JP2020037663A - Flame-retardant resin composition - Google Patents

Abstract

To provide a resin composition excellent in balance of high flame retardancy, impact resistance, and heat resistance.SOLUTION: The present invention provides the resin composition which contains (a) 55-75 mass% of a polyphenylene ether resin, (b) 3-15 mass% of a hydrogenated block copolymer obtained by hydrogenating a block copolymer containing two or more polymer blocks A mainly composed of a vinyl aromatic compound and one or more polymer blocks B mainly composed of a conjugated diene compound, (c) 15-25 mass% of a condensed phosphate-based flame retardant, and (d) 5-20 mass% of glass fibers and contains (e) less than 5 mass% of a polystyrene resin as an optional component.SELECTED DRAWING: None

Description

  The present invention relates to a resin composition having excellent flame retardancy, heat resistance, and impact resistance.

  Polyphenylene ether-based resin is widely used as a molding material with excellent heat resistance, dimensional stability, flame retardancy, and electrical insulation in electronic and electrical parts, OA equipment parts, audio-visual equipment parts, and automobile parts. I have.

2. Description of the Related Art In recent years, there has been a strong demand for improved flame retardancy in a protective case for a battery system of a hybrid or electric vehicle. However, it is difficult to use halogen-based flame retardants with high flame-retardant improvement effects due to environmental problems. Also, increasing the amount of flame retardants improves flame retardancy, but there is a problem that heat resistance and impact resistance decrease. Is becoming In order to prevent the impact resistance from lowering, an elastomer is added, but this method also improves the impact resistance but decreases the flame retardancy and heat resistance.
For this reason, many improvements have been proposed.

  As these techniques, a resin composition in which a polyphenylene ether resin, rubber-modified polystyrene, an organic phosphate, and glass fiber are blended (for example, see Patent Document 1) has been proposed.

JP 2006-520702 A

  Patent Literature 1 discloses a resin composition having excellent impact resistance by blending a specific rubber-modified polystyrene. However, although the impact resistance of the resin composition obtained by this technique is improved, it does not satisfy the current requirements in terms of flame retardancy and heat resistance. There is a need for a protective housing for an automotive battery system.

  An object of the present invention is to provide a resin composition having an excellent balance between high flame retardancy, impact resistance, and heat resistance.

  As a result of intensive studies to solve the above-described problems, a specific block copolymer and a condensed phosphate ester-based flame retardant are added at a specific ratio to the polyphenylene ether-based resin, and the content of the polystyrene-based resin is less than a certain value. The present inventors have found that the resin composition has an excellent balance of high flame retardancy, impact resistance, and heat resistance, and have reached the present invention.

That is, the present invention is as follows.
[1]
(A) 55 to 75% by mass of a polyphenylene ether-based resin;
(B) hydrogenation obtained by hydrogenating a block copolymer containing two or more polymer blocks A mainly composed of a vinyl aromatic compound and one or more polymer blocks B mainly composed of a conjugated diene compound; 3 to 15% by mass of the block copolymer,
(C) 15 to 25% by mass of a condensed phosphate ester flame retardant;
(D) 5 to 20% by mass of glass fiber,
A resin composition comprising (e) less than 5% by mass of a polystyrene resin as an optional component.
[2]
The resin composition according to [1], wherein the content of the (e) polystyrene resin is 3% by mass or less.
[3]
The resin composition according to [1] or [2], wherein the (b) hydrogenated block copolymer has a number average molecular weight of 120,000 to 300,000.
[4]
The resin composition according to any one of [1] to [3], wherein the (c) condensed phosphate ester flame retardant is bisphenol A-bis (diphenyl phosphate).
[5]
The resin composition according to any one of [1] to [4], wherein in the UL94V test, the flame retardancy when tested on a 1.6 mm thick test piece is class V-0.
[6]
A protective case for a battery system of a hybrid vehicle or an electric vehicle, comprising the resin composition according to any one of [1] to [5].

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

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

(Resin composition)
The resin composition of the present embodiment comprises (a) a polyphenylene ether-based resin, (b) two or more polymer blocks A mainly composed of a vinyl aromatic compound and one or more polymers mainly composed of a conjugated diene compound. Hydrogenated block copolymer obtained by hydrogenating a block copolymer containing block B, (c) a condensed phosphate ester flame retardant, (d) glass fiber, and (e) a polystyrene resin as an optional component And
In the resin composition of the present embodiment, the content of the component (a) is 55 to 75% by mass, the content of the component (b) is 3 to 15% by mass, and the component (c) is 100% by mass of the resin composition. The content of the component is 15 to 25% by mass, the content of the component (d) is 5 to 20% by mass, and the content of the component (e) is less than 5% by mass. With the above configuration, the resin composition of the present embodiment can exhibit a more excellent balance of physical properties in flame retardancy, impact resistance, and heat resistance.

  Hereinafter, the components of the resin composition of the present embodiment will be described.

((A) polyphenylene ether resin)
The resin composition of the present embodiment contains a polyphenylene ether-based resin (hereinafter sometimes simply referred to as “PPE-based resin”) as the component (a). Since it contains a polyphenylene ether-based resin, the resin composition of the present embodiment has excellent heat resistance.

The PPE-based resin is not particularly limited, and includes, for example, polyphenylene ether (hereinafter sometimes simply referred to as “PPE”), modified polyphenylene ether, and a mixture of both. As the component (a), one type may be used alone, or two or more types may be used in combination.
Since the PPE-based resin contains PPE, the resin composition of the present embodiment is more excellent in heat resistance.

上記式（１）中、Ｒ¹、Ｒ²、Ｒ³、及びＲ⁴は、各々独立して、水素原子、ハロゲン原子、炭素数１〜７の第１級アルキル基、炭素数１〜７の第２級アルキル基、フェニル基、ハロアルキル基、アミノアルキル基、炭化水素オキシ基、及び少なくとも２個の炭素原子がハロゲン原子と酸素原子とを隔てているハロ炭化水素オキシ基からなる群から選択される一価の基である。 Examples of the PPE include a homopolymer having a repeating unit structure represented by the following formula (1) and a copolymer having a repeating unit structure represented by the following formula (1).
The PPE may be used alone or in combination of two or more.

In the above formula (1), R ¹ , R ² , R ³ , and R ⁴ are each independently a hydrogen atom, a halogen atom, a primary alkyl group having 1 to 7 carbon atoms, and a primary 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 a halogen atom from an oxygen atom. Is a monovalent group.

  From the viewpoint of fluidity, toughness and chemical resistance during processing, the reduced viscosity of a PPE measured with a Ubbelohde type viscosity tube at 30 ° C. using a chloroform solution having a concentration of 0.5 g / dL is as follows: It is preferably 0.15 to 2.0 dL / g, more preferably 0.20 to 1.0 dL / g, and still more preferably 0.30 to 0.70 dL / 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). And homopolymers such as poly (2-methyl-6-phenyl-1,4-phenylene ether) and poly (2,6-dichloro-1,4-phenylene ether); 2,6-dimethylphenol and other phenols (For example, copolymers with 2,3,6-trimethylphenol and 2-methyl-6-butylphenol). Among them, poly (2,6-dimethyl-1,4-phenylene ether) and 2,6-dimethylphenol are used from the viewpoint of the balance between toughness and rigidity when a resin composition is formed and the availability of raw materials. A copolymer with 2,3,6-trimethylphenol is preferred, and poly (2,6-dimethyl-1,4-phenylene ether) is more preferred.

  The PPE can be manufactured by a known method. The method for producing PPE is not limited to the following. For example, using a complex of a cuprous salt and an amine according to Hay described in U.S. Pat. No. 3,308,874 as a catalyst, 2,6-xylenol is used. Oxidative polymerization method, U.S. Pat. No. 3,308,875, U.S. Pat. No. 3,257,357, U.S. Pat. No. 3,257,358, JP-B-52-17880, JP-A-50-51197, JP-A-63 And a method described in JP-A-152628.

  The PPE resin is modified by reacting the homopolymer and / or the copolymer with a styrene monomer or a derivative thereof and / or an α, β-unsaturated carboxylic acid or a derivative thereof. It may be PPE. Here, the graft amount or the addition amount of the styrene monomer or its derivative and / or the α, β-unsaturated carboxylic acid or its derivative is 0.01 to 10% by mass relative to 100% by mass of the component (a). %.

Examples of the method for producing the modified PPE include a method in which a reaction is performed at a temperature of 80 to 350 ° C. in a molten state, a solution state, or a slurry state in the presence or absence of a radical generator.
As the PPE-based resin, a mixture of the above-mentioned homopolymer and / or the above-mentioned copolymer and the above-mentioned modified PPE at an arbitrary ratio may be used.

  The content of the component (a) in the resin composition of the present embodiment is 55 to 75% by mass when the resin composition is 100% by mass from the viewpoint of flame retardancy and heat resistance. %, More preferably from 57 to 67% by mass. When the content of the component (a) is in the range of 55 to 75% by mass, the balance between flame retardancy and heat resistance can be sufficiently improved.

((B) hydrogenated block copolymer)
The resin composition of this embodiment has excellent impact resistance by containing (b) a hydrogenated block copolymer.
(B) The hydrogenated block copolymer imparts impact resistance to the resin composition of the present embodiment, and comprises two or more polymer blocks A mainly composed of a vinyl aromatic compound and a conjugated diene compound. A hydrogenated block copolymer obtained by hydrogenating a block copolymer containing one or more polymer blocks B as a main component.

  The component (b) may contain a block copolymer other than the above-mentioned hydrogenated block copolymer as long as the effects of the present invention are not impaired.

The polymer block A mainly composed of a vinyl aromatic compound refers to a homopolymer block of the vinyl aromatic compound or a content of the vinyl aromatic compound in the polymer block A of more than 50% by mass, preferably 70% by mass. % Of a copolymer block of a vinyl aromatic compound and a conjugated diene compound. The polymer block A may not substantially contain a conjugated diene compound or may not contain a conjugated diene compound. In addition, "substantially does not include" includes a case where the effects of the present invention are included within a range that does not impair the effects of the present invention, and may be, for example, 3% by mass or less based on the total amount of the blocks.
The polymer block B mainly composed of a conjugated diene compound is defined as a homopolymer block of the conjugated diene compound or a content of the conjugated diene compound in the polymer block B of more than 50% by mass, preferably 70% by mass. The above refers to a copolymer block of a conjugated diene compound and a vinyl aromatic compound. The polymer block B may not substantially contain a vinyl aromatic compound or may not contain a vinyl aromatic compound. In addition, "substantially does not include" includes a case where the effects of the present invention are included within a range that does not impair the effects of the present invention, and may be, for example, 3% by mass or less based on the total amount of the blocks.

  (B) The hydrogenated block copolymer is preferably a combination of two types of hydrogenated block copolymers, and may be a combination of conventionally known and sold hydrogenated block copolymers. )) Any component can be used as long as it belongs to the component.

  (B) As the vinyl aromatic compound constituting the hydrogenated block copolymer, for example, one or more of styrene, α-methylstyrene, vinyltoluene, p-tert-butylstyrene, diphenylethylene and the like are used. And styrene is particularly preferred.

(B) As the conjugated diene compound constituting the hydrogenated block copolymer, for example, one or two of butadiene, isoprene, 1,3-pentadiene, 2,3-dimethyl-1,3-butadiene and the like are used. The above are selected, and butadiene, isoprene and a combination thereof are particularly preferred.
The binding form of butadiene before hydrogenation can usually be known by an infrared spectrophotometer, NMR, or the like.

  (B) The hydrogenated block copolymer is a hydrogenated block copolymer containing two or more blocks A and one or more blocks B, and is preferably an ABA type (two A, B may have the same or different molecular weights.) Is a hydrogenated product of a vinyl aromatic compound-conjugated diene compound block copolymer having a structure in which the block units are bonded.

  The individual structures of the polymer block A mainly composed of a vinyl aromatic compound and the polymer block B mainly composed of a conjugated diene compound are determined by the distribution of the vinyl aromatic compound or the conjugated diene compound in the molecular chain of each polymer block. May be random or tapered (a monomer component increases or decreases along a molecular chain). (B) When the hydrogenated block copolymer contains two or more of the polymer blocks A or B, the polymer blocks may have the same structure or different structures. There may be.

  (B) At least one polymer block B contained in the hydrogenated block copolymer is a polymer block in which the 1,2-vinyl bond content of the conjugated diene compound before hydrogenation is 70 to 90%. You may. Further, (b) at least one polymer block B contained in the hydrogenated block copolymer is a polymer block in which the 1,2-vinyl bond amount of the conjugated diene compound before hydrogenation is 70 to 90%. Even if it is a polymer block having both (polymer block B1) and a polymer block (polymer block B2) in which the 1,2-vinyl bond amount of the conjugated diene compound before hydrogenation is less than 30 to 70%. Good. A block copolymer having such a block structure is, for example, a known copolymer represented by AB2-B1-A in which the amount of 1,2-vinyl bond is controlled based on the adjusted feed sequence of each monomer unit. It can be obtained by a polymerization method.

  (B) The content of the vinyl aromatic compound bonded in the hydrogenated block copolymer is preferably 15 to 80% by mass, more preferably 25 to 80% by mass, and still more preferably 30 to 75% by mass. is there.

(B) The hydrogenated block copolymer is subjected to a hydrogenation reaction to hydrogenate an aliphatic double bond such as in a polymer block B mainly composed of a conjugated diene compound, thereby obtaining a hydrogenated copolymer block ( (A hydrogenated product of a vinyl aromatic compound-conjugated diene compound block copolymer). The hydrogenation rate of such an aliphatic double bond is preferably at least 80%, more preferably at least 95%.
And this hydrogenation rate can usually be known by an infrared spectrophotometer, NMR or the like.

(B) The number average molecular weight (Mnc) of the hydrogenated block copolymer is preferably from 120,000 to 300,000, more preferably from 120,000 to 250,000, and from 150,000 to 250. More preferably, it is 2,000. The number average molecular weight is preferably 120,000 or more from the viewpoint of impact resistance, and is preferably 300,000 or less from the viewpoint of dispersibility in the component (a) and fluidity.
(B) The number average molecular weight (Mnc) of the hydrogenated block copolymer was measured by using Gel Permeation Chromatography System 21 (column: Showa Denko K-G1). , One K-800RL and one K-800R in series in this order, column temperature: 40 ° C, solvent: chloroform, solvent flow rate: 10 mL / min, sample concentration: 1 g of hydrogenated block copolymer / L chloroform solution) to prepare a calibration curve using standard polystyrene (the molecular weight of the standard polystyrene is 3650000, 21700, 1090000, 681000, 204000, 52000, 30200, 13800, 3360, 1300, 550), and The wavelength of (UV) is the same for standard polystyrene and hydrogenated block copolymer components. At 254 nm.

(B) Among the polymer blocks A contained in the hydrogenated block copolymer, the number average molecular weight (MncA) of at least one block A is preferably 10,000 or more, and is 15,000 or more. It is more preferable, and from the viewpoint of further improving the impact resistance, it is more preferable that it is more than 15,000. Further, from the viewpoint of further improving the impact resistance, it is preferable that the number average molecular weight (MncA) of all the polymer blocks A contained in the (b) hydrogenated block copolymer is 10,000 or more. When a polymer block A having a number average molecular weight (MncA) of 10,000 or more is contained, a block copolymer satisfying this condition has a weight average molecular weight (Mwppe) of 15,000 to 25,000 and a molecular weight distribution (Mwppe / Mnppe). ) Is preferable because it can be mixed well with the PPE in the component (a) of 1.5 to 3.0, and the resulting resin composition has excellent heat resistance and mechanical properties.
In addition, (b) the number average molecular weight (MncA) of the polymer block A mainly composed of a vinyl aromatic compound contained in the hydrogenated block copolymer is, for example, as described above in the case of an ABA type structure. Based on the number average molecular weight (Mnc) of the hydrogenated block copolymer, the molecular weight distribution of the hydrogenated block copolymer is 1, and two polymer blocks A mainly composed of a vinyl aromatic compound are present as the same molecular weight. Assuming that (MncA) = (Mnc) × the ratio of the amount of the bound vinyl aromatic compound ÷ 2, it can be determined. Similarly, in the case of an ABAB type block copolymer component, it can be determined by a calculation formula of (MncA) = (Mnc) × the ratio of the amount of the bound vinyl aromatic compound ÷ 3. When the sequence of the block structure A and the block structure B is clear at the stage of synthesizing the vinyl aromatic compound-conjugated diene compound block copolymer, the measurement is performed without depending on the above formula. The ratio may be calculated from the ratio of the block structure A based on the number average molecular weight (Mnc) of the block copolymer.

(B) It is preferable that the hydrogenated block copolymer contains a polymer block B having a number average molecular weight (MncB) of 15,000 or more, and from the viewpoint of more excellent impact resistance, the number average molecular weight is 40,000. It is more preferable to include the polymer block B described above.
The number average molecular weight (MncB) of (b) the polymer block B mainly composed of a conjugated diene compound contained in the hydrogenated block copolymer can be calculated by the same method as described above.

  Among them, (b) the hydrogenated block copolymer has a polymer block A having a number average molecular weight (Mnc) of 120,000 to 300,000 and a number average molecular weight (MncA) of 10,000 or more. It is preferred to include.

  (B) The hydrogenated block copolymer may be obtained by any production method as long as it has the above structure. Examples of the production method include, for example, JP-A-47-11486, JP-A-49-66743, JP-A-50-75651, JP-A-54-126255, and JP-A-56-126255. 10542, JP-A-56-62847, JP-A-56-100840, JP-A-2004-269665, British Patent No. 1130770, U.S. Pat. No. 3,281,383, U.S. Pat. And US Patent No. 3,330,024, US Patent No. 4,501,857, and the like.

  The hydrogenated block copolymer of the component (b) is obtained by combining the above hydrogenated block copolymer with an α, β-unsaturated carboxylic acid or a derivative thereof (an ester compound or an acid anhydride compound such as maleic anhydride). A modification (for example, α, β-unsaturated carboxylic acid) obtained by reacting in the presence or absence of a radical generator in a molten state, a solution state, or a slurry state at a temperature of 80 to 350 ° C. Alternatively, the grafted amount or the added amount of the derivative thereof is 0.01 to 10% by mass with respect to 100% by mass of the component (b). It may be a mixture of the polymer and the modified block copolymer in any ratio.

  The content of the component (b) in the resin composition of the present embodiment is 3 to 15% by mass when the resin composition is 100% by mass from the viewpoints of flame retardancy, heat resistance, and impact resistance. And preferably 3 to 10% by mass, more preferably 5 to 10% by mass. When the content of the component (b) is in the range of 3 to 15% by mass, the balance between flame retardancy, heat resistance, and impact resistance can be sufficiently improved.

((C) condensed phosphate ester flame retardant)
The resin composition of the present embodiment contains a condensed phosphate ester flame retardant as the component (c). In the resin composition of the present embodiment, the effect of improving the flame retardancy of the phenylene ether-based resin of the component (a) and the effect of imparting the flame retardancy of the condensed phosphate ester-based flame retardant of the component (c) are combined. Flammability is significantly improved.

［式中、Ｒ¹¹、Ｒ¹²、Ｒ¹³、及びＲ¹⁴は、それぞれ独立して、水素原子、ハロゲン原子、アルキル基、シクロアルキル基、アリール置換アルキル基、アリール基、ハロゲン置換アリール基、及びアルキル置換アリール基からなる群から選択される一価の基である。Ｘはアリーレン基を表す。ｎは０〜５の整数である。］
なお、縮合リン酸エステル系難燃剤が、上記ｎが異なるリン酸エステル及び／又はその縮合物の混合物である場合、ｎはそれらの平均値を表す。ｎ＝０である場合は、一般式（２）の化合物は、リン酸エステル単量体を示す。 The condensed phosphate ester flame retardant is not particularly limited, but an aromatic condensed phosphate ester flame retardant is preferred.
Examples of the condensed phosphoric ester-based flame retardant include, but are not limited to, phosphoric esters represented by the following general formula (2) and / or condensates thereof.

[Wherein, R ¹¹ , R ¹² , R ¹³ , and R ¹⁴ each independently represent 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, It is a monovalent group selected from the group consisting of alkyl-substituted aryl groups. X represents an arylene group. n is an integer of 0-5. ]
When the condensed phosphate ester-based flame retardant is a mixture of different phosphoric esters and / or condensates thereof, n represents an average value thereof. When n = 0, the compound of the general formula (2) indicates a phosphate ester monomer.

  Representative phosphate ester monomers are not limited to the following, but include, for example, triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, and the like.

  As the condensate of the above-mentioned phosphate ester, n can usually take an average value of 1 to 5, but preferably an average value of 1 to 3.

It is preferable that at least one of the R ¹¹ , the R ¹² , the R ^13, and the R ¹⁴ is an aryl group from the viewpoint of flame retardancy and heat resistance developed when kneaded with another resin. Is more preferably an aryl group. From the same viewpoint, preferred aryl groups include a phenyl group, a xylenyl group, a cresyl group, and halogenated derivatives of these groups.

  As the arylene group for X, resorcinol, hydroquinone, bisphenol A, biphenol, or a residue obtained by removing two hydroxyl groups from a halogenated derivative thereof are preferable.

  Examples of the condensed phosphoric ester compound include, but are not limited to, a resorcinol-bisphenyl phosphate compound, a bisphenol A-polyphenyl phosphate compound, a bisphenol A-polycresyl phosphate compound, and the like. Among them, bisphenol A-bis (diphenyl phosphate) and (1,3-phenylenebis (diphenyl phosphate)) are preferred.

  The content of the component (c) in the resin composition of the present embodiment is 15 to 25% by mass with respect to 100% by mass of the resin composition from the viewpoint of flame retardancy, heat resistance, and impact resistance. Preferably it is 15-23 mass%, More preferably, it is 17-22 mass%. By setting the content of the component (c) to 15 to 25% by mass, the balance of flame retardancy, heat resistance, and impact resistance of the resin composition of the present embodiment can be sufficiently improved.

((D) glass fiber)
The resin composition of the present embodiment contains glass fiber as the component (d). As the glass fiber used as the component (d), a known glass fiber can be used.
It is preferable that the glass fiber has been subjected to a surface treatment for improving the adhesion to the resin. The surface treatment includes, for example, those treated with various coupling agents such as silane-based and titanate-based ones. Among them, it is preferable to use those to which aminosilane and epoxysilane-based coupling agents are added.
(D) From the viewpoint of the reinforcing effect of the glass fiber, L / D represented by the ratio of the average diameter (D) to the average length (L) of the fiber is preferably 5 or more, and more preferably 10 or more. More preferably, it is more preferably 20 or more.

  The content of the glass fiber (d) in the resin composition of the present embodiment is 5 to 20% by mass with respect to 100% by mass of the resin composition from the viewpoint of flame retardancy, impact resistance, and heat resistance. Preferably it is 5-18 mass%, More preferably, it is 5-15 mass%.

((E) polystyrene resin)
Examples of the (e) polystyrene resin that may be included in the resin composition of the present embodiment include atactic polystyrene, rubber-reinforced polystyrene (high impact polystyrene, HIPS), and styrene having a styrene content of 50% by weight or more. -Acrylonitrile copolymer (AS), and an AS resin in which the styrene-acrylonitrile copolymer is rubber-reinforced, and the like, and atactic polystyrene and / or high-impact polystyrene are preferable.
The polystyrene resins may be used alone or in combination of two or more.

  The content of the (e) polystyrene resin in the resin composition of the present embodiment is less than 5% by mass and 3% by mass or less based on 100% by mass of the resin composition from the viewpoint of flame retardancy and heat resistance. Is preferably 1% by mass or less, and may be 0% by mass.

  The mass ratio (PPE / polystyrene resin) of PPE and (e) polystyrene resin in the component (a) is preferably 90/10 to 100/0 from the viewpoint of flame retardancy and heat resistance. , 94.5 / 5.5 to 100/0, more preferably 96/4 to 100/0.

(Other components)
The resin composition of the present embodiment, in addition to the components described above, the thermal conductivity of the resin composition, electrical resistance, fluidity, low volatile components, within a range that does not impair the heat resistance and flame retardancy, as needed And other components may be contained.
The content of the other components may be 10% by mass or less when the resin composition is 100% by mass.

  Examples of the other components include, but are not limited to, thermoplastic elastomers (polyolefin-based elastomers, etc.), heat stabilizers, antioxidants, metal deactivators, nucleating agents, flame retardants ( Organophosphate compound, ammonium polyphosphate compound, silicone flame retardant, phosphazene flame retardant, etc.), plasticizer (low molecular weight polyethylene, epoxidized soybean oil, polyethylene glycol, fatty acid esters, etc.), weather resistance (light) Properties improvers, slip agents, inorganic or organic fillers and reinforcing materials (carbon fibers, polyacrylonitrile fibers, aramid fibers, etc.), various coloring agents, release agents and the like.

In the UL94V test, the resin composition of the present embodiment preferably has a flame retardancy of class V-0 when tested with a 1.6 mm thick test piece.
In addition, the flame retardancy of the resin composition can be evaluated by a method described in Examples described later.

(Production method of resin composition)
The resin composition of the present embodiment can be produced by melt-kneading the components (a) to (e) and, if necessary, other components.

  Examples of the melt kneader for performing melt kneading include, but are not limited to, a single-screw extruder, a multi-screw extruder including a twin-screw extruder, a roll, kneader, a Brabender plastograph, and heat-melt kneading with a Banbury mixer. A twin-screw extruder is particularly preferred from the viewpoint of kneading properties. Specific examples include ZSK series manufactured by WERNER & PFLEIDERER, TEM series manufactured by Toshiba Machine Co., Ltd., and TEX series manufactured by Japan Steel Works, Ltd.

  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 20 or more and 60 or less, more preferably 30 or more and 50 or less.

  The configuration of the extruder is not particularly limited. For example, a first raw material supply port is provided upstream, a first vacuum vent is provided downstream of the first raw material supply port, and a first vacuum vent is provided. A second material supply port is provided downstream (if necessary, third and fourth material supply ports may be provided downstream of the second material supply port), and further downstream of the second material supply port. The one provided with the second vacuum vent is preferable. 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 material supply port, and the kneading section is provided between the second to fourth material supply ports and the second vacuum vent. It is more preferable to provide a kneading section between them.

  The method of supplying the raw materials to the second to fourth raw material supply ports is not particularly limited, but the extruder is opened to the side of the extruder rather than simply added and supplied from the open ports of the second to fourth raw material supply ports. A method of supplying from the mouth using a forced side feeder is preferable because it tends to supply more stably.

  In particular, when the raw material contains powder and it is desired to reduce the generation of cross-linked products and carbides due to the heat history of the resin, a method using a forced side feeder supplied from the extruder side is more preferable. To 4th raw material supply ports, and a method of supplying these raw material powders in a divided manner is more preferable.

  In addition, when a liquid raw material is added, a method of adding the raw material into an extruder using a plunger pump, a gear pump, or the like is preferable.

  And the upper open port of the extruder second to fourth raw material supply ports can be used as an open port for removing the air to be carried.

  The melt-kneading temperature in the melt-kneading step of the resin composition and the screw rotation speed are not particularly limited, but heating is performed at a temperature higher than the melting point of the crystalline resin for a crystalline resin, and higher than the glass transition temperature for a non-crystalline resin. It is possible to select a temperature at which the resin can be melted and processed without difficulty. The temperature is usually arbitrarily selected from 200 to 370 ° C., and the screw rotation speed is set to 100 to 1200 rpm.

  As one of the specific manufacturing modes of the resin composition of the present embodiment using a twin-screw extruder, for example, a polyphenylene ether-based resin as the component (a), a hydrogenated block copolymer as the component (b), (E) The polystyrene-based resin as the component is supplied to the first raw material supply port of the twin-screw extruder, and the heating and melting zone is set to the melting temperature of the polyphenylene ether-based resin. And the condensed phosphate ester-based flame retardant of component (c) from the second raw material supply port and the glass fiber of component (d) from the third raw material supply port are respectively added to the molten resin and melt-kneaded. Method. The components (a) to (e) are supplied to the twin-screw extruder by providing the second raw material supply port and the third raw material supply port as described above to divide and supply each component. Alternatively, all components may be supplied collectively from the first raw material supply port of the extruder.

Furthermore, when reducing the generation of crosslinked products and carbides due to the thermal history of the resin in the presence of oxygen, the oxygen concentration of each process line in the route of adding each raw material to the extruder is kept at less than 1.0% by volume. Is preferred. The addition route is not particularly limited, but specific examples include, in order from the stock tank, a pipe, a weight feeder having a refill tank, a pipe, a supply hopper, a twin-screw extruder, and the like. A method for maintaining the low oxygen concentration as described above is not particularly limited, but a method of introducing an inert gas into each of the process lines with improved airtightness is effective. Usually, it is preferable to maintain the oxygen concentration at less than 1.0% by volume by introducing nitrogen gas.

  The above-mentioned method for producing a resin composition is characterized in that, in the case where the polyphenylene ether-based resin as the component (a) contains a powdery component (having a volume average particle size of less than 10 μm), the resin composition of the present embodiment is subjected to a twin-screw extruder When producing using, the effect of further reducing the residue in the screw of the twin-screw extruder, and further, in the resin composition obtained by the above-described production method, to reduce the occurrence of black spot foreign matter and carbides and the like Bring effect.

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 less than 1.0% by volume, and any one of the following methods 1 to 3 is used. Is preferred.
1. The components (a), (b), and (e) contained in the resin composition of the present embodiment are all melt-kneaded (first kneading step) and kneaded in a molten state obtained in the first kneading step. The whole amount of the component (c) is supplied to the mixture, followed by melt kneading (second kneading step), and the total amount of the component (d) is added to the kneaded material in the molten state obtained in the second kneading step. Supplying, and continuously performing melt kneading (third kneading step).
2. The total amount of the components (a) to (c) and the component (e) contained in the resin composition of the present embodiment is melt-kneaded (first kneading step), and the molten state obtained in the first kneading step is kneaded. A production method in which the whole amount of the component (d) is supplied to the product, followed by melt-kneading (second kneading step).
3. A method of melting and kneading all the components (a) to (e) contained in the resin composition of the present embodiment.

In particular, the polyphenylene ether, which is the raw material of the component (a), may be in powder form, and the condensed phosphate ester-based flame retardant of component (c) may be in a liquid form. It is difficult to increase the amount and the residence time of the resin in the extruder is prolonged, so that thermal deterioration is likely to occur. Further, the glass fiber of the component (d) is relatively easily broken.
From the above, the resin composition obtained by the above-mentioned production method 1 is superior in the mixing property of each component as compared with the resin compositions obtained by the production methods 2 and 3, and is decomposed due to thermal deterioration, crosslinked product or carbide. This is more preferable because it can reduce the occurrence of odors, reduce the breaking of glass fibers, and increase the amount of resin produced per hour, and provide a resin composition with excellent productivity and quality.

〔Molding〕
Molded articles containing the resin composition of this embodiment include optical device mechanism parts, parts around light source lamps, sheets or films for metal film laminated substrates, hard disk internal parts, optical fiber connector ferrules, printer parts, copier parts, automobile radiators It can be widely used as molded parts such as parts in automobile engine room such as tank parts and lamp parts of automobile. The molded article containing the resin composition of the present embodiment is particularly suitable for a protective housing for a battery system of a hybrid vehicle or an electric vehicle, for which regulations on flame retardancy have become strict in recent years.

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

The methods for measuring physical properties used in Examples and Comparative Examples are shown below.
((1) Flame retardancy)
Pellets of the resin compositions obtained in Examples and Comparative Examples described later are supplied to a screw in-line injection molding machine set at 290 ° C. in a cylinder and 80 ° C. in a mold, and are 127 mm long, 12.7 mm wide and 12.7 mm thick. A 0.6 mm flame-retardant test piece was molded. Using this test piece, five samples were tested per sample in accordance with UL94 (a standard defined by Under Writers Laboratories Inc., USA).

((2) Impact resistance)
Pellets of the resin compositions obtained in Examples and Comparative Examples described later are supplied to a screw in-line injection molding machine set at a cylinder 290 ° C. and a mold 80 ° C., and a test piece type A is formed according to ISO 10724-1. did. Using this test piece, the Charpy impact strength (KJ / m ² ) was measured according to JIS K7111-1. The higher the value, the better the impact resistance was evaluated.

((3) Heat resistance)
Pellets of the resin compositions obtained in Examples and Comparative Examples described later are supplied to a screw in-line injection molding machine set at a cylinder 290 ° C. and a mold 80 ° C., and a test piece type A is formed according to ISO 10724-1. did. Using this test piece, the deflection temperature under load (° C.) was measured according to JIS K7191-1. The higher the value, the better the heat resistance.

((4) Mold contamination test)
Pellets of the resin composition obtained in Examples and Comparative Examples described later are supplied to a screw in-line injection molding machine set at a cylinder temperature of 290 ° C., and a gas vent portion is not particularly provided at a mold temperature of 80 ° C. A weld mold (a plate having a length of 38 mm, a width of 79 mm, and a thickness of 5 mm, having a gate portion at a position 8 mm left and right from the center of the plate-shaped mold and having a weld portion at the horizontal center of the mold) is used. The mold is continuously molded, and the gloss of the weld portion of the mold is measured using a high gloss gloss checker IG-410 (manufactured by HORIBA, Ltd.) (range 1,000 mode). , The number of molding shots until the difference in glossiness reached 300 was determined, and evaluation of mold contamination was made. The larger the number of molding shots, the lower the contamination of the mold.

Raw materials used in Examples and Comparative Examples are shown below.
<(A) component: polyphenylene ether resin>
(A1): PPE (polyphenylene ether)
Polyphenylene ether obtained by oxidative polymerization of 2,6-xylenol (reduced viscosity measured at 30 ° C. with a chloroform solution having a concentration of 0.5 g / dL: 0.51 dL / g).

<(B) component: hydrogenated block copolymer>
The following hydrogenated block copolymer was synthesized.
(B1) Polystyrene-hydrogenated polybutadiene-polystyrene structure having a bound styrene content of 32%, a number average molecular weight of 108,300, a molecular weight distribution of 1.05, and a 1,2-vinyl bond content of polybutadiene before hydrogenation Is a hydrogenated block copolymer having a polybutadiene moiety having a hydrogenation rate of 99.9%.
(B2) Polystyrene-hydrogenated polybutadiene-polystyrene structure having a bound styrene content of 35%, a number average molecular weight of 124,800, a molecular weight distribution of 1.06, and a 1,2-vinyl bond content of polybutadiene before hydrogenation Is a hydrogenated block copolymer having a polybutadiene moiety hydrogenation rate of 99.8%.
(B3) Polystyrene-hydrogenated polybutadiene-polystyrene structure, bonded styrene content 34%, number average molecular weight 256,000, molecular weight distribution 1.08, 1,2-vinyl bond content of polybutadiene before hydrogenation Is a block copolymer having a polybutadiene moiety hydrogenation rate of 99.6%.
(B4) Polystyrene-hydrogenated polybutadiene-polystyrene structure, bonded styrene amount 34%, number average molecular weight 334,000, molecular weight distribution 1.09, 1,2-vinyl bond amount of polybutadiene before hydrogenation Is a hydrogenated block copolymer having a polybutadiene moiety having a hydrogenation rate of 99.9%.

<Component (c): condensed phosphate ester flame retardant>
(C1) Aromatic condensed phosphoric ester (CR-741 (bisphenol A-bis (diphenyl phosphate)): manufactured by Daihachi Chemical Industry Co., Ltd.)
(C2) Aromatic condensed phosphate ester (CR-733S (1,3-phenylenebis (diphenyl phosphate)): manufactured by Daihachi Chemical Industry Co., Ltd.)
<(C ′) component: other flame retardant>
(C'3) Phosphate ester (TPP: manufactured by Daihachi Chemical Industry Co., Ltd.)

<(D) component: glass fiber>
(D1) Glass fibers having an average diameter of 13 μm and an average length of 3 mm and surface-treated with an aminosilane coupling agent.

<Component (e): polystyrene resin>
(E1): High impact polystyrene (Polystyrene H9405: manufactured by PS Japan Co., Ltd.).

[Examples 1 to 13], [Comparative Examples 1 to 10]
The resin composition was manufactured using a twin screw extruder ZSK-40 (manufactured by Coperion). In this twin-screw extruder, a first raw material supply port is provided on the upstream side with respect to the flow direction of the raw material, and a first vacuum vent, a second raw material supply port, and a third raw material supply port are provided downstream therefrom. A second vacuum vent was provided downstream.
Using the extruder set as described above, the components (a) to (e) having the compositions shown in Tables 1 and 2 were added, and the conditions were as follows: extrusion temperature 270 to 320 ° C., screw rotation speed 300 rpm, and discharge rate 100 kg / hour. To produce pellets.

Each evaluation described above was performed using the obtained resin composition pellets. Tables 1 and 2 show details of these production methods and evaluation results.
The addition amounts of the components (a) to (e) in the table are ratios when the total amount of the components (a) to (e) is 100% by mass.

As shown in Tables 1 and 2, it was found that the resin compositions of Examples 1 to 13 were excellent in flame retardancy and impact resistance, and were also excellent in balance between heat resistance and mold contamination.
Comparative Examples 1 to 10 were inferior to any of the examples in any of flame retardancy, impact resistance, heat resistance, and mold contamination.

  The molded article molded with the resin composition of the present embodiment has excellent flame retardancy, high impact resistance, and excellent heat resistance, so that the degree of freedom in designing the resin molded article can be increased. . For this reason, it can be used as various components in electric / electronic devices, automobile devices, chemical devices, and optical devices.For example, chassis and cabinets such as digital versatile disks, optical device mechanism components such as optical pickup slide bases, light source lamp peripheral components, Parts in the car engine room such as metal film laminated board sheets or films, hard disk inner parts, optical fiber connector ferrules, laser beam printer inner parts (toner cartridges, etc.), inkjet printer inner parts, copier inner parts, automobile radiator tank parts, etc. It has industrial applicability as an automotive lamp part and the like.

Claims (6)

(A) 55 to 75% by mass of a polyphenylene ether-based resin;
(B) hydrogenation obtained by hydrogenating a block copolymer containing two or more polymer blocks A mainly composed of a vinyl aromatic compound and one or more polymer blocks B mainly composed of a conjugated diene compound; 3 to 15% by mass of the block copolymer,
(C) 15 to 25% by mass of a condensed phosphate ester flame retardant;
(D) 5 to 20% by mass of glass fiber,
A resin composition comprising (e) less than 5% by mass of a polystyrene resin as an optional component.   The resin composition according to claim 1, wherein the content of the (e) polystyrene-based resin is 3% by mass or less.   The resin composition according to claim 1, wherein the number average molecular weight of the (b) hydrogenated block copolymer is 120,000 to 300,000. 4.   The resin composition according to any one of claims 1 to 3, wherein the (c) condensed phosphate ester flame retardant is bisphenol A-bis (diphenyl phosphate).   The resin composition according to any one of claims 1 to 4, wherein in the UL94V test, the flame retardancy when tested on a 1.6 mm thick test piece is class V-0.   A protective housing for a battery system of a hybrid vehicle or an electric vehicle, comprising the resin composition according to claim 1.