 3,257,357, U.S. Pat. Other methods described in Japanese Patent Laid-Open No. 63-152628 are listed.

  The polyphenylene ether resin (PPE resin) which is the component (a) in the present invention may be 100% by mass of the PPE component, but the PPE resin may contain components other than the PPE component. . Examples of such components include polystyrene-based components and α, β-unsaturated carboxylic acid-based components.

  When using a polystyrene component as a component other than the PPE component, the mass ratio of the PPE component to the polystyrene component is preferably 1% by mass or more from the viewpoint of improving the processability and heat resistance of the composition. The content is more preferably 20% by mass or more, more preferably 99% by mass or less, and still more preferably 90% by mass or less.

The polystyrene component is not particularly limited, and is a homopolymer of a styrene compound, a copolymer of two or more styrene compounds, and a matrix composed of a homopolymer and a copolymer of these styrene compounds. Examples thereof include a rubber-modified styrene resin in which a rubbery polymer is dispersed in the form of particles.
A polystyrene type component may be used individually by 1 type, and may be used in combination of 2 or more type.

  Of the styrene compound homopolymers and copolymers, styrene compound homopolymers are preferred.

  Here, the styrene compound is not particularly limited, and examples thereof include styrene, o-methylstyrene, p-methylstyrene, m-methylstyrene, α-methylstyrene, ethylstyrene, α-methyl-p-methyl. Examples thereof include styrene, 2,4-dimethylstyrene, monochlorostyrene, p-tert-butylstyrene.

As the homopolymer of the styrene compound, polystyrene is particularly preferable.
As polystyrene, general-purpose polystyrene (GPPS) is preferable.
The stereoregularity of polystyrene may be any of isotactic, syndiotactic and atactic.

The rubber-modified styrenic resin is obtained by polymerizing one or more styrenic compounds in the presence of a rubbery polymer by a known polymerization method such as bulk polymerization, bulk suspension polymerization, solution polymerization, or emulsion polymerization. Can be obtained.
Here, examples of the rubber-like polymer include diene rubbers such as polybutadiene and poly (styrene-butadiene); saturated rubber obtained by hydrogenating a diene type rubber; isoprene rubber; chloroprene rubber; polybutyl acrylate, etc. Acrylic rubber; EPDM rubber, which is a terpolymer composed of ethylene-propylene-diene monomer, and the like, and diene rubber is particularly preferable.
As the rubber-modified styrene-based resin, impact-resistant polystyrene (HIPS) obtained by adding a rubber component to general-purpose polystyrene (GPPS) is preferable.

  In the rubber-modified polystyrene resin, the content of the rubber-like polymer in the rubber-modified polystyrene resin is 1% by mass or more from the viewpoint of improving the heat resistance, impact resistance and rigidity of the composition in a balanced manner. Is preferably 5% by mass or more, particularly preferably 7% by mass or more, and preferably 15% by mass or less; the content of the styrene compound in the rubber-modified polystyrene resin is , 85% by mass or more, preferably 99% by mass or less, more preferably 95% by mass or less, and particularly preferably 93% by mass or less.

  The content of the component (a) in the flame retardant resin composition of the present embodiment is 60% by mass or more from the viewpoint of improving the workability, heat resistance, impact resistance, and flame retardancy of the composition in a balanced manner. It is preferably 65% by mass or more, more preferably 70% by mass or more, and can be 94% by mass or less, preferably 90% by mass or less, and 85% by mass. More preferably, it is as follows.

-(B) Cyclic phosphazene compound-
The flame retardant resin composition of this embodiment contains a cyclic phosphazene compound as the component (b). Since the flame retardant resin composition of this embodiment contains a cyclic phosphazene compound, it can have excellent processability, heat resistance, impact resistance and flame retardancy.

［式中、ｎは３〜２５の整数であり；Ｒはアリールオキシ基（式中、Ｙ₁、Ｙ₂、Ｙ₃、Ｙ₄、Ｙ₅は、それぞれ独立して、水素原子、フッ素原子、１〜５個の炭素原子を有するアルキル基又はアルコキシ基、フェニル基、ヘテロ原子含有基からなる群から選択される置換基である）、ナフチルオキシ基、１〜６個の炭素原子を有するアルコキシ基、アルコキシ置換アルコキシ基からなる群から選択される置換基であり；Ｒ上の水素原子の全部又は一部はフッ素原子で置換されていてもよい。］ Examples of the cyclic phosphazene compound used in the present invention include James E. et al. Mark, Harry R. Allcock, Robert West, “Inorganic Polymers” Precise-Hall International, Inc. , 1992, p61-p140, and those containing a compound represented by the following formula (4) are particularly preferred.

[Wherein n is an integer of 3 to 25; R is an aryloxy group (wherein Y ₁ , Y ₂ , Y ₃ , Y ₄ , Y ₅ are each independently a hydrogen atom, a fluorine atom, An alkyl or alkoxy group having 1 to 5 carbon atoms, a phenyl group, a substituent selected from the group consisting of heteroatom-containing groups), a naphthyloxy group, and an alkoxy group having 1 to 6 carbon atoms And a substituent selected from the group consisting of alkoxy-substituted alkoxy groups; all or some of the hydrogen atoms on R may be substituted with fluorine atoms. ]

In the above formula (4), R is a phenoxy group (in the formula, Y ₁ , Y ₂ , Y ₃ , Y ₄ , and Y ₅ are hydrogen atoms) from the viewpoint of availability and cost of the cyclic phosphazene compound. Are particularly preferred.

  As the cyclic phosphazene compound, from the viewpoint of processability of the composition, a cyclic trimer (n is 3 in the above formula (4)) and / or a cyclic tetramer (n is 4 in the above formula (4)). It is preferable that the content rate of is high. Specifically, the cyclic trimer and / or cyclic tetramer compound content in the cyclic phosphazene compound is preferably 80% by mass or more, and the cyclic trimer content is 70% by mass or more. It is preferable that it is 80% by mass or more.

  The said cyclic phosphazene compound may be used individually by 1 type, and may be used in combination of 2 or more type.

  The cyclic phosphazene compound used in the present invention preferably contains 95% by mass or more of the cyclic phosphazene compound represented by the above formula (4).

  The form of the cyclic phosphazene compound may be any form as long as the effects of the present invention are not impaired, and may vary depending on the type and structure of the substituent, but may be various forms such as a liquid form, a wax form, and a solid form. .

If the cyclic phosphazene compound is a solid, the bulk density of the cyclic phosphazene compounds may as 0.45 g / cm ³ or more, preferably 0.45 g / cm ³ or more, also, 0.75 g / cm ³ or less It is preferable that

  The alkali metal such as sodium and potassium contained in the cyclic phosphazene compound is preferably 50 ppm or less, and here, each alkali metal contained in the cyclic phosphazene compound is preferably 200 ppm or less, and 50 ppm or less. Is more preferable.

  The amount of water contained in the cyclic phosphazene compound is preferably 1000 ppm or less, more preferably 800 ppm or less, particularly preferably 650 ppm or less, and 500 ppm or less from the viewpoints of electrical characteristics, hydrolysis resistance and the like. Is more particularly preferred, and most preferred is 300 ppm or less.

  The acid value measured based on JIS K6751 of the cyclic phosphazene compound is desirably 1.0 or less, and more desirably 0.5 or less.

The solubility of the cyclic phosphazene compound in water is preferably 100 ppm or less, more preferably 50 ppm, and particularly preferably 25 ppm or less from the viewpoints of hydrolysis resistance and moisture absorption resistance.
The solubility in water refers to the amount (ppm) of the sample dissolved in water after mixing a cyclic phosphazene compound sample in distilled water at a rate of 0.1 g / mL and stirring at room temperature for 1 hour.

  The content of the component (b) in the flame retardant resin composition of the present embodiment can be 0.6% by mass or more from the viewpoint of improving workability, impact resistance and flame retardancy in a balanced manner. It is preferably 2% by mass or more, more preferably 5% by mass or more, and can be 36.0% by mass or less, preferably 31.5% by mass or less, and 27.0%. More preferably, it is at most mass%.

-(C) condensed phosphate ester flame retardant-
The flame retardant resin composition of the present embodiment contains a condensed phosphate ester flame retardant as the component (c). Since the flame retardant resin composition of this embodiment contains a condensed phosphate ester flame retardant, excellent flame retardancy is combined with the effect of improving the flame retardant of the cyclic phosphazene compound which is the component (b) described above. Can be given.

［式中、ｍは１〜５の整数であり；Ｒ₁、Ｒ₂、Ｒ₃、Ｒ₄は、それぞれ独立して、水素原子、ハロゲン原子、アルキル基、シクロアルキル基、アリール置換アルキル基、アリール基、ハロゲン置換アリール基、アルキル置換アリール基からなる群から選択される置換基であり；Ｒ₁、Ｒ₂、Ｒ₃、Ｒ₄は、互いに同一でも異なっていてもよく；Ｘはアリーレン基である］ Examples of the condensed phosphate ester flame retardant used in the present invention include compounds represented by the following formula (2).

[Wherein, m is an integer of 1 to 5; R ₁ , R ₂ , R ₃ , R ₄ are each independently a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an aryl-substituted alkyl group, A substituent selected from the group consisting of an aryl group, a halogen-substituted aryl group, and an alkyl-substituted aryl group; R ₁ , R ₂ , R ₃ , and R ₄ may be the same or different from each other; X is an arylene group Is]

  In the above formula (2), m is preferably 1 to 3. When condensates of a plurality of types of phosphate esters having different values corresponding to n are used, n in the above formula (2) indicates an average value thereof.

In the above formula (2), from the viewpoint of flame retardancy and heat resistance of the composition, at least one of R ₁ , R ₂ , R ₃ , and R ₄ is preferably an aryl group, and R ₁ , R ₂ , More preferably, R ₃ and R ₄ are all aryl groups. Here, examples of the aryl group include phenyl, xylenyl, cresyl, and halogenated derivatives thereof.

  In the above formula (2), from the viewpoints of flame retardancy and heat resistance of the composition, the arylene group represented by X includes two hydroxyl groups in resorcinol, hydroquinone, bisphenol A, biphenol, or halogenated derivatives thereof. Residues and the like when desorbed.

  Representative condensed phosphate ester flame retardants are not particularly limited. For example, resorcinol bisphenyl phosphate, bisphenol A-polyphenyl phosphate, bisphenol A-polycresyl phosphate, bisphenol A bis (diphenyl phosphate) , Aromatic condensed phosphoric esters such as 1,3-phenylenebis (diphenylphosphate) and 1,3-phenylenebis (di-2,6-xylenylphosphate), and the like. From the viewpoint of enhancing, bisphenol A bis (diphenyl phosphate) is preferable.

  The said condensed phosphate ester type flame retardant may be used individually by 1 type, and may be used in combination of 2 or more type.

  The content of the component (c) in the flame-retardant resin composition of the present embodiment is 0.6% by mass or more from the viewpoint of improving the workability, heat resistance, impact resistance, and flame retardancy of the composition in a balanced manner. 2 mass% or more, preferably 5 mass% or more, more preferably 36.0 mass% or less, and 31.5 mass% or less. Is preferable, and it is further more preferable that it is 27.0 mass% or less.

  And in the flame-retardant resin composition of this embodiment, the mass ratio with respect to the sum of (b) component and (c) component of (b) component is workability, heat resistance, impact resistance, and flame retardancy. From the viewpoint of improving in a balanced manner, in particular, from the viewpoint of achieving a flame retardance level of V-1 or higher in the UL94 VB test, it is preferably 0.10 or higher, more preferably 0.15 or higher, and It is preferably 90 or less, and more preferably 0.85 or less.

-(D) Other components-
The flame retardant resin composition of the present embodiment is necessary as long as the processability, heat resistance, impact resistance or flame retardancy of the resin composition is not impaired, in addition to the components (a) to (c) described above. Depending on, other components may be contained.
Other components are not particularly limited, and include, for example, antioxidants, metal deactivators, flame retardants other than (b) component and (c) component (for example, organic phosphate ester compounds, polyphosphoric acid) Ammonium compounds, silicone flame retardants, etc.), plasticizers (for example, low molecular weight polyethylene, epoxidized soybean oil, polyethylene glycol, fatty acid esters, etc.), weather resistance (light) improver, slip agent, inorganic or organic filling Examples thereof include materials, reinforcing materials (for example, polyacrylonitrile fiber, aramid fiber, etc.), various colorants, release agents, and the like.

(Molding)
A molded product comprising the flame retardant resin composition of the present embodiment can be obtained by molding the flame retardant resin composition of the present embodiment described above.

  The molded product of the flame retardant resin composition of the present embodiment is not particularly limited, and for example, a compact disk / read only memory (CD-ROM), a digital versatile disk / read only memory (DVD-ROM), Compact Disc Recordable (CD-R), Digital Versatile Disc Recordable -R Standard (DVD-R), Digital Versatile Disc Recordable + R Standard (DVD + R), Compact Disc Rewritable (CD-RW), Digital versatile discs / rewritable / R standard (DVD-RW), digital versatile discs / rewritable / R standard (DVD + RW), digital versatile discs / random access memory (DVD-RAM) Optical parts such as nets, optical pickup slide bases, parts around light source lamps, sheets or films for metal film laminated substrates, hard disk internal parts, optical fiber connector ferrules, laser beam printer internal parts, inkjet printer internal parts, etc. In-vehicle engine compartment parts such as copy machine parts, automobile radiator tank parts, automobile lamp parts, and the like.

  The molding method of the resin composition is not particularly limited, and examples thereof include injection molding, metal in-mold molding, outsert molding, extrusion molding, sheet molding, film molding, hot press molding, rotational molding, and lamination molding. A molding method is mentioned.

(Method for producing flame retardant resin composition)
The flame-retardant resin composition of the present embodiment can be produced by melt-kneading the aforementioned components (a) to (c), optionally (d) other components.

  The method for producing the flame retardant resin composition of the present embodiment is not particularly limited as long as the components (a) to (c) and optionally (d) other components can be melt-kneaded.

  As an example of the method for producing the flame-retardant resin composition of the present embodiment, there is a method in which (a) component and (b) component are melt-kneaded, and then (c) component is added and further melt-kneaded. It is done. In this method, for example, the component (a) and the component (b) may be supplied to the extruder using different feeders.

  Here, in the manufacturing method of the flame retardant resin composition of this embodiment, the deterioration of the polyphenylene ether resin as the component (a) due to heat is prevented, and the cyclic phosphazene compound as the component (b) is uniformly mixed. Therefore, it is preferable to prepare a premix by previously mixing the component (a) and the component (b).

  In view of the above, as another example of the method for producing a flame retardant resin composition of the present embodiment, a preliminary mixture is prepared by previously mixing the components (a) to (c), and then the preliminary mixture. The method of melt kneading is mentioned. In this method, for example, the premix may be supplied to the extruder using a single feeder.

  Here, in the method for producing a flame retardant resin composition of the present embodiment, from the viewpoint of reducing the amount of raw materials used and eliminating classification of powder and pellets, It is preferable to use a part of the component (a) instead of all of the component a) in the preliminary mixture.

  In view of the above, as a further example of the method for producing a flame retardant resin composition of the present embodiment, a preliminary mixture is prepared by previously mixing a part of component (a) and component (b), and then There is a method in which the preliminary mixture and the rest of the component (a) are melt-kneaded, and then the component (c) is added and further melt-kneaded.

  According to this method, the production amount per unit time of the flame retardant resin composition can be increased, and the unmelted material can be greatly reduced, so that the occurrence of crosslinked products and carbides due to the thermal history of the resin. Since it can reduce, a high-quality flame-retardant resin composition can be manufactured with high productivity.

  In this method, the mass ratio of the (a) component to the sum of the (a) component and the (b) component in the preliminary mixture composed of a part of the (a) component and the (b) component is By stably adding to the extruder, it is possible to suppress fluctuations in the composition ratio of the obtained flame retardant resin composition, and to increase the amount of component (b) added, From the viewpoint of increasing the discharge amount at the time, it is preferably 0.55 or more, more preferably 0.60 or more, and preferably 0.95 or less, and 0.90 or less. Is more preferable.

  Further, in this method, by improving the stickiness of the component (a) and the component (b), it is possible to stably add continuously to the extruder, and from the viewpoint of further increasing the productivity of the flame retardant composition. It is preferable that powder is used as the components (a) and (b) and the pre-mixture is a powder blend.

  In this method, with respect to the component (a) that is appropriately divided and added to the extruder, the number of melt-kneading may be set to 1 to 3 from the viewpoint of reducing the generation of cross-linked products and carbides due to the thermal history of the resin. It is preferable to set it once.

  As an apparatus suitably used for premixing each component in each example of the aforementioned production method, for example, an extruder such as a single screw extruder or a multi-screw extruder such as a twin screw extruder, a roll, a kneader, Examples include Brabender Plastograph and Banbury Mixer.

  When mixing each component in advance, the mixing temperature is not particularly limited and may be usually 200 to 350 ° C. When a stirrer is used, the stirring speed is not particularly limited and may be usually 50 to 800 rpm. .

  Examples of the melt-kneader suitably used for melt-kneading each component in each of the above-described production methods include, for example, an extruder such as a multi-screw extruder such as a single-screw extruder or a twin-screw extruder, a roll , Kneaders, Brabender plastographs, Banbury mixers, and the like. Among these, from the viewpoint of kneadability, a twin screw extruder is particularly preferable. Specific examples of the twin screw extruder include the ZSK series manufactured by WERNER & PFLIDEERER, the TEM series manufactured by Toshiba Machine Co., Ltd., and the TEX series manufactured by Nippon Steel Works.

  When melt-kneading each component, the melt-kneading temperature is not particularly limited, and may be usually 220 to 280 ° C., and the screw rotation speed is not particularly limited, and may be usually 100 to 1200 rpm.

Hereinafter, it describes about suitable embodiment at the time of using extruders, such as multi-screw extruders, such as a single screw extruder and a twin screw extruder.
The extruder includes, for example, a first raw material supply port (top feed) on the upstream side in the flow direction of the raw material, a first vacuum vent downstream of the first raw material supply port, and a second downstream of the first vacuum vent. Raw material supply port (top feed or side feed, the same for the raw material supply port after the second raw material supply port), if necessary, the raw material supply port after the third raw material supply port downstream from the second raw material supply port, A second vacuum vent may be provided downstream of these raw material supply ports. Further, the extruder is provided between the first raw material supply port and the first vacuum vent, between the first vacuum vent and the second raw material supply port, and between the raw material supply port after the second raw material supply port and the second vacuum vent. It is preferable to further include a kneading section.

  Here, L / D (screw barrel effective length / screw barrel inner diameter) of the extruder is preferably 20 or more, more preferably 30 or more, and preferably 60 or less, 50 or less. More preferably.

The method of supplying the raw material at the raw material supply port after the second raw material supply port is not particularly limited, and a forced side feeder is used from the side open port as a method of simply adding from the upper open port of each raw material supply port. In particular, from the viewpoint of stable supply, a method of adding from the side opening using a forced side feeder is preferable.
When adding the raw material of the powder, from the viewpoint of reducing the occurrence of cross-linked products and carbides due to the thermal history of the resin, a method of using a forced side feeder from the side open port is preferable, and the raw material after the second raw material supply port More preferably, the raw material containing the powder is divided and added using a forced side feeder at all the supply ports.
When adding a liquid raw material, the method of adding from a top open port using a plunger pump, a gear pump, etc. is preferable.
The upper opening of the raw material supply port after the second raw material supply port of the extruder can be opened in order to remove air carried along with the raw material.

  The oxygen concentration of each line in the route (specifically, the route of stock feeder, piping, feed hopper with refill tank, piping, supply hopper, extruder) until each raw material is put into the extruder is From the viewpoint of reducing the generation of crosslinked products and carbides due to the thermal history of the resin in the presence of oxygen, the content is preferably less than 1.0% by volume. From the viewpoint of maintaining such a low oxygen concentration, each line is assumed to be highly airtight, and it is preferable to introduce an inert gas therein.

  In the preferred embodiment described above, for example, when a twin screw extruder is used as the extruder and (a) polyphenylene ether-based resin is used as a powder, the raw material adhering to the screw of the twin screw extruder is dramatically reduced. Effect is obtained. Moreover, the effect which reduces generation | occurrence | production of a sunspot foreign material, a carbide | carbonized_material, etc. is acquired about the flame-retardant resin composition manufactured according to the above-mentioned suitable embodiment.

  In the preferred embodiment described above, when (b) the cyclic phosphazene compound is powdered, stickiness occurs depending on the environment (for example, temperature, humidity, etc.) of the handling place, and it is difficult to continuously add a desired amount. There is a possibility. Here, (a) polyphenylene ether-based resin is used as powder, and (b) component is mixed in advance with all and / or part of (a) component, or (b) component is heated to obtain a liquid. By adding to the extruder using a pump above, a desired amount can be continuously added.

  Hereinafter, the present invention will be described with reference to specific examples and comparative examples, but the present invention is not limited thereto.

The raw materials used for the flame retardant resin compositions of Examples and Comparative Examples are shown below.
-(A) Polyphenylene ether resin-
(A1): PPE resin having a reduced viscosity of 0.55 dl / g obtained by oxidative polymerization of 2,6-xylenol (a2): General-purpose polystyrene (trade name: Polystyrene 685, manufactured by PS Japan)
(A3): impact-resistant polystyrene (trade name: polystyrene H9405, manufactured by PS Japan)
-(B) Cyclic phosphazene compound-
(B1): Cyclic phenoxyphosphazene (n ≧ 3, R = −OPh) (trade name: Ravitor (trademark) FP-110, manufactured by Fushimi Pharmaceutical Co., Ltd.)
-(C) condensed phosphate ester flame retardant-
(C1): Aromatic condensed phosphate ester (1,3-phenylenebis (diphenyl phosphate)) (trade name: CR-741, manufactured by Daihachi Chemical Industry Co., Ltd.)
-(D) Other components-
(D1): Aromatic phosphate ester (trade name: TPP, manufactured by Daihachi Chemical Industry Co., Ltd.)
(D2): Aluminum phosphinate (trade name: Exolit (trademark) OP1230, manufactured by Clariant Japan KK)

The measuring methods (1) to (5) of physical properties in Examples and Comparative Examples are shown below.
(1) Molding fluidity Based on JIS-K7210, the melt flow rate (MFR) (g / 10min) of the flame-retardant resin composition was measured on condition of temperature 250 degreeC and load 98N. As an evaluation standard, the higher the measured value, the better the molding fluidity.
(2) Deflection temperature under load The flame-retardant resin composition is supplied to a screw in-line injection molding machine (trade name: IS-80EPN, manufactured by Toshiba Machine Co., Ltd.) set at 200 to 280 ° C., and the mold temperature is 80 ° C. In accordance with JIS K7152-1 and K7313-2, the JIS K7139 test piece was manufactured under the conditions described above.
In accordance with JIS K7191-1, the deflection temperature under load (DTUL) of the test piece was measured. As an evaluation standard, it was determined that the higher the measured value, the better the heat resistance.
(3) Charpy impact strength JIS K7139 test piece was manufactured in the same manner as the test piece in (2).
In accordance with JIS K7111-1, the Charpy impact strength of the test piece was measured. As an evaluation standard, it was determined that the higher the measured value, the better the impact resistance.
(4) Flame retardancy Using the injection molding machine used in (2) for the flame retardant resin composition, a test piece having a length of 127 mm, a width of 2.7 mm, a thickness of 1.6 mm, and a thickness of 0.8 mm Manufactured.
The flame retardancy of the test pieces (2 types) was measured based on the vertical combustion test method of UL94 (standard established by Under Writer's Laboratories Inc., USA) (5 per sample). In particular, in the case of determination of flame retardance level V-1 or higher, it was determined that the flame retardant resin composition of this embodiment is desirable.
(5) Productivity When 200 kg of the flame retardant resin composition was produced, the mass of the raw material adhering to the screw of the extruder was measured. As an evaluation standard, it was determined that the lower the measured value, the better the productivity of the flame retardant resin composition.

Hereinafter, each example and each comparative example will be described in detail.
[Examples 1-11, Comparative Examples 1-10]
A twin-screw extruder (trade name: ZSK-40) equipped with a weight feeder for extruder (trade name: K2-ML-T35 / DR, manufactured by K-TRON Co., Ltd.) equipped with a screw TSF as a melt kneader. , WERNER & PFLIDEERER).
A first raw material supply port on the upstream side with respect to the flow direction of the raw material, a first vacuum vent downstream of the first raw material supply port, a second raw material supply port downstream of the first vacuum vent, and the second raw material supply port The 2nd vacuum vent was provided downstream from.
In addition, the raw material was supplied from the upper raw material supply port using a gear pump from the upper opening.
Then, (a) polyphenylene ether resin, (b) cyclic phosphazene compound, (c) condensed phosphate ester flame retardant, (d) other components, using the extruder set as described above, the following table The composition shown in 1 was melt-kneaded to produce a flame retardant resin composition in pellet form. The kneading conditions were an extrusion temperature of 220 to 280 ° C., a screw rotation speed of 300 rpm, and a discharge rate of 100 to 200 kg / hour.
About each Example and each comparative example, the physical-property test was done by the above-mentioned measuring method (1)-(5). The results are shown in Table 1.

As shown in Table 1, the flame retardant resin compositions of Examples 1 to 11 are excellent in workability and heat resistance as compared with the flame retardant resin compositions of Comparative Examples 1 to 14, and further, impact resistance. It was also found to be excellent in flame retardancy.
Moreover, as shown in Table 1, compared with the manufacturing method of the flame-retardant resin composition of Examples 9 and 10, the manufacturing method of the flame-retardant resin composition of Examples 1-8 is a flame-retardant resin composition. It was also found that the productivity of things can be dramatically improved.

According to the present invention, it is possible to provide a polyphenylene ether-based flame-retardant resin composition having a good balance of processability, heat resistance, impact resistance, and flame retardancy. Molded articles of the flame-retardant resin composition of the present invention include optical device mechanism parts, parts around light source lamps, sheets or films for metal film laminated substrates, hard disk internal parts, optical fiber connector ferrules, printer parts, copier parts, automobiles It can be used as an engine room component, an automobile lamp component, or the like.
According to the present invention, a polyphenylene ether-based flame retardant resin composition having a good balance of workability, heat resistance, impact resistance, and flame retardancy can be produced with high productivity.

Claims (4)

(A) polyphenylene ether resin 60 to 94% by mass, (b) cyclic phosphazene compound 0.6 to 36.0% by mass, (c) condensed phosphate ester flame retardant 0.6 to 36.0% by mass the (b) weight ratio to the sum of the components (b) and component wherein the component (c) Ri der 0.10 to 0.90,
The component (b) is a cyclic phosphazene compound represented by the following formula (1):

[Wherein n is an integer of 3 to 25]
The component (c) is a condensed phosphate ester flame retardant represented by the following formula (2).

[Wherein, m is an integer of 1 to 5; R ₁ , R ₂ , R ₃ and R ₄ are each independently a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an aryl-substituted alkyl group, A substituent selected from the group consisting of an aryl group, a halogen-substituted aryl group and an alkyl-substituted aryl group; R ₁ , R ₂ , R ₃ and R ₄ may be the same or different from each other; X is an arylene group Is]
A flame retardant resin composition characterized by that.   The flame-retardant resin composition according to claim 1, wherein a mass ratio of the component (b) to the sum of the component (b) and the component (c) is 0.15 to 0.85. A method for producing a flame retardant resin composition according to claim 1 or 2 ,
Part of the component (a) and the component (b) are premixed to prepare a premix, then the premix and the rest of the component (a) are melt-kneaded, and then the component (c) A method for producing a flame retardant resin composition, characterized by further adding melt kneading. In the preliminary mixture, the mass ratio of the component (a) to the sum of the components (a) and (b) is 0.6 to 0.9, and the step of melt-kneading the component (a) is performed once. The method for producing a flame retardant resin composition according to claim 3 , wherein