JP2015218203A - Resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composition which is balanced in fire retardancy, molding processability and impact resistance.SOLUTION: A resin composition comprises (a) a polyphenylene ether of a reduced viscosity (measured with chloroform solution of 0.5 g/dL, 30°C) of 0.35-0.45 dL/g, (b) a rubber-modified polystyrene, (c) an impact improver, (d) a phosphoric acid-based fire retardant and (e) polytetrafluoroethylene, in a content of ingredient (a) to the total of (a), (b), (c) and (d) of 100 pts.mass of 60-70 pts.mass, a combined content of ingredients (b) and (c) of 10-20 pts.mass, a mass ratio of (b)/(c) of 5-15, a content of ingredient (d) of 13-20 pts.mass and a content of ingredient (e) to the total of (a), (b), (c) and (d) of 100 pts.mass of 0.02-0.3 pt.mass.

Description

  The present invention relates to a resin composition.

Polyphenylene ether resins are excellent in mechanical properties, electrical properties, acid resistance, alkali resistance, heat resistance, etc., and have properties such as low water absorption and good dimensional stability. Widely used as a housing for equipment, chassis materials, and the like, these materials are required to have high flame resistance from the viewpoint of safety.
Therefore, a technique for blending a phosphoric ester compound such as triphenyl phosphate or cresyl diphenyl phosphate as a flame retardant has been conventionally known for the purpose of improving the flame retardancy of polyphenylene ether resins.

  However, when the phosphoric acid ester compound is added to the polyphenylene ether-based resin, heat resistance may be reduced, and the phosphoric acid ester compound may volatilize or bleed during molding. In order to improve such inconvenience, a resorcinol / bisphenyl phosphate compound, a bisphenol A-polyphenyl phosphate compound or the like, which is a condensed phosphate compound having a large molecular weight, has been used.

On the other hand, in recent years, safety against fire has been strongly demanded, and regulations of US UL (Underwriters Laboratory) vertical combustion test for home appliances, OA equipment and the like have become strict. Specifically, development of a dripping prevention technique is strongly desired in order to prevent fire types from dripping onto other products and parts during combustion and damaging these other products and parts.
As a technique for preventing dripping of a polyphenylene ether resin, a technique of blending polytetrafluoroethylene (PTFE) having a specific molecular weight and a specific crystallinity with a polyphenylene ether resin is disclosed (for example, Patent Document 1). reference.).

Furthermore, in recent years, in order to reduce weight and improve economy, the thickness of products and parts tends to be reduced, and high moldability and impact resistance are required.
By adding the phosphoric acid ester compound to the polyphenylene ether resin, flame retardancy and molding processability can be improved, but there is a case where impact resistance is lowered, and improvement is desired.

Japanese Patent Laid-Open No. 11-209600

However, if the addition amount of the phosphate ester compound is reduced in order to suppress a decrease in impact resistance, sufficient flame retardancy cannot be obtained, and further dripping occurs during combustion.
Therefore, in the prior art, it has been difficult to obtain a good property balance in flame retardancy, molding processability, and impact resistance.

  Therefore, an object of the present invention is to provide a resin composition capable of realizing an excellent property balance in flame retardancy, molding processability, and impact resistance.

As a result of intensive studies to solve the above problems, the present inventors have found that a specific proportion of polyphenylene ether resin, rubber-modified polystyrene, impact modifier, phosphoric flame retardant, and polytetrafluoroethylene having a specific viscosity are specified. In the resin composition contained in the above, the inventors have found that the above-described problems of the prior art can be solved by setting the ratio of the rubber-modified polystyrene and the impact-improving material to a specific range, thereby completing the present invention.
That is, the present invention is as follows.

[1]
(A) polyphenylene ether having a reduced viscosity (0.5 g / dL chloroform solution, measured at 30 ° C.) of 0.35 to 0.45 dL / g;
(B) rubber-modified polystyrene;
(C) an impact modifier;
(D) a phosphoric acid flame retardant;
(E) polytetrafluoroethylene,
Containing,
For a total of 100 parts by mass of the component (a), the component (b), the component (c), and the component (d),
The component (a) is 60 to 70 parts by mass,
The sum of the component (b) and the component (c) is 10 to 20 parts by mass, and the mass ratio of (b) / (c) is 5 to 15,
The component (d) is 13 to 20 parts by mass,
And
For a total of 100 parts by mass of the component (a), the component (b), the component (c), and the component (d),
A resin composition containing 0.02 to 0.3 parts by mass of the component (e).
[2]
At least a part of a block copolymer in which the component (c) includes at least one polymer block mainly composed of an aromatic vinyl compound and at least one polymer block mainly composed of a conjugated diene compound. The resin composition according to [1], wherein is a hydrogenated block copolymer in which is hydrogenated.
[3]
The resin composition according to [1] or [2], wherein the component (d) is a condensed phosphate ester.
[4]
A molded article containing the resin composition according to any one of [1] to [3].

  ADVANTAGE OF THE INVENTION According to this invention, the resin composition excellent in the balance of a flame retardance, a moldability, and impact resistance can be provided.

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

(Resin composition)
The resin composition of the present embodiment is
(A) polyphenylene ether having a reduced viscosity (0.5 g / dL chloroform solution, measured at 30 ° C.) of 0.35 to 0.45 dL / g;
(B) rubber-modified polystyrene;
(C) an impact modifier;
(D) a phosphoric acid flame retardant;
(E) polytetrafluoroethylene,
Containing,
For a total of 100 parts by mass of the component (a), the component (b), the component (c), and the component (d),
The component (a) is 60 to 70 parts by mass,
The sum of the component (b) and the component (c) is 10 to 20 parts by mass, and the mass ratio of (b) / (c) is 5 to 15,
The component (d) is 13 to 20 parts by mass,
And
For a total of 100 parts by mass of the component (a), the component (b), the component (c), and the component (d),
The component (e) is contained in an amount of 0.02 to 0.3 parts by mass.

The resin composition of this embodiment is excellent in the balance of flame retardancy, moldability, and impact resistance.
(A) Component content is 60-70 mass with respect to a total of 100 mass parts of (a) component, (b) component, (c) component, and (d) component from a flame-retardant and fluid viewpoint. Part. Specifically, it is 60 parts by mass or more from the viewpoint of flame retardancy, and 70 parts by mass or less from the viewpoint of fluidity. Moreover, 62-69 mass parts is preferable, and 65-68 mass parts is more preferable.

From the viewpoint of molding processability, the content of the component (b) and the component (c) is 100 parts by mass in total of the component (a), the component (b), the component (c), and the component (d). The sum of the component b) and the component (c) is 10 parts by mass or more, and 20 parts by mass or less from the viewpoint of flame retardancy. Preferably it is 12-19 mass parts, More preferably, it is 13-18 mass parts.
In addition, the mass ratio of (b) / (c) is 5 or more from the viewpoint of fluidity, and 15 or less from the viewpoint of impact resistance. Preferably it is 6-13, More preferably, it is 7-12.
When the total mass of the component (b) and the component (c) and the mass ratio of (b) / (c) satisfy the above range, the balance between flame retardancy, moldability, and impact resistance was excellent. A resin composition is obtained.

  (D) Content of a component is 13-20 mass parts with respect to a total of 100 mass parts of (a) component, (b) component, (c) component, and (d) component. Preferably it is 14-19 mass parts, More preferably, it is 15-18 mass parts. When the component (d) is within the above range, the flame retardancy and impact resistance are excellent.

  The content of the component (e) is 0.02 to 0.3 parts by mass with respect to a total of 100 parts by mass of the components (a), (b), (c), and (d), preferably Is 0.03-0.2 parts by mass, more preferably 0.03-0.1 parts by mass. The component (e) exhibits a certain degree of drip prevention performance even when added in a small amount. When the component (e) is within the above range, the fluidity and flame retardancy (anti-dripping property) are excellent.

((A) component)
The resin composition of this embodiment is a polyphenylene ether (a) having a reduced viscosity (0.5 g / dL chloroform solution, measured at 30 ° C.) of 0.35 to 0.45 dL / g (in this specification, (a) May be described as a component).
(A) The polyphenylene ether (hereinafter sometimes abbreviated as “PPE”) is not particularly limited, and may be a homopolymer of phenylene ether (polyphenylene ether homopolymer), or phenylene ether and other monomers. It may also be a copolymer (polyphenylene ether copolymer).
Among these, a homopolymer and / or a copolymer having a repeating unit structure represented by the following formula (1) is preferable.
The reduced viscosity of component (a) (0.5 g / dL chloroform solution, measured at 30 ° C.) is 0.35 dL / g or more from the viewpoint of fluidity, and 0.45 dL / g from the viewpoint of impact resistance. Or less, preferably 0.37 to 0.44 dL / g, more preferably 0.39 to 0.43 dL / g.

In formula (1), R ¹ , R ² , R ³ , and R ⁴ each independently represent a hydrogen atom, a halogen atom, a primary or secondary alkyl group having 1 to 7 carbon atoms, or a phenyl group. , A haloalkyl group, an aminoalkyl group, a hydrocarbonoxy group, and any one selected from the group consisting of a halohydrocarbonoxy group in which at least two carbon atoms separate a halogen atom and an oxygen atom.

Examples of the component (a) include, but are not limited to, poly (2,6-dimethyl-1,4-phenylene ether) and poly (2-methyl-6-ethyl-1,4-phenylene). Ethers), poly (2-methyl-6-phenyl-1,4-phenylene ether), poly (2,6-dichloro-1,4-phenylene ether) and other homopolymers; 2,6-dimethylphenol and others And polyphenylene ether copolymers with 2,3,6-trimethylphenol and 2-methyl-6-butylphenol.
Of these, poly (2,6-dimethyl-1,4-phenylene ether), 2,6-dimethylphenol and 2,3,6-trimethylphenol are preferred, and poly (2,6-dimethyl) is more preferred. -1,4-phenylene ether).

  (A) The manufacturing method of a component is not specifically limited, A conventionally well-known method is applicable. Although not limited to the following, it can be produced, for example, by the methods described in JP-A-50-150798, JP-A-50-051197, JP-A-63-152628, and the like.

((B) component)
The resin composition of the present embodiment contains (b) rubber-modified polystyrene (may be described as component (b) in the present specification).
(B) The rubber-modified polystyrene is a polymer obtained by polymerizing a styrene compound and a compound copolymerizable with the styrene compound in the presence of a rubbery polymer.
Examples of the styrenic compound include, but are not limited to, styrene, α-methylstyrene, 2,4-dimethylstyrene, monochlorostyrene, p-methylstyrene, p-tert-butylstyrene, and ethylstyrene. Is mentioned. Of these, styrene is preferred.
The compound copolymerizable with the styrenic compound is not limited to the following, for example, methacrylic acid esters such as methyl methacrylate and ethyl methacrylate; unsaturated nitrile compounds such as acrylonitrile and methacrylonitrile. And acid anhydrides such as maleic anhydride.
The amount of the compound copolymerizable with the styrene compound is preferably 20% by mass or less, more preferably 15% by mass or less, based on the total amount with the styrene compound.
Examples of the rubbery polymer include, but are not limited to, conjugated diene rubbers, copolymers of conjugated dienes and aromatic vinyl compounds, and ethylene-propylene copolymer rubbers. Specifically, polybutadiene, a styrene-butadiene random copolymer and a styrene-butadiene block copolymer, and a rubber component obtained by partially or almost completely hydrogenating them can be mentioned.

(Component (c))
The resin composition of the present embodiment contains (c) an impact modifier (may be referred to as (c) component in the present specification).
(C) The impact modifier is a block copolymer having at least one polymer block mainly composed of an aromatic vinyl compound and at least one polymer block mainly composed of a conjugated diene compound and its hydrogen. A thermoplastic elastomer having a hydrogenated random copolymer block obtained by hydrogenating a polymer block mainly composed of an aromatic vinyl compound and / or a random copolymer of an aromatic vinyl compound and a conjugated diene compound. .

(C) The impact modifier is at least a block copolymer containing at least one polymer block mainly composed of an aromatic vinyl compound and at least one polymer block mainly composed of a conjugated diene compound. A hydrogenated block copolymer partially hydrogenated is preferred.
A block copolymer comprising a polymer block mainly composed of at least one aromatic vinyl compound and a polymer block mainly composed of at least one conjugated diene compound, wherein a part of the block copolymer is The aromatic vinyl compound constituting is not limited to the following, and examples thereof include styrene, α-methylstyrene, vinyltoluene and the like.
These aromatic vinyl compounds may be used alone or in combination of two or more. Styrene is preferred from the viewpoint of impact resistance.
The conjugated diene compound constituting a part of the block copolymer is not limited to the following, and examples thereof include butadiene, isoprene, 1,3-pentadiene and the like.
These conjugated diene compounds may be used alone or in combination of two or more. In particular, from the viewpoint of impact resistance, butadiene, isoprene, or a combination thereof is preferable.

  In the present specification, “mainly” means that it contains an amount of at least 50% by mass or more, more preferably 70% by mass or more.

When butadiene is used as the conjugated diene compound of the block copolymer, the microstructure of the polybutadiene block portion is the sum of 1,2-vinyl bond amount and 3,4-vinyl bond amount from the viewpoint of impact resistance. The amount is preferably 5 to 80%, more preferably 10 to 50%, and still more preferably 15 to 45%.
Usually, there are 1,2-vinyl bond, 3,4-vinyl bond, and 1,4-vinyl bond as the bond form of the conjugated diene compound. The ratio of the bonding form is shown. For example, the amount of 1,2-vinyl bond means the ratio of 1,2-vinyl bond in the above three bond forms.
The total amount of 1,2-vinyl bonds and 3,4-vinyl bonds in the block copolymer can be measured with an infrared spectrophotometer, a nuclear magnetic resonance apparatus, or the like.

  The block copolymer containing at least one polymer block mainly containing an aromatic vinyl compound and at least one polymer block mainly containing a conjugated diene compound is a polymer block mainly containing an aromatic vinyl compound. (S) and the polymer block (B) mainly composed of a conjugated diene compound have a bond type selected from SB type, SBS type, and SBS type. It is preferable that it is a block copolymer. Among these, from the viewpoint of impact resistance, the SBS type and the SBS type are more preferable, and the SBS type is more preferable. These may be used alone or in a mixture of two or more.

The hydrogenated product of the block copolymer is a hydrogenated product of the above-described block copolymer of an aromatic vinyl compound and a conjugated diene compound.
The hydrogenated product of the block copolymer is obtained by hydrogenating an aliphatic double bond in the block copolymer of the above-mentioned aromatic vinyl compound and conjugated diene compound, and exceeds 0 to 100%. The hydrogenation treatment ratio for the double bond within the range is controlled.
A preferable hydrogenation rate of the hydrogenated product of the block copolymer is 50% or more from the viewpoint of thermal stability, more preferably 80% or more, and further preferably 95% or more.
The hydrogenation rate can be measured with a nuclear magnetic resonance apparatus (NMR).

The block copolymer of the aromatic vinyl compound and the conjugated diene compound and the hydrogenated product of the block copolymer preferably have a number average molecular weight of 100,000 or more from the viewpoint of impact resistance. More preferably, it is 150,000 or more, More preferably, it is 170,000 or more. The number average molecular weight of the block copolymer and the hydrogenated product of the block copolymer is preferably 400,000 or less from the viewpoint of fluidity.
The number average molecular weight refers to the number average molecular weight measured with an ultraviolet spectroscopic detector using a gel permeation chromatography measuring device and converted to standard polystyrene.

A specific method for measuring the number average molecular weight is shown below.
Using a gel permeation chromatography measuring device [GPC SYSTEM21: manufactured by Showa Denko KK], an ultraviolet spectroscopic detector [UV-41: manufactured by Showa Denko KK] is used, and the block is converted into standard polystyrene. The number average molecular weight of the polymer is determined.
[Measurement conditions Solvent: Chloroform, Temperature: 40 ° C., Column: Sample side (KG, K-800RL, K-800R), Reference side (K-805L × 2), Flow rate 10 ml / min, Measurement wavelength: 254 nm , Pressure 15-17 kg / cm ² )]
At this time, a low molecular weight component resulting from catalyst deactivation during polymerization may be detected. In this case, the low molecular weight component is not included in the molecular weight calculation.
Usually, the calculated correct molecular weight distribution (weight average molecular weight / number average molecular weight) is in the range of 1.0 to 1.1.

The number average molecular weight of one polymer block mainly composed of the aromatic vinyl compound constituting the block copolymer is preferably 15,000 or more. More preferably, it is 30,000 or more.
By setting the number average molecular weight of one polymer block mainly composed of an aromatic vinyl compound to 15,000 or more, variation in impact resistance of the resin composition can be suppressed.
When there are a plurality of polymer blocks mainly composed of the aromatic vinyl compound in the molecule of the block copolymer, all the number average molecular weights of the plurality of polymer blocks are not less than the above values. Is more preferable.
In addition, the number average molecular weight of one polymer block mainly composed of an aromatic vinyl compound can be obtained by the following equation using the number average molecular weight of the block copolymer described above.
Mn (a) = {Mn × a / (a + b)} / N
(In the above formula, Mn (a) is the number average molecular weight of one polymer block mainly composed of an aromatic vinyl compound, and Mn is at least 1 polymer block composed mainly of at least one aromatic vinyl compound. The number average molecular weight of a block copolymer composed of a polymer block mainly composed of one conjugated diene compound, and a is the content of the polymer block mainly composed of all aromatic vinyl compounds in the block copolymer (mass %), B is the content (% by mass) of the polymer block mainly composed of all conjugated diene compounds in the block copolymer, and N is a polymer mainly composed of the aromatic vinyl compound in the block copolymer. Represents the number of blocks.)
Here, as described above, Mn can be obtained by a gel permeation chromatography measuring apparatus.
The measurement of a (content of polymer block mainly composed of vinyl aromatic compound) can be performed by NMR, and b (content of polymer block mainly composed of conjugated diene compound) is 100-a. (%).
From these values, Mn (a) can be obtained by the above formula.

  The block copolymers described above may have different bond types, different aromatic vinyl compound types, different conjugated diene compound types, 1,2-vinyl bond amounts, or 1 unless the object of the present invention is contrary. 2 or more types are mixed for each of those having different total amount of 2-vinyl bond and 3,4-vinyl bond, different aromatic vinyl compound components, different hydrogenation rates, etc. May be used.

(Component (d))
The resin composition of the present embodiment contains (d) a phosphoric acid flame retardant (may be referred to as component (d) in this specification).
As the (d) phosphoric acid flame retardant, any phosphorus-containing flame retardant known in the art such as an organic phosphoric acid compound and an inorganic phosphate can be used. Among these, phosphate ester compounds are preferably used.
Examples of the phosphoric acid ester compound include, but are not limited to, trimethyl phosphate, triethyl phosphate, tripropyl phosphate, tributyl phosphate, tripentyl phosphate, trihexyl phosphate, tricyclohexyl phosphate, triphenyl phosphate, triphenyl phosphate, and triphenyl phosphate. Examples include cresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, dicresyl phenyl phosphate, dimethyl ethyl phosphate, methyl dibutyl phosphate, ethyl dipropyl phosphate, hydroxyphenyl diphenyl phosphate, etc. Examples thereof include phosphate ester compounds and condensed phosphate ester flame retardants obtained by condensing them. Among these, a condensed phosphate ester flame retardant is preferable.

Among the condensed phosphate ester flame retardants, those containing as a main component at least one selected from the group consisting of condensed phosphate esters represented by the following formula (2) and the following formula (3) are preferable.
The “main component” as used herein means that the component is contained in 90% by mass or more in the component (d), preferably 95% by mass or more, and more preferably 100% by mass.

In formulas (2) and (3), Q ¹ , Q ² , Q ³ , and Q ⁴ each independently represent an alkyl group having 1 to 6 carbon atoms, and R ⁵ and R ⁶ represent a methyl group. R ⁷ and R ⁸ each independently represents a hydrogen atom or a methyl group.
n is an integer of 0 or more, n ¹ and n ² are each independently an integer of 0 to 2, and m ¹ , m ² , m ³ and m ⁴ are each independently 0 It is an integer of ~ 3.
In addition, n of Formula (2) and (3) is an integer greater than or equal to 0, Preferably it is an integer of 1-3.

Among them, R ⁷ and R ⁸ in Formula (2) represent a methyl group, and m ¹ , m ² , m ³ , m ⁴ , n ¹ , and n ² are 0, a condensed phosphate ester; Q ¹ , Q ² , Q ³ , Q ⁴ , R ⁷ and R ⁸ in (2) represent a methyl group, n ¹ and n ² are 0, m ¹ , m ² , m ³ and m ⁴ is an integer of 1 to 3, which is a condensed phosphate ester, and the range of n is an integer of 1 to 3, in particular, the phosphoric acid ester in which n is 1 contains 50% by mass or more in total. preferable. By using these condensed phosphate esters, the volatility during the molding process of the resin composition can be further reduced.

((E) component)
The resin composition of this embodiment contains (e) polytetrafluoroethylene.
(E) Polytetrafluoroethylene (PTFE) may be a tetrafluoroethylene homopolymer or a copolymer of tetrafluoroethylene and difluoroethylene, trifluoroethylene, hexafluoropropylene or the like. As a method for producing these PTFEs, for example, tetrafluoroethylene is used in an aqueous medium using a radical initiator such as ammonium persulfate and potassium persulfate at a temperature of 0 to 200 ° C. under a pressure of 7 to 70 kg / cm ^2. A method of polymerizing and then obtaining a polytetrafluoroethylene powder from a suspension, dispersion or emulsion by coagulation or by precipitation is mentioned.
As another production method, for example, a method of producing by an emulsion polymerization method by radical polymerization using a tetrafluoroethylene monomer as a raw material or a suspension polymerization method is used.
As (e) polytetrafluoroethylene, 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 the method described above takes the form of a powder or a dispersion.
Any of the production methods described above may be used, but those that are particularly highly crystalline and easily fibrillated are preferred.

(Additive)
In order to impart other characteristics to the resin composition of the present embodiment, other additives may be added as long as the effects of the present invention are not impaired.
Examples of additives include, but are not limited to, stabilizers such as plasticizers, antioxidants, and ultraviolet absorbers, antistatic agents, mold release agents, dyes and pigments, and other resins. .
Further, as various conventionally known flame retardants and flame retardant aids, for example, magnesium hydroxide or aluminum hydroxide containing crystal water may be used; zinc borate compound, zinc stannate compound, silica, kaolin It is possible to further improve flame retardancy by adding inorganic silicon compounds such as clay and talc.

[Method for producing resin composition]
The resin composition of the present embodiment comprises (a) polyphenylene ether having a reduced viscosity (0.5 g / dL chloroform solution, measured at 30 ° C.) of 0.35 to 0.45 dL / g, and (b) rubber modification. It can be produced by mixing polystyrene, (c) an impact modifier, (d) a phosphoric acid flame retardant, and (e) polytetrafluoroethylene.
The mixing method of said (a)-(e) is not specifically limited, For example, the method of melt-kneading each above-mentioned component using a twin-screw extruder is mentioned.
Such a twin screw extruder is not particularly limited, and examples thereof include a ZSK series manufactured by Coperion, a TEM series manufactured by Toshiba Machine Co., Ltd., and a TEX series manufactured by Nippon Steel Works.

The melt-kneading temperature, screw rotation speed, etc. in the method for producing a resin composition of the present embodiment are not particularly limited, and usually suitable conditions are suitably selected from the range of melt-kneading temperature 200-370 ° C. and screw rotation speed 100-1200 rpm. You can choose.
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.

〔Molding〕
The resin composition of this embodiment can be formed into a molded product by molding it.
Although it does not limit as a shaping | molding method below, For example, well-known shaping | molding methods, such as injection molding, hollow shaping | molding, extrusion molding, sheet shaping | molding, film shaping | molding, can 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 electrical component applications, battery applications, various exterior materials, and the like. That is, the molded product of this embodiment is a molded product including the above-described resin composition.
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. Specific examples of such an injection molding machine are not particularly limited, and examples thereof include “IS100GN” manufactured by TOSHIBA.
The melting temperature, mold temperature, etc. in the molding method of the resin composition of the present embodiment can be appropriately selected from the range of a melting temperature of 200 to 320 ° C. and a mold temperature of 30 to 100 ° C. It is not limited to these.

  Hereinafter, the present invention will be described in detail with specific examples and comparative examples, but the present invention is not limited to the following examples.

In addition, the measuring method and raw material which were used for the Example and the comparative example are shown below.
〔Measuring method〕
<Flame retardance>
Based on the UL-94 vertical combustion test, flame retardancy was evaluated using an injection molded specimen having a thickness of 0.75 mm. First, the resin compositions obtained in the examples and comparative examples were supplied to a screw in-line type injection molding machine (“TOSHIBA”, “IS100GN”) set at 270 to 230 ° C., and injection was performed at a mold temperature of 60 ° C. By molding, a test piece having a size specified in the standard was manufactured.
A gas burner flame was applied to the test piece, and the degree of combustion was evaluated.
As the flame retardancy grade based on UL94, evaluation was performed based on the criteria of V-0, V-1, V-2, and HB in order from the highest flame retardance.

<Melt flow rate (MFR)>
About the pellet of the resin composition obtained by the Example and the comparative example, melt flow rate (MFR) was measured on condition of 250 degreeC and a load of 10 kg based on ISO1133.

<Charpy impact strength>
The resin compositions obtained in Examples and Comparative Examples are supplied to a screw in-line injection molding machine (TOSHIBA, “IS100GN”) set at 270 to 230 ° C. and injection molded under conditions of a mold temperature of 60 ° C. Thus, a test piece having a size defined by the ISO-179 standard was manufactured.
Using the test piece, Charpy impact strength was measured with a notch in accordance with ISO-179 as an impact resistance test.

〔raw materials〕
(A) Polyphenylene ether resin (a-1) Reduced viscosity (0.5 g / dL chloroform solution, measured at 30 ° C.) 0.5 dL / g poly (2,6-dimethyl-1,4-phenylene ether)
(A-2) Reduced viscosity (0.5 g / dL chloroform solution, measured at 30 ° C.) 0.4 dL / g poly (2,6-dimethyl-1,4-phenylene ether)
(B) Rubber-modified polystyrene “CT60” manufactured by Petrochemical Co., Ltd.
(C) Impact modifier (c-1)
Polystyrene block-hydrogenated polybutadiene-polystyrene block TSRC (Nanton) Industries. "TAIPOL 6151" made by Ltd.
(C-2)
Polymer block mainly composed of SOE and styrene-hydrogenated random copolymer block obtained by hydrogenation of random copolymer of styrene and butadiene, manufactured by Asahi Kasei Chemicals, "SOE L605"
(D) Phosphoric acid flame retardant “E890” manufactured by Daihachi Chemical Industry Co., Ltd.
(E) Polytetrafluoroethylene “Maybrene A3800” manufactured by Mitsubishi Rayon Co., Ltd.

[Example 1]
A twin screw extruder “ZSK40MC” (manufactured by Coperion) was used as a resin composition production apparatus. In the twin-screw extruder, a first raw material supply port was provided upstream of the raw material flow direction. A liquid pump was provided downstream of the first raw material supply port. A second raw material supply port was provided downstream of the liquid pump. A vacuum vent was provided downstream of the second raw material supply port. Moreover, the raw material supply method to a 2nd supply port was set as the method of supplying using a forced side feeder from an extruder side open port.
The components (a) to (e) are supplied to the twin-screw extruder set as described above in the composition shown in Table 1, and the maximum temperature of the heating cylinder is 300 ° C., the screw rotation speed is 150 rpm, and the discharge amount is 150 kg / hour. The mixture was melt-kneaded under conditions to obtain resin composition pellets.

[Example 2]
The components (a) to (e) were supplied to the twin screw extruder with the compositions shown in Table 1. Other conditions were the same as in Example 1 to obtain pellets of the resin composition.

[Comparative Examples 1-5]
The components (a) to (e) were supplied to the twin screw extruder with the compositions shown in Table 1. Other conditions were the same as in Example 1 to obtain pellets of the resin composition.

The properties of pellets of the resin compositions obtained in Examples and Comparative Examples were evaluated according to the above methods.
The evaluation results of the component compositions and physical properties of each example and each comparative example are shown in Table 1 below.

  Examples 1 to 5 are all excellent in moldability, flame retardancy, and impact resistance, and the resin composition according to this embodiment has a balance of moldability, flame retardancy, and impact resistance. It was shown to be excellent.

  The resin composition of the present invention has industrial applicability as a material for electric parts, batteries, various exterior materials and the like.

Claims (4)

(A) polyphenylene ether having a reduced viscosity (0.5 g / dL chloroform solution, measured at 30 ° C.) of 0.35 to 0.45 dL / g;
(B) rubber-modified polystyrene;
(C) an impact modifier;
(D) a phosphoric acid flame retardant;
(E) polytetrafluoroethylene,
Containing,
For a total of 100 parts by mass of the component (a), the component (b), the component (c), and the component (d),
The component (a) is 60 to 70 parts by mass,
The sum of the component (b) and the component (c) is 10 to 20 parts by mass, and the mass ratio of (b) / (c) is 5 to 15,
The component (d) is 13 to 20 parts by mass,
And
For a total of 100 parts by mass of the component (a), the component (b), the component (c), and the component (d),
A resin composition containing 0.02 to 0.3 parts by mass of the component (e).   At least a part of a block copolymer in which the component (c) includes at least one polymer block mainly composed of an aromatic vinyl compound and at least one polymer block mainly composed of a conjugated diene compound. The resin composition according to claim 1, which is a hydrogenated block copolymer that is hydrogenated.   The resin composition according to claim 1 or 2, wherein the component (d) is a condensed phosphate ester.   The molded article containing the resin composition as described in any one of Claims 1 thru | or 3.