JP6181478B2 - Resin composition - Google Patents

Description

  The present invention relates to a resin composition.

Conventionally, polyphenylene ether resins are used in home appliances, OA equipment, automobile parts, etc. because they have excellent electrical insulation properties, as well as good heat resistance, hydrolysis resistance, and flame resistance. ing.
In recent years, in addition to these properties such as electrical insulation, heat resistance, hydrolysis resistance, and flame resistance, slidability, chemical resistance, and grease resistance are required depending on the application. It is becoming.
In response to such demands, conventionally, a resin composition in which polyethylene resin or polypropylene resin is added to impart high slidability, chemical resistance, and grease resistance to a polyphenylene ether resin is known. .
However, since both of the polyethylene resin and the polypropylene resin have a low melting point, the resin composition has a problem that sufficient heat resistance is not obtained although the processability is excellent.

Conventionally, a resin composition in which polytetrafluoroethylene is added to a polyphenylene ether resin to impart slidability has also been disclosed (for example, see Patent Document 1).
In addition, since it is difficult to disperse polytetrafluoroethylene in a polyphenylene ether resin, a technique for making it into a fibril form and dispersing it in a polyphenylene ether resin has also been disclosed (for example, Patent Document 2). reference.).

JP 2002-2335011 A Japanese Patent Laid-Open No. 11-5879

However, like the technique disclosed in Patent Document 2, a resin composed of polytetrafluoroethylene dispersed in a fibril form in a polyphenylene ether resin has a problem that the fluidity is extremely low and the processability is poor. .
In order to solve such a problem, a method of adding polytetrafluoroethylene crosslinked by an electron beam to a polyphenylene ether resin has been studied, but it has a problem that the cost is very high.

  As described above, conventionally, a resin composition that satisfies the level required by the market for improving the slidability and chemical resistance while maintaining the heat resistance and workability of the polyphenylene ether resin has not been obtained. .

  Therefore, in the present invention, in view of the above-mentioned problems of the prior art, a polyphenylene ether-based resin composition having excellent heat resistance and workability and good sliding properties, chemical resistance, and impact resistance is provided. For the purpose.

As a result of intensive studies in order to solve the above problems, the present inventor has found that a polyphenylene ether resin or a mixed resin of a polyphenylene ether resin and a polystyrene resin, an ethylene-tetrafluoroethylene copolymer, a specific resin It has been found that by including a specific amount of a block copolymer, a polyphenylene ether-based resin composition having excellent slidability, chemical resistance and impact resistance can be obtained while maintaining heat resistance and workability. The present invention has been completed.
That is, the present invention is as follows.

[1]
(A) Polyphenylene ether resin or mixed resin of polyphenylene ether resin and polystyrene resin: 70 to 96% by mass;
(B) ethylene-tetrafluoroethylene copolymer: 40-2% by mass;
(C) a number average molecular weight of 62,000 or more, a block copolymer of an aromatic vinyl compound and a conjugated diene compound and / or a hydrogenated product of the block copolymer: 2 to 20% by mass,
The, only including,
In the block copolymer (c) of the aromatic vinyl compound and the conjugated diene compound and / or the hydrogenated product of the block copolymer, the binding amount of the aromatic vinyl compound is 30 to 50% by mass, The proportion of the total amount of 1,2-vinyl bonds and 3,4-vinyl bonds to the total amount of bonds in the conjugated diene compound in the block copolymer is 20 to 45%.
Resin composition.
[2]
The resin composition according to [1], wherein (b) MFR (ASTM-D3159) of the ethylene-tetrafluoroethylene copolymer is 10 to 40 g / 10 minutes.
[3]
The resin composition according to [1] or [2] , further including a condensed phosphate ester flame retardant.

  ADVANTAGE OF THE INVENTION According to this invention, the polyphenylene ether-type resin composition which is excellent also in slidability, chemical resistance, and impact resistance can be provided, maintaining the outstanding heat resistance and workability.

  Hereinafter, a mode for carrying out the present invention (hereinafter 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.

(Resin composition)
The resin composition of the present embodiment is
(A) polyphenylene ether resin or mixed resin of polyphenylene ether resin and polystyrene resin: 58 to 96% by mass;
(B) ethylene-tetrafluoroethylene copolymer: 40-2% by mass;
(C) a block copolymer of an aromatic vinyl compound and a conjugated diene compound and / or a hydrogenated product of the block copolymer: 2 to 20% by mass;
Is a resin composition containing

Hereinafter, the components of the resin composition of the present embodiment will be described.
((A) Polyphenylene ether resin or mixed resin of polyphenylene ether resin and polystyrene resin)
The resin composition of the present embodiment contains (a) a polyphenylene ether-based resin or a mixed resin of a polyphenylene ether-based resin and a polystyrene resin (hereinafter, may be referred to as (a) component).
That is, the resin composition of the present embodiment contains, as component (a), a polyphenylene ether resin (hereinafter sometimes referred to as PPE) or a mixed resin of a polyphenylene ether resin and a polystyrene resin.
By containing a polyphenylene ether-based resin, the resin composition of the present embodiment has excellent flame retardancy and heat resistance.
PPE includes a bond unit represented by the following (formula 1).
The PPE may be a homopolymer or a copolymer.

In the above (formula 1), R1, R2, R3, and R4 are each hydrogen, halogen, primary or secondary alkyl group having 1 to 7 carbon atoms, phenyl group, haloalkyl group, aminoalkyl group, A hydrocarbon oxy group or any one selected from the group consisting of a halohydrocarbon oxy group in which at least two carbon atoms separate a halogen atom and an oxygen atom may be the same or different.
The polyphenylene ether resin has a reduced viscosity of 0.15 measured at 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. Is preferably in the range of -2.0 (dl / g), more preferably in the range of 0.20-1.0 (dl / g), still more preferably in the range of 0.3-0.7 (dl / g). g).

  Examples of the PPE include, but are not limited to, poly (2,6-dimethyl-1,4-phenylene ether) and poly (2-methyl-6-ethyl-1,4-phenylene ether). , Poly (2-methyl-6-phenyl-1,4-phenylene ether), poly (2,6-dichloro-1,4-phenylene ether) and the like, and further, 2,6-dimethylphenol and other Polyphenylene ether copolymers such as copolymers with phenols (for example, 2,3,6-trimethylphenol and 2-methyl-6-butylphenol) are also included. In particular, poly (2,6-dimethyl-1,4-phenylene ether), 2,6-dimethylphenol and 2,3 from the viewpoint of the balance between toughness and rigidity when used as a resin composition and easy availability. , 6-trimethylphenol copolymer is preferred, and poly (2,6-dimethyl-1,4-phenylene ether) is more preferred.

The PPE can be produced by a known method.
The method for producing PPE is not limited to the following, for example, a method of oxidative polymerization of 2,6-xylenol using a complex of cuprous salt and amine described in US Pat. No. 3,306,874 as a catalyst, In addition, the methods described in US Pat. Nos. 3,306,875, 3,257,357, 3,257,358, JP-B-52-17880, JP-A-50-51197, and JP-A-63-152628 are disclosed. Can be mentioned.

In the present embodiment, as the component (a), a mixed resin obtained by mixing a polystyrene resin with a polyphenylene ether resin can be used.
By adding a polystyrene resin to PPE, the effect of being able to design heat resistance, fluidity, etc. can be obtained by simply changing the addition amount.
The polystyrene resin is not limited to the following, but a homopolymer of a styrene compound, a copolymer of two or more styrene compounds, and a rubber-like material in a matrix made of the polymers of these styrene compounds. Examples thereof include a rubber-modified styrene resin in which a polymer is dispersed in the form of particles.
Polystyrene resins may be used alone or in combination of two or more.
(A) In the mixed resin of polyphenylene ether resin and polystyrene resin, the composition ratio of PPE / polystyrene resin is polystyrene when the total of PPE and polystyrene resin is 100% by mass from the viewpoint of heat resistance and fluidity. It is preferable that resin is 1-95 mass%, More preferably, it is 1-90 mass%, More preferably, it is 5-85 mass%, More preferably, it is 10-80 mass%.

  The content of the component (a) in the resin composition of the present embodiment is 58 to 96 mass%, preferably 70 to 96 mass%, more preferably 75 to 96 mass%, from the viewpoints of flame retardancy and heat resistance. It is.

((B) ethylene-tetrafluoroethylene copolymer)
The resin composition of the present embodiment contains (b) an ethylene-tetrafluoroethylene copolymer (hereinafter may be referred to as (b) component).
The content of the (b) ethylene-tetrafluoroethylene copolymer in the resin composition of the present embodiment is 40 to 2% by mass and 40 to 5% by mass from the viewpoint of obtaining excellent slidability and chemical resistance. %, And more preferably 35 to 10% by mass.

  (B) The ethylene-tetrafluoroethylene copolymer is not limited to the following. For example, Daikin Industries, Ltd. Neoflon (registered trademark) ETFE EP-506, Asahi Glass Co., Ltd., Fullon LM- ETFE (registered trademark) LM-720AP, LM-730AP, LM-740AP may be mentioned.

The MFR value of the component (b) is preferably 10 to 40 g / 10 minutes, more preferably 13 to 37 g / 10 minutes, and further preferably 15 to 35 g / 10 minutes.
When the MFR value of the component (b) is 10 to 40 g / 10 minutes, the component (b) can be uniformly and finely dispersed in the resin composition. For this reason, even if a sufficient amount of (b) ethylene-tetrafluoroethylene copolymer is added to improve the slidability and chemical resistance of the resin composition, good processability can be obtained.
The MFR value of the component (b) can be measured by the method described in ASTM-D3159 as described in Examples described later.

  In order to adjust the MFR of the component (b) to 10 to 40 g / 10 minutes, for example, it is effective to control the molecular weight of the component (b) or to adjust the ratio of the raw material ethylene to tetrafluoroethylene. It is.

((C) Block copolymer of aromatic vinyl compound and conjugated diene compound and / or hydrogenated product of the block copolymer)
The resin composition of the present embodiment comprises (c) a block copolymer of an aromatic vinyl compound and a conjugated diene compound and / or a hydrogenated product of the block copolymer (hereinafter referred to as (c) a block copolymer, ( c) may be described as a component).
The component (c) is a block copolymer obtained by copolymerizing an aromatic vinyl compound and a conjugated diene compound and / or a hydrogenated block copolymer obtained by hydrogenating the block copolymer.
The component (c) functions as an admixture of the components (a) and (b) described above, and has a great effect from the viewpoint of imparting toughness to the resin composition of the present embodiment.

  The component (c) is not limited to the following when the aromatic vinyl compound polymer block is A and the conjugated diene compound polymer block is B. For example, AB, A-B-A , B-A-B-A, (A-B-) 4-Si, A-B-A-B-B, and the like. The hydrogenated product of the block copolymer is also included.

In the component (c), the binding amount of the aromatic vinyl compound is preferably 30 to 50% by mass, more preferably 30 to 45% by mass, from the viewpoint of miscibility of the component (a) and the component (b). More preferably, it is 30-40 mass%.
Examples of the method for adjusting the binding amount of the aromatic vinyl compound in the component (c) to 30 to 50% by mass include a method for adjusting the ratio of the aromatic vinyl compound and the conjugated diene compound as a raw material.
The binding amount of the aromatic vinyl compound in component (c) can be measured with an infrared spectrophotometer or the like.

In the block structure constituting the component (c), the aromatic vinyl compound polymer block A is more than 50% by mass of the homopolymer block of the aromatic vinyl compound or the aromatic vinyl compound, preferably 70 It is a copolymer block of an aromatic vinyl compound and a conjugated diene compound that are contained by mass% or more.
In the block structure constituting the component (c), the conjugated diene compound polymer block B is more than 50% by mass, preferably 70% by mass or more, of the homopolymer block of the conjugated diene compound or the conjugated diene compound. It is a copolymer block of the conjugated diene compound and aromatic vinyl compound to contain.
Since the aromatic vinyl compound polymer block A and the conjugated diene compound polymer block B have the above structure, the resin composition of this embodiment has excellent miscibility and toughness imparting effects. can get.
In these aromatic vinyl compound polymer block A and conjugated diene compound polymer block B, the distribution of the conjugated diene compound or aromatic vinyl compound in the molecular chain in each polymer block is random, tapered (along the molecular chain). In which the monomer component is increased or decreased), a partly block shape, or any combination thereof. When the aromatic vinyl compound polymer block A and the conjugated diene compound polymer block B are each two or more in the component (c), the polymer blocks may have the same structure or different structures. There may be.

The aromatic vinyl compound constituting the component (c) is not limited to the following, and examples thereof include styrene, α-methylstyrene, vinyltoluene, p-tert-butylstyrene, diphenylethylene and the like. These may be used alone or in combination of two or more. Of these, styrene is preferred.
The conjugated diene compound constituting the component (c) is not limited to the following, and examples thereof include butadiene, isoprene, 1,3-pentadiene, 2,3-dimethyl-1,3-butadiene and the like. . These may be used alone or in combination of two or more. Of these, butadiene, isoprene, and combinations thereof are preferable.

The conjugated diene compound polymer block B in the component (c) can arbitrarily select the microstructure of the bonding form in the block.
The conjugated diene compound may be bonded to an adjacent monomer through a 1,2-vinyl bond, a 3,4-vinyl bond, or a 1,4-conjugated bond. Therefore, the total amount of 1,2-vinyl bonds, 3,4-vinyl bonds, and 1,4-conjugated bonds in the block is defined as the total bond amount.
At this time, from the viewpoint of miscibility, the proportion of the total amount of 1,2-vinyl bonds and 3,4-vinyl bonds to the total amount of bonds of the conjugated diene compound is preferably 20 to 45%. More preferably, it is 25-40%, More preferably, it is 30-40%.
For example, when the component block (c) has a polymer block mainly composed of butadiene, the proportion of the 1,2-vinyl bond amount to the total bond amount in the butadiene portion, and isoprene in the component (c) When the polymer block is mainly composed of 1, the ratio of the total amount of 1,2-vinyl bonds and 3,4-vinyl bonds to the total amount of bonds in the isoprene portion is 20 to 45%. Preferably, it is 25 to 45%, more preferably 30 to 40%.
As a method of adjusting the ratio of the total amount of 1,2-vinyl bonds and 3,4-vinyl bonds to the total number of bonds of the conjugated diene compound in component (c) to the above numerical range, polymerization conditions And adjustment of vinyl bond accelerators and the like.
The ratio of the amount of 1,2-vinyl bonds and 3,4-vinyl bonds to the total amount of conjugated diene compounds in component (c) is determined by infrared spectrophotometer, nuclear magnetic resonance apparatus (NMR), infrared. It can be measured with a spectrophotometer.

The number average molecular weight of the component (c) is preferably from 5,000 to 1,000,000, more preferably from 20,000 to 500,000, further preferably from the viewpoint of mixing with the resin and imparting impact resistance. Is 30,000 to 300,000.
(C) Component molecular weight distribution [ratio of weight average molecular weight (Mw) and number average molecular weight (Mn) measured by gel permeation chromatography and converted to polystyrene] is 10 or less from the viewpoint of mixing with resin and imparting impact resistance. Is preferable, 8 or less is more preferable, and 5 or less is more preferable.

Furthermore, the molecular structure of the component (c) may be linear, branched or radial, or any combination thereof.
In addition, the hydrogenated product of the block copolymer as the component (c) is to carry out a hydrogenation reaction on the aliphatic double bond of the conjugated diene compound polymer block B of the block copolymer described above. Is obtained.
The hydrogenation rate of the aliphatic double bond in the hydrogenated block copolymer as the component (c) is preferably more than 20% from the viewpoint of thermal stability and impact resistance during processing. Preferably it is 50% or more, more preferably 80% or more.
Such a hydrogenation rate can be measured using, for example, a nuclear magnetic resonance apparatus (NMR).

  The content of the component (c) in the resin composition of the present embodiment is 2 when the total of the components (a) to (c) is 100% by mass from the viewpoint of miscibility, impact resistance, and mechanical properties. It is made into -20 mass%, More preferably, it is 5-20 mass%, More preferably, it is 5-15 mass%.

  Examples of the component (c) include, but are not limited to, SBS (styrene-butadiene-styrene) block copolymer, SIS (styrene-isoprene-styrene) block copolymer, and the like. Examples of hydrogenated products of aromatic vinyl compounds and conjugated diene compound block copolymers include SEBS (styrene-ethylene-butylene-styrene) block copolymers and SEPS (styrene-ethylene-propylene-styrene) block copolymers. . These may be used alone or in combination of two or more.

(Condensed phosphate ester flame retardant)
When the resin composition of this embodiment is applied to an application that requires flame retardancy, it is preferable that the component (a) further contains a condensed phosphate ester flame retardant.
This condensed phosphate ester flame retardant has a great effect on imparting flame retardancy to the resin composition of this embodiment, coupled with the auxiliary flame retardant effect of the polyphenylene ether resin of component (a) described above.

  The condensed phosphate ester flame retardant is, for example, a phosphate ester represented by the following general formula (formula 2) and / or a condensate thereof.

In the formula (2), R11, R12, R13 and R14 are each a group consisting of a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an aryl-substituted alkyl group, an aryl group, a halogen-substituted aryl group, and an alkyl-substituted aryl group. Represents one selected from the above, and may be the same or different.
X represents an arylene group.
n is an integer of 0-5.
In addition, when it is the condensate of the phosphate ester which has different n value, said n represents those average values.

When n = 0, the compound of (Formula 2) represents a phosphate ester monomer.
Typical phosphoric acid ester monomers include, but are not limited to, triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, and the like.
As a condensate, n can take the value of 1-5 normally, Preferably it is 1-3 at an average value.
From the viewpoint of flame retardancy and heat resistance when kneaded into a resin, it is preferable that at least one of R11, R12, R13 and R14 in the above (Formula 2) is an aryl group, more preferably R11, R12, R13 and R14 are all aryl groups.
From the viewpoint of flame retardancy and heat resistance when kneaded into a resin, preferred aryl groups include phenyl, xylenyl, cresyl, or halogenated derivatives thereof.
Preferred arylene groups for X include residues in which two hydroxyl groups are eliminated from resorcinol, hydroquinone, bisphenol A, biphenol, or halogenated derivatives thereof.
Representative condensed phosphate compounds include, but are not limited to, resorcinol / bisphenyl phosphate compounds, bisphenol A-polyphenyl phosphate compounds, bisphenol A-polycresyl phosphate compounds, and the like.

  The content of the condensed phosphate ester flame retardant in the resin composition of the present embodiment is the sum of (a) the polyphenylene ether resin and the condensed phosphate ester flame retardant from the viewpoints of flame retardancy, heat resistance, and mechanical properties. When it is 100 mass%, 40-2 mass% is preferable, More preferably, it is 30-2 mass%, More preferably, it is 25-2 mass%. If the content of the condensed phosphate ester flame retardant is 2% by mass or more, sufficient flame retardancy is easily exhibited, and if it is 40% by mass or less, heat resistance and impact resistance are not deteriorated.

(Other ingredients)
In addition to the components described above, the resin composition of the present embodiment may contain other components as necessary within a range that does not impair the slidability or chemical resistance of the resin composition.
Such other components include, but are not limited to, for example, antioxidants, metal deactivators, flame retardants (organic phosphate esters other than the above-described condensed phosphate ester flame retardants) Compounds, ammonium polyphosphate compounds, silicone flame retardants, etc.), plasticizers (low molecular weight polyethylene, epoxidized soybean oil, polyethylene glycol, fatty acid esters, etc.), weather resistance (light) improvers, slip agents, inorganic or organic Fillers and reinforcing materials (polyacrylonitrile fiber, aramid fiber, etc.), various colorants, release agents and the like.

[Method for producing resin composition]
The resin composition of the present embodiment can be produced by melt-kneading the above-described components (a) to (c) and, if necessary, a condensed phosphate ester flame retardant and other components.
Examples of the melt kneader for performing melt kneading include, for example, a single screw extruder, a multi-screw extruder including a twin screw extruder, a heat melt kneader such as a roll, a kneader, a Brabender plastograph, and a Banbury mixer. In particular, from the viewpoint of kneadability, a twin screw extruder is preferable. Specific examples include the ZSK series manufactured by WERNER & PFLEIDERER, the TEM series manufactured by Toshiba Machine Co., Ltd., and the TEX series manufactured by Nippon Steel Works.

A preferred production method using an extruder will be described below.
The L / D (barrel effective length / barrel inner diameter) of the extruder is preferably in the range of 20 or more and 60 or less, more preferably 30 or more and 50 or less.
The extruder is provided with a first raw material supply port on the upstream side, a first vacuum vent on the downstream side, and a second raw material supply port on the downstream side with respect to the flow direction of the raw material. A material supply port is provided) and a second vacuum vent is further provided downstream thereof. In particular, a kneading section is provided upstream of the first vacuum vent, a kneading section is provided between the first vacuum vent and the second raw material supply port, and between the second to fourth raw material supply ports and the second vacuum vent. It is more preferable to provide a kneading section.

Although the raw material supply method to the said 2nd-4th raw material supply port is not specifically limited, Extruder side opening is rather than the mere addition supply from the open port of an extruder 2nd-4th raw material supply port. A method of supplying from the mouth using a forced side feeder is preferable because it can be stably supplied.
In particular, when the raw material contains a large amount of powder and it is desired to reduce the generation of cross-linked products and carbides due to the thermal history of the resin, a method using a forced side feeder supplied from the extruder side is more preferable. More preferably, the method is provided in the second to fourth raw material supply ports and the powder of these raw materials is divided and supplied.
Moreover, when adding a liquid raw material, the method of adding in an extruder using a plunger pump, a gear pump, etc. is preferable.
And the upper open port of the extruder 2nd-4th raw material supply port can also be made open in order to extract the air to carry.
Although it does not specifically limit regarding the melt-kneading temperature and screw rotation speed in the melt-kneading process of a resin composition, Usually, melt-kneading temperature shall be 260-350 degreeC, and screw rotation speed shall be 100-1200 rpm.

  Furthermore, when reducing the occurrence of cross-linked products and carbides due to the thermal history in the presence of oxygen in the resin, the addition route of each raw material to the extruder, specifically, the weight type feeder that has stock tank → piping → refill tank → Piping → Supply hopper → Oxygen concentration in each process line of the twin-screw extruder is preferably kept below 1.0% by volume. In order to maintain such a low oxygen concentration, it is effective to introduce an inert gas into individual process lines with improved airtightness. Usually, nitrogen gas is introduced to maintain the oxygen concentration below 1.0% by volume.

  When the resin composition of this embodiment is manufactured using a biaxial extruder using the powdery (a) polyphenylene ether resin, the method for producing the resin composition described above, This has the effect of dramatically reducing the residue in the screw, and further has the effect of reducing the occurrence of sunspot foreign materials, carbides, etc. in the resin composition obtained by the above-described production method.

As a specific method for producing the resin composition of the present embodiment, an extruder in which the oxygen concentration of each raw material supply port is controlled to be less than 1.0% by volume and the following methods 1 to 4 may be carried out. preferable.
1. A method in which the components (a) and (c) described above are melt kneaded and then the components (b) are supplied and melt kneaded.
2. (A) A method in which the components are melt-kneaded and then the components (b) and (c) are added and melt-kneaded.
3. A method in which the components (a) and (b) are melt-kneaded, and then the component (c) is added, followed by melt-kneading.
4). A method in which the whole amount of the components (a) to (c) is melt-kneaded.
In particular, the resin composition obtained by the production method 1 has a uniform dispersion form in which the components (a) to (c) are superior to the resin composition obtained by the production methods 2 to 4 above. These compounding effects can be expressed most remarkably, the occurrence of cross-linked products and carbides due to the thermal history of the resin can be reduced, and a resin composition excellent in slidability and chemical resistance can be obtained. Therefore, it is more preferable.

〔Molding〕
A desired molded product can be obtained by molding the resin composition of the present embodiment.
The molding method is not limited to the following, for example, molding such as injection molding, metal in-mold molding, outsert molding, extrusion molding, sheet molding, film molding, hot press molding, rotational molding, and lamination molding. A method is mentioned. Molded articles of the resin composition of the present embodiment include optical device mechanism parts, light source lamp surrounding parts, metal film laminated substrate sheets or films, hard disk internal parts, optical fiber connector ferrules, printer parts, copier parts, automobile radiator tanks It can be widely used as a molded product such as a part in a car engine room such as a part or a car lamp part.

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

The measuring method of the physical property used for the Example and the comparative example is shown below.
((1) MFR of ethylene-tetrafluoroethylene copolymer)
Measurement was performed by the method described in ASTM-D3159.
((2) Specific gravity of ethylene-tetrafluoroethylene copolymer)
Measurement was performed by the method described in ISO-1183.
((3) MFR of resin composition)
Based on JIS-K7210, MFR was measured on condition of temperature 250 degreeC and load 98N.
((4) Friction coefficient)
Using a JIS K7139 test piece, with a reciprocating friction and wear tester (trade name “AFT-15MS type” manufactured by Toyo Seimitsu Co., Ltd.), a load of 0.5 kg, a linear velocity of 60 mm / sec, a reciprocating distance of 10 mm, A reciprocating test was performed 10,000 times at an environmental temperature of 23 ° C., and the 10,000th friction coefficient was measured.
As the counterpart material, a SUS ball (SUS304, R = 2.5 mm) was used.
((5) Chemical resistance)
JIS K7139 test piece was attached to a bending bar, and a cloth soaked with Daphne Punch Oil (made by Idemitsu Kosan Co., Ltd.) was contacted with the surface of the test piece with a strain of 0.3%, and after 1 hour. The occurrence of cracks on the surface of the test piece was observed and evaluated according to the following criteria.
<Evaluation criteria for chemical resistance>
If the strip breaks completely after 1 hour: ×
When fine cracks occur on the surface of the strip after 1 hour:
If no cracks occur on the surface of the strip after 1 hour: ○
((6) Charpy impact strength)
It measured based on JISK7111-1.
((7) Deflection temperature under load)
It measured based on JISK7191-1.
((8) Flame retardancy (UL-94))
According to the vertical combustion test method of UL94 (standard defined by Under Writers Laboratories Inc., USA), five tests were performed for each sample.

The raw materials used in the examples and comparative examples are shown below.
<(A) Component: Polyphenylene ether resin, polystyrene resin>
(A1): PPE having a reduced viscosity of 0.55 (dl / g) obtained by oxidative polymerization of 2,6-xylenol
(A2): Dry blend product of high impact polystyrene (polystyrene H 9405 manufactured by PS Japan) / polystyrene (polystyrene 680 manufactured by PS Japan) = 15/20 (mass ratio)

  Aromatic condensed phosphate ester (CR-741: manufactured by Daihachi Chemical Industry Co., Ltd.)

<(B) Component ethylene-tetrafluoroethylene copolymer>
(B1): Ethylene-tetrafluoroethylene copolymer (trade name Fullon (registered trademark) LM-720AP: manufactured by Asahi Glass Co., Ltd.)
(B2): Ethylene-tetrafluoroethylene copolymer (trade name Fullon (registered trademark) LM-730AP: manufactured by Asahi Glass Co., Ltd.)
(B3): Ethylene-tetrafluoroethylene copolymer (trade name Fullon (registered trademark) LM-740AP: manufactured by Asahi Glass Co., Ltd.)
(B4): Ethylene-tetrafluoroethylene copolymer (trade name NEOFLON (registered trademark) ETFE EP-610: manufactured by Daikin Industries, Ltd.)
(B5): ethylene-tetrafluoroethylene copolymer (trade name NEOFLON (registered trademark) ETFE EP-546: manufactured by Daikin Industries, Ltd.)

<(C) Aromatic vinyl compound and conjugated diene compound block copolymer>
(C1): Polystyrene-polybutadiene-polystyrene block structure, the amount of bound styrene measured with an infrared spectrophotometer was 35%, and 1,2-vinyl bond and 3,4-vinyl measured with an infrared spectrophotometer A block copolymer having a total amount of bonds of 40% and a number average molecular weight of 70000.
(C2): A hydrogenated block copolymer obtained by hydrogenating the above (c1) and having a polybutadiene portion hydrogenation rate of 99.3%.
(C3): Polystyrene-hydrogenated polyisoprene-polystyrene block structure, the amount of bound styrene measured with an infrared spectrophotometer is 33%, and 1,2 before hydrogenation measured with an infrared spectrophotometer A hydrogenated block copolymer having a total amount of vinyl bonds and 3,4-vinyl bonds of 43%, a number average molecular weight of 62,000, and a hydrogenation rate of the polyisoprene portion of 98.1%.
(C4): having a polystyrene-polybutadiene-polystyrene block structure, the amount of bound styrene measured with an infrared spectrophotometer was 48%, and 1,2-vinyl bond and 3,4-vinyl measured with an infrared spectrophotometer A block copolymer having a total amount of bonds of 22% and a number average molecular weight of 80000.
(C5): having a polystyrene-polybutadiene-polystyrene block structure, the amount of bound styrene measured with an infrared spectrophotometer was 36%, and 1,2-vinyl bond and 3,4-vinyl measured with an infrared spectrophotometer A block copolymer having a total amount of bonds of 15% and a number average molecular weight of 100,000.
(C6): Polystyrene-hydrogenated polybutadiene-polystyrene block structure, 25% of bound styrene measured with an infrared spectrophotometer, 1,2- before hydrogenation measured with an infrared spectrophotometer A hydrogenated block copolymer having a total amount of vinyl bonds and 3,4-vinyl bonds of 39%, a number average molecular weight of 51,000, and a hydrogenation rate of the polybutadiene part of 99.2%.
(C7): Polystyrene-hydrogenated polybutadiene-polystyrene block structure, 40% of bound styrene measured by infrared spectrophotometer, 1,2- before hydrogenation measured by infrared spectrophotometer A hydrogenated block copolymer having a total amount of vinyl bonds and 3,4-vinyl bonds of 49%, a number average molecular weight of 88000, and a hydrogenation rate of the polybutadiene part of 99.3%.
(C8): Polystyrene-hydrogenated polybutadiene-polystyrene block structure, the amount of bound styrene measured with an infrared spectrophotometer was 53%, and 1,2- before hydrogenation measured with an infrared spectrophotometer A hydrogenated block copolymer having a total amount of vinyl bonds and 3,4-vinyl bonds of 41%, a number average molecular weight of 62,000, and a hydrogenation rate of the polybutadiene portion of 99.4%.

<(D) Other components>
(D1): Low density polyethylene (trade name Suntec (registered trademark) LD M2004: manufactured by Asahi Kasei Chemicals Corporation)
(D2): High density polyethylene (trade name Suntec (registered trademark) HD F371: manufactured by Asahi Kasei Chemicals Corporation)
(D3): Polytetrafluoroethylene (trade name Polyflon (registered trademark) FA-500: manufactured by Daikin Industries, Ltd.)

  The predetermined | prescribed characteristic of the said (b) component was measured, the resin composition of Examples 1-20 and Comparative Examples 1-9 was manufactured using the said raw material, and the characteristic evaluation was performed.

[Examples 1-8, Reference Examples 9-13, Example 14, Reference Example 15, Examples 16-20], [Comparative Examples 1-9]
First, ethylene as component (b) used in Examples 1 to 8, Reference Examples 9 to 13, Example 14, Reference Example 15, Examples 16 to 20, Comparative Examples 4 to 6, and Comparative Examples 8 and 9 -MFR and specific gravity of the tetrafluoroethylene copolymer were measured by the methods (1) and (2) described above.
Next, using a twin screw extruder ZSK-40 (manufactured by WERNER & PFLIDEERER), the first raw material supply port on the upstream side, the second raw material supply port on the downstream side, and the third raw material supply port with respect to the flow direction of the raw material And a vacuum vent was provided downstream thereof.
Moreover, the raw material supply to the 2nd supply port was performed using the gear pump from the extruder upper open port, and the supply to the 3rd raw material supply port was performed using the forced side feeder from the extruder side open port. Using the extruder set as described above, (a) a mixed resin of a polyphenylene ether resin and a polystyrene resin, (b) an ethylene-tetrafluoroethylene copolymer, (c) an aromatic vinyl compound and a conjugated diene compound, These block copolymers or hydrogenated products thereof are blended in the compositions shown in Tables 1 to 3 below, and melt-kneaded under the conditions of an extrusion temperature of 250 to 320 ° C., a screw rotation speed of 300 rpm, and a discharge rate of 80 kg / hour, Resin composition pellets were produced.
The MFR of the resin composition was measured by the method shown in (3) using the pellets.
Further, using each of the pellets of the resin composition and the raw material (b2), it is supplied to a screw in-line type injection molding machine set at 220 to 320 ° C. and is subjected to JIS K7152 at a mold temperature of 60 to 90 ° C. -1 and K7313-2, JIS K7139 test pieces for measuring tensile strength and tensile elongation were produced. Using the JIS K7139 test piece, the (4) coefficient of friction and the (5) chemical resistance were measured.
Next, a JIS K7139 test piece was manufactured, a test piece for measuring Charpy impact strength and a test piece for measuring deflection temperature under load were obtained, and (6) Charpy impact strength and (7) deflection temperature under load were measured, respectively.
In addition, as a flame retardant test piece, a test piece having a length of 127 mm, a width of 12.7 mm, and a thickness of 1.6 mm was molded under the same injection molding conditions as described above, and a vertical combustion test was conducted in accordance with UL94 (8). Flame retardancy (UL94) was evaluated.
These measurements and evaluation results are shown in Table 1, Table 2 and Table 3 below.
Moreover, about the raw material (b2), the characteristic was shown as the reference example 1 in Table 2.

  As shown in Tables 1 to 3, it was found that the resin compositions of Examples 1 to 20 were excellent in heat resistance and workability, and excellent in slidability, chemical resistance and impact resistance. Furthermore, when a flame retardant was added, it turned out that a flame retardance is also excellent.

  The resin composition of the present invention includes a compact disc / read only memory (CD-ROM), a digital versatile disc / read only memory (DVD-ROM), a compact disc / recordable (CD-R), and a digital versatile disc / recordable. -R Standard (DVD-R), Digital Versatile Disc Recordable + R Standard (DVD + R), Compact Disc Rewritable (CD-RW), Digital Versatile Disc Rewritable -R Standard (DVD-RW), Digital Versatile Optical equipment mechanisms such as discs, rewritables, + R standard (DVD + RW), digital versatile discs, random access memory (DVD-RAM) chassis and cabinet, optical pickup slide base, etc. , Parts around light source lamp, sheet or film for metal film laminated substrate, hard disk internal parts, optical fiber connector ferrule, laser beam printer internal parts, inkjet printer internal parts, copier internal parts, automotive radiator tank parts, etc. It has industrial applicability as a material for products and automobile lamp parts.

Claims (3)

(A) Polyphenylene ether resin or mixed resin of polyphenylene ether resin and polystyrene resin: 70 to 96% by mass;
(B) ethylene-tetrafluoroethylene copolymer: 40-2% by mass;
(C) a number average molecular weight of 62,000 or more, a block copolymer of an aromatic vinyl compound and a conjugated diene compound and / or a hydrogenated product of the block copolymer: 2 to 20% by mass,
The, only including,
In the block copolymer (c) of the aromatic vinyl compound and the conjugated diene compound and / or the hydrogenated product of the block copolymer, the binding amount of the aromatic vinyl compound is 30 to 50% by mass, The proportion of the total amount of 1,2-vinyl bonds and 3,4-vinyl bonds to the total amount of bonds in the conjugated diene compound in the block copolymer is 20 to 45%.
Resin composition. The resin composition according to claim 1, wherein the (b) MFR (ASTM-D3159) of the ethylene-tetrafluoroethylene copolymer is 10 to 40 g / 10 min. The resin composition according to claim 1 or 2 , further comprising a condensed phosphate ester flame retardant.