JP2018028061A - Resin composition and molded article - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composition excellent in fluidity, flame retardancy, and impact resistance, and to provide a molded article.SOLUTION: The resin composition of the present invention contains (a) 25-60 pts.mass of a polyphenylene ether resin, (b) 2-20 pts.mass of a styrene-acrylonitrile copolymer, (c) 5-30 pts.mass of a phosphorus compound, and (d) 10-50 pts.mass of an inorganic filler (the total of the component (a), the component (b), the component (c) and the component (d) is 100 pts.mass). In a test piece prepared according to ISO-15103, dispersed particles containing the component (b) and having a major axis of 0.1 μm or more do not exist.SELECTED DRAWING: None

Description

  The present invention relates to a resin composition and a molded body.

  Conventionally, polyphenylene ether-based resins have been widely used in home appliances / OA equipment, automobile parts and the like because they have heat resistance, hydrolysis resistance, and flame resistance in addition to excellent electrical insulation.

  These materials are required to have high flame resistance due to fire problems, etc., and polyphenylene ether resins are highly flame retardant by adding phosphorus compounds without using halogen compounds. The utility value is also increasing.

  In recent years, parts have become smaller and more complicated in structure, and these materials are often molded with a thin wall, and have good fluidity (molding processability) and mechanical properties during injection molding. It is also required to be.

  Conventionally, a technique using a polyphenylene ether resin excellent in balance between fluidity and mechanical properties and flame retardancy has been disclosed (for example, see Patent Document 1).

JP-A-9-31321

  However, the resin material disclosed in Patent Document 1 has a problem that the flame retardancy (particularly the flame retardancy when a molded product having a thickness of 1 mm or less) is not necessarily sufficient when it is a thin molded article. Have.

  Then, in this invention, it aims at providing the resin composition and molded object which were excellent in fluidity | liquidity, a flame retardance, and impact resistance.

  As a result of intensive studies to solve the above problems, the present inventors have mixed polyphenylene ether resin, styrene-acrylonitrile copolymer, phosphorus compound, and inorganic filler at a specific ratio, and have a specific morphology. The present inventors have found that a resin composition having a fluidity, flame retardancy, and impact resistance can be improved, and the present invention has been completed.

  That is, the present invention is as follows.

[1]
(A) 25-60 parts by mass of a polyphenylene ether resin,
(B) 2-20 parts by mass of a styrene-acrylonitrile copolymer;
(C) 5 to 30 parts by mass of a phosphorus compound;
(D) 10 to 50 parts by mass of an inorganic filler;
(However, the total of the component (a), the component (b), the component (c), and the component (d) is 100 parts by mass),
In the test piece produced according to ISO-15103, the resin composition characterized by the absence of dispersed particles having a major axis of 0.1 μm or more containing the component (b).

[2]
The component (a) is
(A-1) a polyphenylene ether resin having a reduced viscosity of 0.30 to 0.40 dL / g;
(A-2) a polyphenylene ether resin having a reduced viscosity of 0.45 to 0.55 dL / g,
Including
Ratio of content of component (a-2) to total content of component (a-1) and component (a-2) (content of component (a-2) / content of component (a-1) The resin composition according to [1], wherein (amount + content of (a-2) component) × 100) is 10 to 60%.

[3]
The resin composition according to [1] or [2], wherein the component (b) is a copolymer containing 5 to 15% by mass of an acrylonitrile unit.

[4]
(E) 0.02-0.3 parts by mass of polytetrafluoroethylene is further added to 100 parts by mass in total of the component (a), the component (b), the component (c), and the component (d). The resin composition according to any one of [1] to [3].

[5]
A molded article comprising the resin composition according to any one of [1] to [4].

[6]
(A) 25-60 parts by mass of a polyphenylene ether resin,
(B) 2-20 parts by mass of a styrene-acrylonitrile copolymer;
(C) 5 to 30 parts by mass of a phosphorus compound;
(D) 10 to 50 parts by mass of an inorganic filler;
(However, a molded body made of a resin composition comprising (a) component, (b) component, (c) component, and (d) component is 100 parts by mass),
(B) A molded article characterized by the absence of dispersed particles having a major axis of 0.1 μm or more containing the component.

[7]
An ink jet printer component or member comprising the resin composition according to any one of [1] to [4].

[8]
The molded product according to [5] or [6], which is an inkjet printer component or member.

  ADVANTAGE OF THE INVENTION According to this invention, the resin composition and molded object which were excellent in fluidity | liquidity, a flame retardance, and impact resistance can be provided.

FIG. 1 is a schematic view showing a screw configuration of a twin-screw extruder used in Examples and Comparative Examples, and a set temperature of a barrel.

  Hereinafter, a mode for carrying out the present invention (hereinafter referred to as “the present embodiment”) will be described in detail. The following embodiment is an exemplification for explaining the present invention, and the present invention is not limited to the following embodiment. In addition, the present invention can be implemented with appropriate modifications within the scope of the gist.

<Resin composition>
The resin composition of the present invention comprises (a) 25-60 parts by mass of a polyphenylene ether resin, (b) 2-20 parts by mass of a styrene-acrylonitrile copolymer, (c) 5-30 parts by mass of a phosphorus compound, (D) 10 to 50 parts by mass of the inorganic filler (provided that the total of the component (a), the component (b), the component (c), and the component (d) is 100 parts by mass) In a test piece prepared according to ISO-15103, there is no dispersed particle having a major axis of 0.1 μm or more containing the component (b).
Note that “there is no dispersed particle having a major axis of 0.1 μm or more including the component (b)” in the image observation at the SEM magnification of 4000 times of the specimen prepared according to ISO-15103, the component (b) This means that there is no dispersed particle having a major axis of 0.1 μm or more. The dispersed particles containing the component (b) can be discriminated by observing the Os and Ru stained test pieces. Specifically, in the method described in the examples described later, this means that no dispersed particles containing the component (b) having a major axis of 0.1 μm or more are detected.

  The number of the dispersed particles in the test piece prepared according to ISO-15103 is the content of the components (a) to (d) in the resin composition, the method of charging the raw material into the extruder, and the extrusion in the kneading stage. It can be adjusted by the number of rotations of the machine screw, screw configuration, kneading temperature, cylinder temperature (melting temperature) during molding, molding cycle time, and the like.

-(A) Polyphenylene ether resin-
The (a) polyphenylene ether-based resin (in this specification, sometimes referred to as “PPE” or simply “component (a)”) may be a phenylene ether homopolymer. It may also be a copolymer (copolymer) of phenylene ether and another monomer.
As the component (a), only one type may be used alone, or two or more types may be used in combination.

As said (a) component, the homopolymer and / or copolymer which have a repeating unit structure (unit structure derived from phenylene ether) represented by following formula (1) are mentioned, for example.
[Wherein, R ¹ , R ² , R ³ , and R ⁴ each independently represent a hydrogen atom, a halogen atom, a primary alkyl group having 1 to 7 carbon atoms, or a first alkyl group having 1 to 7 carbon atoms. Selected from the group consisting of secondary alkyl groups, phenyl groups, haloalkyl groups, aminoalkyl groups, hydrocarbonoxy groups, and halohydrocarbonoxy groups in which at least two carbon atoms separate the halogen and oxygen atoms. Represents a monovalent group. ]

  Examples of the component (a) include poly (2,6-dimethyl-1,4-phenylene ether), poly (2-methyl-6-ethyl-1,4-phenylene ether), poly (2-methyl- Homopolymers such as 6-phenyl-1,4-phenylene ether) and poly (2,6-dichloro-1,4-phenylene ether); 2,6-dimethylphenol and other phenols (for example, 2,3 , 6-trimethylphenol, 2-methyl-6-butylphenol) and the like. Among them, poly (2,6-dimethyl-1,4-phenylene ether), 2,6-dimethylphenol and 2,3,6-trimethylphenol are preferable, and poly (2,6-dimethyl-1,4-phenylene ether) is preferable. ) Is more preferable.

  A conventionally well-known method can be applied to the manufacturing method of the said (a) component. As the method for producing the component (a), for example, a method for producing by oxidative polymerization of 2,6-xylenol or the like using a complex of cuprous salt and amine as a catalyst, JP-A-50-150798 And the methods described in JP-A No. 50-051197, JP-A No. 63-152628, and the like.

  The reduced viscosity of the component (a) (0.5 g / dL chloroform solution, measured at 30 ° C., measured with an Ubbelohde viscometer) is preferably 0.7 dL / g or less from the viewpoint of fluidity. More preferably, it is 0.6 dL / g or less, preferably 0.15 dL / g or more, more preferably 0.2 dL / g or more from the viewpoint of flame retardancy.

  As the component (a), two or more polyphenylene ethers having different reduced viscosities may be mixed and used. As the component (a), from the viewpoint of balance between fluidity and flame retardancy, (a-1) a polyphenylene ether resin having a reduced viscosity of 0.30 to 0.40 dL / g, and (a-2) A polyphenylene ether resin having a reduced viscosity of 0.45 to 0.55 dL / g, and the content of the component (a-2) relative to the total content of the component (a-1) and the component (a-2) The ratio (content of (a-2) component / (content of (a-1) component + content of (a-2) component) × 100) is preferably 10 to 60%, more preferably. Is 20% to 50%.

The component (a) may contain a modified polyphenylene ether that is modified in whole or in part.
The modified polyphenylene ether as used herein has at least one carbon-carbon double bond and / or triple bond in the molecular structure and is composed of a carboxylic acid group, an acid anhydride group, an amino group, a hydroxyl group and a glycidyl group. A polyphenylene ether modified with a modified compound having at least one group selected from the group (hereinafter sometimes simply referred to as “modified compound”). Only one type of modifying compound may be used alone, or two or more types may be used in combination.

  The method for producing the modified polyphenylene ether is not limited to the following. For example, in the presence or absence of a radical initiator, (1) in the range of 100 ° C. or higher and lower than the glass transition temperature of the polyphenylene ether. A method of reacting a polyphenylene ether and a modifying compound without melting the polyphenylene ether at a temperature; (2) melt-kneading the polyphenylene ether and the modifying compound at a temperature in the range of the glass transition temperature of the polyphenylene ether to 360 ° C. or less. And (3) a method of reacting a polyphenylene ether and a modified compound in a solution at a temperature lower than the glass transition temperature of the polyphenylene ether, and any of these methods may be used. Therefore, the method (1) or (2) is preferable.

  Next, the modified compound used for producing the modified polyphenylene ether will be described.

Examples of the modified compound having a carbon-carbon double bond and a carboxylic acid group and / or an acid anhydride group include maleic acid, fumaric acid, chloromaleic acid, cis-4-cyclohexene-1,2- Examples thereof include dicarboxylic acids and acid anhydrides thereof.
Among these, from the viewpoint of reactivity with the polyphenylene ether resin, maleic acid, fumaric acid, and maleic anhydride are preferable, and fumaric acid and maleic anhydride are more preferable. A compound in which one or two of the two carboxyl groups of the unsaturated dicarboxylic acid is an ester can also be used as the modifying compound.

Examples of the modified compound having a carbon-carbon double bond and a hydroxyl group include a general formula C _n H _2n-1 OH (n is a positive integer) such as allyl alcohol and 4-penten-1-ol. Unsaturated alcohol represented by the general formula C _n H _2n-3 OH (n is a positive integer of 2 or more) such as unsaturated alcohol represented by 1,4-pentadien-3-ol, general formula C _n H _Examples include unsaturated alcohols represented by _2n-5 OH (n is a positive integer of 3 or more), unsaturated alcohols represented by C _n H _2n-7 OH (n is a positive integer of 4 or more), and the like. .

  Examples of the modified compound having a carbon-carbon double bond and a glycidyl group include allyl glycidyl ether, glycidyl acrylate, glycidyl methacrylate, and epoxidized natural fats and oils. Among these, glycidyl acrylate and glycidyl methacrylate are preferable.

  The amount of the modifying compound added when producing the modified polyphenylene ether is preferably 0.1 to 10 parts by weight, more preferably 0.3 to 5 parts by weight, and more preferably 0.5 to 3 parts per 100 parts by weight of the polyphenylene ether. Part by mass is more preferable. If the amount is 0.1 parts by mass or more, the effect of denaturation of polyphenylene ether is likely to be exhibited, and if the amount is 10 parts by mass or less, side effects due to denaturation are difficult to occur.

  When the modified polyphenylene ether is produced using the radical initiator, the amount of the radical initiator added is preferably 0.001 to 1 part by mass, more preferably 0.01 to 0, relative to 100 parts by mass of the polyphenylene ether. 0.5 parts by mass, more preferably 0.05 to 0.3 parts by mass. If it is 0.001 part by mass or more, the modification efficiency is excellent. On the other hand, if it is 1 part by mass or less, the molecular weight of the modified polyphenylene ether is hardly lowered, and the balance between the modification rate and the physical properties is excellent.

  Further, the addition ratio of the modifying compound to the modified polyphenylene ether is preferably 0.01 to 5% by mass, more preferably 0.05 to 3% by mass, and still more preferably 0.8% to 100% by mass of the modified polyphenylene ether. It is 1-1 mass%. The residual amount of the unreacted modified compound and / or polymer of the modified compound in the modified polyphenylene ether is preferably less than 5% by mass, more preferably 3% by mass or less, and even more preferably 1% by mass or less.

  The content of the component (a) in the resin composition of the present embodiment is the sum of the component (a), the component (b), the component (c), and the component (d) from the viewpoint of fluidity and flame retardancy balance. It is 25-60 mass parts with respect to 100 mass parts, Preferably it is 25-50 mass parts, More preferably, it is 30-40 mass parts.

-(B) Styrene-acrylonitrile copolymer-
The resin composition of the present embodiment contains (b) a styrene-acrylonitrile copolymer (sometimes referred to simply as “component (b)” in this specification).
As the component (b), only one type may be used alone, or two or more types may be used in combination.

  The content of the acrylonitrile unit (unit structure derived from acrylonitrile) in the component (b) is preferably 5 to 15% by mass, more preferably 7 to 11% by mass, still more preferably 8 to 10% by mass, and particularly preferably. It is 8.5 to 9.5% by mass. In the component (b), the content of the acrylonitrile unit is preferably 5% by mass or more from the viewpoint of fluidity. On the other hand, the content of the acrylonitrile unit is preferably 15% by mass or less from the viewpoint of obtaining good compatibility and improving the mechanical properties of the molded article and the anti-dripping property during combustion.

The melt flow rate of the component (b) is preferably 5 to 100 g / 10 minutes, more preferably 30 to 80 g / 10 minutes. The higher the melt flow rate of the component (b), the better the fluidity of the resin composition in the present embodiment. However, in the molded product, 100 g / 10 min or less from the viewpoint of securing practically sufficient mechanical properties. It is preferable that
In addition, a melt flow rate says the value measured on condition of 220 degreeC and a 10-kg load based on ASTMD1238.

In the resin composition of the present embodiment, it is preferable that no dispersed particles having a major axis of 0.1 μm or more containing the component (b) exist. Thereby, the dripping prevention property at the time of combustion and the impact resistance are expressed.
The dispersed particles in the resin composition can also be measured by a method similar to “Presence / absence of dispersed particles having a major axis of 0.1 μm or more containing the component (b)” in Examples described later.

  In the resin composition of the present embodiment, the content of the component (b) is (a) component, (b) component, (c) component, and (c) from the viewpoints of dripping prevention during combustion and mechanical property balance. d) It is 2-20 mass parts with respect to a total of 100 mass parts of a component, Preferably it is 3-18 mass parts, More preferably, it is 5-15 mass parts.

-(C) Phosphorus compound-
The resin composition of the present embodiment contains (c) a phosphorus compound (in this specification, sometimes simply referred to as “component (c)”).
As the component (c), only one type may be used alone, or two or more types may be used in combination.

As the component (c), any phosphorus-containing flame retardant known in the art such as an organic phosphorus compound, red phosphorus, and inorganic phosphate can be used. Of these, phosphate ester compounds are preferred.
Examples of the component (c) include, but are not limited to, trimethyl phosphate, triethyl phosphate, tripropyl phosphate, tributyl phosphate, tripentyl phosphate, trihexyl phosphate, tricyclohexyl phosphate, triphenyl phosphate, triphenyl phosphate, Phosphate ester compounds such as cresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, dicresyl phenyl phosphate, dimethyl ethyl phosphate, methyl dibutyl phosphate, ethyl dipropyl phosphate, hydroxyphenyl diphenyl phosphate; modified with various substituents Modified phosphoric acid ester compounds; condensed phosphoric acid ester compounds of various condensation types, and the like. Among these, condensed phosphate ester compounds are preferable.

As the condensed phosphoric acid ester-based compound, those containing at least one selected from the group consisting of condensed phosphoric acid esters represented by the following formula (2) and the following formula (3) as a main component are preferable.
The “main component” as used herein means that at least one content selected from the group consisting of aromatic condensed phosphate esters represented by the following formula (2) and the following formula (3) is (c) component 100 It is said that 90 mass% or more is contained with respect to mass%, preferably 95 mass% or more, more preferably 100 mass%.
[In the formula (2), Q ⁴¹ , Q ⁴² , Q ⁴³ and Q ⁴⁴ are each independently an alkyl group having 1 to 6 carbon atoms; R ⁴¹ and R ⁴² are methyl groups; Each of R ⁴³ and R ⁴⁴ is independently a hydrogen atom or a methyl group; x is an integer of 0 or more; p ₁ , p ₂ , p ₃ , and p ₄ are each 0 to 3 is an integer of 3; q ₁ and q ₂ are each an integer of 0 to 2]
[In the formula (3), Q ⁵¹ , Q ⁵² , Q ⁵³ and Q ⁵⁴ are each independently an alkyl group having 1 to 6 carbon atoms; R ⁵¹ is a methyl group; Each of r ₁ , r ₂ , r ₃ , and r ₄ is an integer of 0 to 3; and s ₁ is an integer of 0 to 2]

  In addition, the condensed phosphate compound represented by the above formula (2) and the above formula (3) may each include a plurality of types of molecules. Moreover, it is preferable that x of Formula (2) and y of Formula (3) are integers of 1 to 3.

Among them, as the component (c), R ⁴³ and R ⁴⁴ in the formula (2) represent a methyl group, and p ₁ , p ₂ , p ₃ , p ₄ , q ₁ , and q ₂ are 0. Acid ester, Q ⁴¹ , Q ⁴² , Q ⁴³ , Q ⁴⁴ , R ⁴³ and R ⁴⁴ in formula (2) represent a methyl group, q ₁ and q ₂ are 0, and p ₁ , p ₂ , p ₃ , And p ₄ is an integer of 1 to 3, and x is an integer of 1 to 3 (especially x is 1), and contains 50% by mass or more of 100% by mass of component (c). It is preferable. By using these condensed phosphate ester compounds, the volatility at the time of molding of the resin composition can be further reduced.

  The content of the component (c) in the resin composition of the present embodiment is the components (a), (b), (c), and (d) from the viewpoints of fluidity and flame retardancy and mechanical property balance. ) It is 5 to 30 parts by mass, preferably 10 to 25 parts by mass, and more preferably 10 to 20 parts by mass with respect to 100 parts by mass in total of the components.

-(D) Inorganic filler-
Examples of the (d) inorganic filler contained in the resin composition of the present embodiment (sometimes referred to simply as “component (d)” in this specification) include glass fiber, glass flake, mica, and wollastonite. , Talc, calcined clay and the like. Glass beads and glass flakes are used when low dimensional anisotropy is required, glass fibers and whiskers are used when high rigidity and high impact resistance are required, and metal fibers are used for the purpose of imparting electrical conductivity. When high specific gravity is required, iron oxide is preferably selected and used.
The component (d) may be used singly or in combination of two or more, and as long as the object of the present invention is not impaired, surface treatment with a silane coupling agent as desired. Alternatively, those subjected to a sizing treatment with a sizing agent can be used.

  The content of the component (d) in the resin composition of the present embodiment is the components (a), (b), (c), and (d) from the viewpoints of mechanical properties, dimensional characteristics, and fluidity balance. It is 10-50 mass parts with respect to a total of 100 mass parts of a component, Preferably it is 15-45 mass parts, More preferably, it is 20-40 mass parts.

-(E) polytetrafluoroethylene-
The resin composition of the present embodiment may further contain (e) polytetrafluoroethylene (sometimes referred to simply as “(e) component” in this specification) (PTFE).
As the component (e), only one type may be used alone, or two or more types may be used in combination.

  Examples of the component (e) include a homopolymer of tetrafluoroethylene, a copolymer of tetrafluoroethylene and difluoroethylene, trifluoroethylene, hexafluoropropylene, and the like.

Examples of methods for producing these PTFEs include a method of producing a tetrafluoroethylene monomer as a raw material by an emulsion polymerization method by radical polymerization using a peroxide or a suspension polymerization method. Specifically, it is disclosed in US Pat. No. 2,393,697 and US Pat. No. 2,534,058. For example, tetrafluoroethylene in an aqueous medium, ammonium persulfate, potassium persulfate, etc. The polymer is polymerized at a temperature of 0 to 200 ° C. under a pressure of 7 to 70 kg / cm ² and then coagulated from a suspension, dispersion or emulsion, or by precipitation. Examples thereof include a method for obtaining a fluoroethylene powder.
For example, a modified type in which a part of the fluorine atom is replaced with another substituent or element is also used. The PTFE obtained by this method is in the form of powder or dispersion, but is preferably highly crystalline and easily fibrillated.

  The content of the component (e) in the resin composition of the present embodiment is as follows: (a) component, (b) component, (c) component, and (d) from the viewpoints of drip prevention during combustion and fluidity balance. 0.02-0.5 mass part is preferable with respect to a total of 100 mass parts of components, More preferably, it is 0.02-0.4 mass part, More preferably, it is 0.02-0.3 mass part.

<Additives>
In order to impart further characteristics to the resin composition of the present embodiment, for example, a stabilizer such as a plasticizer, an antioxidant, and an ultraviolet absorber, and an antistatic agent, as long as the effects of the present invention are not impaired. Additives such as mold release agents, dyes and pigments, and other resins other than those described above can be added. Further, various conventionally known flame retardants and flame retardant aids, for example, alkaline earth metal hydroxides such as magnesium hydroxide, aluminum hydroxide, alkali metal hydroxides, zinc borate, containing crystal water. It is possible to further improve the flame retardancy by adding a compound, a zinc stannate compound or the like.

  The resin composition of this embodiment may further contain any one selected from the group consisting of polystyrene, syndiotactic polystyrene, and high impact polystyrene as the other component. By using the component (a) and these resins in combination, molding processability can be improved.

<Physical properties of resin composition>
The melt flow rate of the resin composition of the present embodiment is preferably 10 g / 10 min or more, more preferably 15 g / 10 min or more, and further preferably 20 g / 10 min or more from the viewpoint of further improving fluidity. is there. Moreover, it is preferable that it is 50 g / 10min or less from a viewpoint of dripping prevention at the time of a combustion test.
In addition, the melt flow rate of a resin composition can be measured based on ISO1133, and can be specifically measured by the method as described in the below-mentioned Example.

The Charpy impact strength of the resin composition of the present embodiment is preferably ⁴ to 30 kJ / m ² from the viewpoint of further excellent impact resistance.
In addition, the Charpy impact strength of a resin composition can be measured based on ISO179, and can be specifically measured by the method as described in the below-mentioned Example.

In the evaluation of flame retardancy based on the UL-94 vertical combustion test, the resin composition of the present embodiment is an evaluation of V-0 and V-1 using an injection test piece having a thickness of 1.0 mm. preferable.
Moreover, the resin composition of this embodiment is evaluation of V-0 and V-1 in the evaluation of flame retardancy based on the UL-94 vertical combustion test using an injection test piece having a thickness of 0.75 mm. It is preferable.
In addition, the flame retardance of a resin composition can be evaluated by the method as described in the below-mentioned Example.

<Method for producing resin composition>
Examples of the method for producing the resin composition of the present embodiment include a method in which the above-described components are melt-kneaded using a twin-screw extruder. Examples of the twin-screw extruder include a ZSK series manufactured by Coperion, a TEM series manufactured by Toshiba Machine, a TEX series manufactured by Nippon Steel Works, and the like.

  The L / D (barrel effective length / barrel inner diameter) of the extruder is preferably 20 or more and 75 or less, more preferably from the viewpoint that the contained components can be more uniformly kneaded and more excellent flame retardancy can be obtained. 30 or more and 60 or less.

  The configuration of the extruder is not particularly limited. For example, the first raw material supply port on the upstream side with respect to the flow direction of the raw material, the first vacuum vent on the downstream side of the first raw material supply port, and the first vacuum vent A second raw material supply port is provided downstream, a liquid supply pump is provided downstream of the second raw material supply port, a third raw material supply port is provided downstream of the liquid supply pump, and a second raw material supply port is provided downstream of the third raw material supply port. Those provided with two vacuum vents are preferred. In particular, a kneading section is provided upstream of the first vacuum vent, a kneading section is provided between the liquid supply pump and the third raw material supply port, and a kneading section is provided between the third raw material supply port and the second vacuum vent. What was provided is more preferable.

In the method for producing the resin composition of the present embodiment, the melt-kneading temperature, the screw rotation speed, and the like are not particularly limited, and are within a range of a melt-kneading temperature of 200 to 370 ° C. and a screw rotation speed of 100 to 1200 rpm (preferably 160 to 1200 rpm). From these, suitable conditions can be selected as appropriate.
From the standpoint of exhibiting excellent dripping prevention property during combustion and more excellent impact resistance in the resin composition, the melt kneading temperature is preferably 280 to 320 ° C., and the screw rotation speed is 250 to 550 rpm. Is preferred.

  The screw configuration provided in the barrel is not particularly limited, and a right-handed, left-handed, orthogonal (N-type), or reverse-feed (L-type) kneading disk element may be appropriately provided. From the standpoint of exhibiting dripping prevention and impact resistance, at least one orthogonal (N-type) kneading disk element and at least one reverse feed (L) are provided between the first raw material supply port and the second raw material supply port. A configuration in which a type) kneading disk element is provided is preferable. In addition, from the viewpoint that the resin composition can be kneaded more efficiently and the resin composition can be produced without increasing the melt kneading temperature, at least one orthogonal knee is provided between the liquid pump and the second vacuum vent. It is preferable to provide a section including a bonding disk element, more preferably, a section including at least one orthogonal kneading disk element is provided between the liquid pump and the third raw material supply port, and the third raw material supply port and the second vacuum are provided. More preferably, a section including at least one orthogonal kneading disk element and at least one reverse feeding kneading disk element is provided between the vent.

  The raw material supply apparatus for supplying the raw material to the twin screw extruder is not particularly limited, and examples thereof include a single screw feeder, a twin screw feeder, a table feeder, and a rotary feeder. Among these, a loss-in-weight feeder is preferable from the viewpoint that the fluctuation error of the raw material supply is small.

  When the liquid raw material is supplied, the liquid raw material can be directly kneaded into the cylinder system using a liquid pump or the like into the extruder cylinder. The liquid pump is not particularly limited, and examples thereof include a gear pump and a flange type pump. Among these, a gear pump is preferable. In addition, the tank that stores the liquid raw material used for the liquid pump, the piping between the tank and the pump, and the piping between the pump and the extruder cylinder, etc. are heated with a heater or the like. More preferably. Thereby, the viscosity of the liquid raw material can be reduced, so that the load applied to the liquid pump can be reduced, which is preferable from the viewpoint of operability and the like.

  In the method for producing a resin composition of the present embodiment, from the viewpoint of obtaining a resin composition that is superior in fluidity, flame retardancy, and impact resistance, the total amount of component (a) from the first raw material supply port, (b ) All or part of the component, (e) All or part of the component was added, and the rest of the component (b) was added from the second raw material supply port (however, all of the component (b) was added from the first raw material supply port Except for the case), (d) all or part of component, total amount of (c) component from liquefaction pump, remainder of (d) component from third raw material supply port (however, from second raw material supply port (d) It is preferable to add except when all the components are added. Especially, regarding the addition position of (b) component, it is preferable to add simultaneously with (a) component from a 1st raw material supply port from a viewpoint of expressing the dripping prevention property at the time of combustion, and impact resistance.

<Molded body>
The resin composition of this embodiment can be formed into a molded body by molding it. Although it does not specifically limit as a shaping | molding method, For example, well-known shaping | molding methods, such as injection molding, hollow shaping | molding, extrusion molding, sheet shaping | molding, film shaping | molding, can also be used. Molded articles obtained by molding the above-described resin composition can be used as various molded articles, and in particular, can be suitably used for home appliances, OA equipment, and the like. That is, the molded body of the present embodiment is a molded body including the above-described resin composition.

  The molded body of the present embodiment is preferably a thin molded body. The thickness of the molded body of this embodiment is preferably 1 mm or less, more preferably 0.8 mm or less.

The molded body of this embodiment includes (a) 25 to 60 parts by mass of a polyphenylene ether resin, (b) 2 to 20 parts by mass of a styrene-acrylonitrile copolymer, and (c) 5 to 30 parts by mass of a phosphorus compound. (D) 10 to 50 parts by mass of an inorganic filler (provided that the total of the component (a), the component (b), the component (c), and the component (d) is 100 parts by mass) It is preferable that it is a molded object which consists of a resin composition containing this. Furthermore, it is preferable that the molded body does not contain dispersed particles having a major axis of 0.1 μm or more containing the component (b).
Note that "there is no dispersed particles having a major axis containing (b) component of 0.1 µm or more" means that the major axis containing component (b) is 0.1 µm or more in image observation at a SEM magnification of 4000 times of the SEM of the molded product. This means that no dispersed particles exist. The dispersed particles containing the component (b) can be discriminated by observing the Os and Ru dyed compact. Specifically, in the method described in the examples described later, this means that no dispersed particles containing the component (b) having a major axis of 0.1 μm or more are detected.

  The molding method of the resin composition of the present embodiment is not particularly limited, and examples thereof include a molding method using an injection molding machine. Such an injection molding machine is not particularly limited, and examples thereof include “IS100GN” manufactured by TOSHIBA.

  In the molding method of the resin composition of the present embodiment, the melting temperature, the mold temperature, and the like can be appropriately selected from the ranges of a melting temperature of 200 to 320 ° C. and a mold temperature of 30 to 100 ° C. In particular, the melting temperature is preferably 200 to 300 ° C. from the viewpoint of not producing dispersed particles having a major axis of 0.1 μm or more containing the component (b) and obtaining excellent flame retardancy in the UL-94 vertical combustion test. 220 to 280 ° C is more preferable. The molding cycle time is preferably 110 seconds or less, more preferably 100 seconds or less, and even more preferably 60 seconds or less.

  EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention in detail, this invention is not limited by these Examples. In addition, the used raw material is as follows.

(A) Polyphenylene ether resin (a-1) Reduced viscosity (0.5 g / dL chloroform solution, measured at 30 ° C.) 0.35 dL / g poly (2,6-dimethyl-1,4-phenylene ether)
(A-2) Reduced viscosity (0.5 g / dL chloroform solution, measured at 30 ° C.) 0.52 dL / g poly (2,6-dimethyl-1,4-phenylene ether)

(B) Styrene-acrylonitrile copolymer The AS copolymer of (b) was produced as follows.
A mixed liquid consisting of 4.7 parts by mass of acrylonitrile, 73.3 parts by mass of styrene, 22 parts by mass of ethylbenzene, and 0.02 parts by mass of t-butylperoxy-isopropyl carbonate as a polymerization initiator was added at 2.5 liters / hour. The polymer was continuously fed at a flow rate to a 5 liter fully mixed reactor and polymerized at 142 ° C. to obtain a polymerization solution.
The resulting polymerization solution is continuously led to an extruder with a vent, and unreacted monomers and solvent are removed under conditions of 260 ° C. and 40 Torr, the polymer is continuously cooled and solidified, and chopped into particulate styrene. -Acrylonitrile copolymer (hereinafter sometimes referred to as "AS") was obtained.
The composition analysis of this styrene-acrylonitrile copolymer by infrared absorption spectroscopy revealed that it was 9% by mass of acrylonitrile units and 91% by mass of styrene units. The styrene-acrylonitrile copolymer had a melt flow rate of 78 g / 10 min (according to ASTM D 1238, measured at 220 ° C. and 10 kg load).

(C) Phosphorus compound Condensed phosphate ester compound, trade name “E890”, manufactured by Daihachi Chemical Industry Co., Ltd.

(D) Inorganic filler (d-1) Product name “BHT Mica 200D”, manufactured by West Japan Trading Co., Ltd. (d-2) Product name “CSF 3PE 293”, manufactured by Nitto Boseki Co., Ltd.

(E) Polytetrafluoroethylene Product name “METABBRENE A3800”, manufactured by Mitsubishi Rayon Co., Ltd.

(Additive)
Polystyrene, trade name “GPPS 680”, manufactured by PS Japan Ltd.

Evaluation of the resin composition obtained in Examples 1-11 and Comparative Examples 1-12 was performed by the following methods and conditions.
[Preparation of test piece]
The resin composition pellets obtained in Examples 1 to 11 and Comparative Examples 1 to 12 were dried at 90 ° C. for 1 hour. From the dried resin composition pellets, an IS-100GN injection molding machine (manufactured by Toshiba Machine Co., Ltd., cylinder temperature (melting temperature) of 240 ° C. to 280 ° C., molding cycle time of 60 seconds, mold temperature of 80 ° C. A test piece was prepared according to ISO-15103.

<Presence / absence of dispersed particles having a major axis containing (b) component of 0.1 μm or more>
The test specimen was polished to produce a vertical cross section, and after Os and Ru staining, Os coating was applied, SEM (apparatus: HITACHI SU8220, acceleration voltage: 4 kV, WD: 8.0-8.3 mm) , Magnification: 4000 times). Since the dispersed particles are not perfect circles, the longest diameter portion of the dispersed particles observed in the cross section is the major axis, and the presence or absence of the dispersed particles containing the component (b) having a major axis of 0.1 μm or more It was confirmed. When three magnified images corresponding to a cross section of 0.02 mm × 0.03 mm are observed, and there is no dispersed particle having a major axis of 0.1 μm or more including (b) component, “None”, (b) component The case where there was one or more dispersed particles having a major axis of 0.1 μm or more was evaluated as “present”.
In Comparative Examples 1 and 3, since the component (b) was not used, the dispersed particle size could not be measured.

<Melt flow rate (MFR)>
Using the resin composition pellets obtained in Examples 1 to 11 and Comparative Examples 1 to 12, the melt flow rate (g / 10 min) was measured under the conditions of 250 ° C. and 10 kg load according to ISO-1133.
As an evaluation standard, the larger the melt flow rate, the better the fluidity.

<Charpy impact strength>
In accordance with ISO-179, a notch (notch) was provided in the center of the test piece to prepare a notched Charpy impact test piece. About the Charpy impact test piece with this notch, Charpy impact strength (kJ / m < ² >) in 23 degreeC was measured as impact resistance evaluation based on ISO-179.
As an evaluation standard, the larger the measured value, the better the impact resistance.

<Flame retardance>
Based on the UL-94 vertical combustion test, flame retardancy was evaluated using two types of injection-molded test pieces having a thickness of 0.75 mm and a thickness of 1.0 mm.
First, a screw in-line type injection molding machine (trade name “SH100C”, manufactured by Sumitomo Heavy Industries, Ltd.) in which the resin composition pellets obtained in Examples 1 to 11 and Comparative Examples 1 to 12 were set to 220 to 240 ° C. And injection molding under conditions of a mold temperature of 30 ° C. and a cylinder temperature (melting temperature) of 220 ° C. to 240 ° C., the dimensions (length 125 mm × width 13 mm, thickness 0. Two types of test pieces (75 mm and 1.0 mm) were manufactured.
A flame of a gas burner was applied to the test piece, and the degree of combustion was evaluated.
In addition, the flame retardance class indicated the flame retardance class classified by UL94 vertical test. All the test pieces were judged by performing five tests. The outline of the classification method is as follows.
V-1: Total combustion time of 5 tubes 250 seconds or less, maximum combustion time 30 seconds or less, no flaming dripping flaming dripping present: at least one test piece, after flame contact, placed under the dripping material Cotton ignited

<Bending elastic modulus>
Using the test piece, the flexural modulus (GPa) was measured at 2 mm / min according to ISO-178.
As evaluation criteria, it was evaluated that the greater the flexural modulus, the better the rigidity.

  The resin compositions obtained in Example 12 and Comparative Examples 13 to 14 were evaluated by the following methods and conditions.

<Flame retardance>
Based on the UL-94 vertical combustion test, flame retardancy was evaluated using two types of injection-molded test pieces having a thickness of 0.75 mm and a thickness of 1.0 mm.
First, the resin composition pellets obtained in Example 12 and Comparative Examples 13 to 14 are supplied to a screw inline type injection molding machine (trade name “SH100C”, manufactured by Sumitomo Heavy Industries, Ltd.) set at 220 to 240 ° C. Then, the dimensions (length 125 mm x width 13 mm, thickness specified by the standard) are formed by injection molding under conditions of a mold temperature of 30 ° C. and a cylinder temperature (melting temperature) and a molding cycle time shown in Table 3. (2 types of 0.75 mm and 1.0 mm) were manufactured.
A flame of a gas burner was applied to the test piece, and the degree of combustion was evaluated.
In addition, the flame retardance class indicated the flame retardance class classified by UL94 vertical test. All the test pieces were judged by performing five tests. The outline of the classification method is as follows.
V-1: Total combustion time of 5 tubes 250 seconds or less, maximum combustion time 30 seconds or less, no flaming dripping flaming dripping present: at least one test piece, after flame contact, placed under the dripping material Cotton ignited

<Presence / absence of dispersed particles having a major axis containing (b) component of 0.1 μm or more>
The test piece prepared for the above-mentioned flame retardancy evaluation is polished to produce a vertical cross section, subjected to Os and Ru staining, Os coating, SEM (apparatus: HITACHI SU8220, acceleration voltage: 4 kV, (WD: 8.0-8.3 mm, magnification: 4000 times) The cross section was observed. Since the dispersed particles are not perfect circles, the longest diameter portion of the dispersed particles observed in the cross section is the major axis, and the presence or absence of the dispersed particles containing the component (b) having a major axis of 0.1 μm or more It was confirmed. When three magnified images corresponding to a cross section of 0.02 mm × 0.03 mm are observed, and there is no dispersed particle having a major axis of 0.1 μm or more including (b) component, “None”, (b) component The case where there was one or more dispersed particles having a major axis of 0.1 μm or more was evaluated as “present”.
In the above evaluation, a test piece having a length of 125 mm × a width of 13 mm and a thickness of 0.75 mm was used.

Hereinafter, each example and each comparative example will be described in detail. As a resin composition production apparatus, a twin-screw extruder (trade name “ZSK25-WLE”, manufactured by Coperion Co., Ltd.) was used. In the twin-screw extruder, the number of barrels is 12 blocks, and the first barrel from the upstream (first supply port), the sixth barrel (second supply port), and the ninth barrel (third supply port) in the flow direction of the raw material. 3), a total of three supply ports, one at each location, a liquid addition pump at the seventh barrel, and a vacuum vent at two locations at the fifth and eleventh barrels. Moreover, the raw material supply method to the 2nd supply port and the 3rd supply port was set as the method of supplying using a forced side feeder from an extruder side opening port.
In the manufacturing methods 1 to 6, the screw configuration provided in the barrel and the set temperature of the barrel are as described in FIG. In addition, the meaning of the abbreviation of the kneading disk used for the description of the screw configuration is as follows.
・ R1: Kneading disc light (L / D = 0.96)
R2: Kneading disc light (L / D = 0.48)
・ L: Kneading disc left (L / D = 0.48)
・ N: Kneading disc neutral (L / D = 1.04)
・ Reverse: Two-flight flight screw reverse feed (L / D = 0.48)

[Examples 1-12, Comparative Examples 1-14]
It melt-kneaded on the twin-screw extruder set as mentioned above on the conditions of the discharge amount of 15 kg / hour under the composition and manufacturing conditions shown in Tables 1, 2, and 3 to obtain pellets of the resin composition.
Tables 1, 2, and 3 show the results of evaluation of the resin composition and the molded body by the measurement method described above for each of the examples and comparative examples.

  As shown in Tables 1, 2, and 3, Examples 1 to 11 in which no dispersed particles containing a styrene-acrylonitrile copolymer have a major axis of 0.1 μm or more are present in fluidity, flame retardancy, and mechanical properties. I found it excellent. In addition, Example 12 was excellent in flame retardancy.

  ADVANTAGE OF THE INVENTION According to this invention, the resin composition excellent in fluidity | liquidity, a flame retardance, and a mechanical physical property can be provided, and it has industrial applicability as materials, such as a household appliance and OA apparatus use.

Claims (8)

(A) 25-60 parts by mass of a polyphenylene ether resin,
(B) 2-20 parts by mass of a styrene-acrylonitrile copolymer;
(C) 5 to 30 parts by mass of a phosphorus compound;
(D) 10 to 50 parts by mass of an inorganic filler;
(However, the total of the component (a), the component (b), the component (c), and the component (d) is 100 parts by mass),
In the test piece produced according to ISO-15103, the resin composition characterized by the absence of dispersed particles having a major axis of 0.1 μm or more containing the component (b). The component (a) is
(A-1) a polyphenylene ether resin having a reduced viscosity of 0.30 to 0.40 dL / g;
(A-2) a polyphenylene ether resin having a reduced viscosity of 0.45 to 0.55 dL / g,
Including
Ratio of content of component (a-2) to total content of component (a-1) and component (a-2) (content of component (a-2) / content of component (a-1) The resin composition according to claim 1, wherein the amount + content of (a-2) component) × 100) is 10 to 60%.   The resin composition of Claim 1 or 2 whose said (b) component is a copolymer containing 5-15 mass% of acrylonitrile units.   (E) 0.02-0.3 parts by mass of polytetrafluoroethylene is further added to 100 parts by mass in total of the component (a), the component (b), the component (c), and the component (d). The resin composition according to any one of claims 1 to 3, which is contained.   The molded object characterized by including the resin composition of any one of Claims 1-4. (A) 25-60 parts by mass of a polyphenylene ether resin,
(B) 2-20 parts by mass of a styrene-acrylonitrile copolymer;
(C) 5 to 30 parts by mass of a phosphorus compound;
(D) 10 to 50 parts by mass of an inorganic filler;
(However, a molded body made of a resin composition comprising (a) component, (b) component, (c) component, and (d) component is 100 parts by mass),
(B) A molded article characterized by the absence of dispersed particles having a major axis of 0.1 μm or more containing the component.   An ink jet printer part or member comprising the resin composition according to claim 1.   The molded article according to claim 5 or 6, which is an inkjet printer part or member.