JP2013234287A - Flame-retardant resin composition and molded article thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composition with an excellently balanced flame retardancy, fluidity and heat resistance.SOLUTION: A resin composition includes: (a) 40 to 20 pts.mass of a polypropylene resin; (b) 60 to 80 pts.mass of a polyphenylene ether resin; (c) 1 to 20 pts.mass of a hydrogenation block copolymer in which at least a part of a block copolymer containing a polymer block A related mainly to a vinyl aromatic compound unit, and a polymer block B having 30 to 90% of the total amount of a 1,2-vinyl bonding amount and a 3,4-vinyl bonding amount, and also related mainly to a conjugated diene compound unit is subjected to hydrogenation based on 100 pts.mass of the total amount of the (a) component and the (b) component; (d) 25 to 45 pts.mass of a phosphate flame retardant; and (e) 0.5 to 10 pts.mass of a metal oxide, wherein the flame retardancy is not less than V-1.

Description

  The present invention relates to a flame retardant resin composition and a molded product thereof.

  Polyphenylene ether (hereinafter referred to as “PPE”) is known as an engineering plastic having excellent flame retardancy, heat resistance, dimensional stability, non-hygroscopicity, and electrical properties, but has poor melt fluidity. There are drawbacks that molding is difficult and solvent resistance and impact resistance are poor.

  Polypropylene, on the other hand, has excellent processability, solvent resistance, mechanical strength, and gas barrier properties, and is widely used in fields such as automotive parts, electrical / electronic equipment parts, and home appliances as a low specific gravity and inexpensive plastic. .

  Therefore, by mixing these two resins, complementing each other's disadvantages and drawing out the advantages, a resin excellent in moldability, mechanical strength, heat resistance and cost can be obtained. The industrial meaning is very large.

  However, the blend composition of PPE and polypropylene has a problem that the excellent flame retardancy inherent to PPE is lost.

  Conventionally, flame retarding techniques such as adding a halogen-based compound and / or antimony trioxide have been used as flame retarding of flammable resins, but this is not preferable in terms of environmental hygiene. Therefore, improvement of the flame-retarding technique is demanded, and a flame-retardant technique using a flame retardant that does not contain these has been studied.

  In addition, a large amount of flame retardant is required to make the blended composition of PPE and polypropylene flame retardant, but the obtained flame retardant is not always satisfactory, and since a large amount of flame retardant is blended, the physical properties are improved. There is a drawback of significant damage.

  Patent Document 1 describes a resin composition containing a metal oxide and a pentavalent phosphorus compound, and has been proposed as providing a thermoplastic resin excellent in flame retardancy without containing a halogen.

Japanese Patent Laid-Open No. 2006-16587

  However, Patent Document 1 does not specifically disclose a blend composition of PPE and polypropylene, and flame retardancy, fluidity, and heat resistance may be insufficient.

  This invention is made | formed in view of the said problem, Comprising: It aims at providing the resin composition excellent in the balance of a flame retardance, fluidity | liquidity, and heat resistance.

  The present inventors have intensively studied to solve the above problems. That is, in the present invention, in a blend composition of PPE and polypropylene resin, a phosphate ester flame retardant and a metal oxide are used, and these are made into a specific ratio, thereby achieving a balance between flame retardancy, fluidity and heat resistance. The inventors have found that a resin composition excellent in the above can be obtained, and have reached the present invention.

That is, the present invention provides the following.
[1]
(A) 40-20 parts by mass of polypropylene resin;
(B) including 60 to 80 parts by mass of a polyphenylene ether resin,
For a total amount of 100 parts by mass of the component (a) and the component (b),
(C) The polymer block A mainly composed of vinyl aromatic compound units, the total amount of 1,2-vinyl bonds and 3,4-vinyl bonds is 30 to 90%, and conjugated diene compound units 1 to 20 parts by mass of a hydrogenated block copolymer in which at least a part of a block copolymer including the polymer block B as a main component is hydrogenated;
(D) 25 to 45 parts by mass of a phosphate ester flame retardant;
(E) 0.5 to 10 parts by mass of a metal oxide,
A resin composition having flame retardancy of V-1 or higher.
[2]
In a total of 100 parts by mass of the component (a) and the component (b),
35 to 25 parts by mass of the component (a),
The resin composition according to [1], including 65 to 75 parts by mass of the component (b).
[3]
The resin composition according to [1] or [2], wherein the total amount of the 1,2-vinyl bond amount and the 3,4-vinyl bond amount is 65 to 90%.
[4]
The resin composition according to any one of [1] to [3], wherein the component (d) is a condensed phosphate ester flame retardant.
[5]
The resin composition according to any one of [1] to [4], wherein the component (e) is iron oxide.
[6]
The resin composition according to any one of [1] to [5], wherein the flame retardancy is V-0 or more.
[7]
A molded article comprising the resin composition according to any one of [1] to [6].

  ADVANTAGE OF THE INVENTION According to this invention, the resin composition excellent in the flame retardance, fluidity | liquidity, and heat resistance balance is provided.

  Hereinafter, a mode for carrying out the present invention (hereinafter referred to as “the present embodiment”) will be described in detail. In addition, this invention is not restrict | limited to the following embodiment, A various deformation | transformation can be implemented within the range of the summary.

  In the following, the structural unit constituting the polymer is described as “˜unit”, and the monomer component before polymerization is described by a compound name.

(Resin composition)
The resin composition according to this embodiment includes (a) 40 to 20 parts by mass of polypropylene resin,
(B) 60-80 parts by mass of a polyphenylene ether resin,
For a total amount of 100 parts by mass of the component (a) and the component (b),
(C) The polymer block A mainly composed of vinyl aromatic compound units, the total amount of 1,2-vinyl bonds and 3,4-vinyl bonds is 30 to 90%, and conjugated diene compound units 1 to 20 parts by mass of a hydrogenated block copolymer in which at least a part of a block copolymer including the polymer block B as a main component is hydrogenated;
(D) 25 to 45 parts by mass of a phosphate ester flame retardant;
(E) 0.5 to 10 parts by mass of a metal oxide,
Flame retardancy is V-1 or higher.

  When the content of the components (a) to (e) is in the above range, a resin composition having an excellent balance of flame retardancy, fluidity, and heat resistance can be obtained.

  In the resin composition according to this embodiment, (a) component is 40 to 20 parts by mass, and (b) component is 60 to 80 in 100 parts by mass of the total amount of (a) polypropylene resin and (b) polyphenylene ether resin. Preferably, the component (a) is 35 to 25 parts by mass, the component (b) is 65 to 75 parts by mass, and more preferably the component (a) is 35 to 30 parts by mass, (b) The component is 65 to 70 parts by mass. When the content of the component (a) / component (b) is within the above range, the obtained resin composition is excellent in flame retardancy, heat resistance, solvent resistance, and gas barrier properties.

<(A) component>
(A) The polypropylene resin will be described in detail.
The (a) polypropylene resin (hereinafter also abbreviated as “(a) component” or “PP”) used in the present embodiment is not particularly limited, but specifically, a crystalline propylene homopolymer or crystalline propylene— An ethylene block copolymer is preferred. Here, the term “crystalline propylene-ethylene block copolymer” means a crystalline propylene homopolymer portion obtained in the first step of polymerization, propylene, ethylene and / or at least one of the second and subsequent steps of polymerization. A copolymer having a propylene-ethylene random copolymer portion obtained by copolymerizing another α-olefin (for example, butene-1, hexene-1, etc.). Further, (a) the polypropylene resin may be a mixture of these crystalline propylene homopolymer and crystalline propylene-ethylene block copolymer.

  (A) The manufacturing method of a polypropylene resin is not specifically limited, A well-known thing can be used. For example, in the presence of a titanium trichloride catalyst or a titanium halide catalyst supported on a carrier such as magnesium chloride and an alkylaluminum compound, polymerization is carried out at a polymerization temperature in the range of 0 to 100 ° C. and a polymerization pressure in the range of 3 to 100 atm. The method of doing is mentioned. At this time, a chain transfer agent such as hydrogen can be added in order to adjust the molecular weight of the polymer. Further, the polymerization method is not particularly limited, but specifically, any of batch method and continuous method is possible. The polymerization method is not particularly limited, and specifically, a solution polymerization method in a solvent such as butane, pentane, hexane, heptane, octane, or a slurry polymerization method can also be selected. Such as bulk polymerization, gas phase polymerization method in gaseous monomer, and the like can be applied.

  In addition to the polymerization catalyst described above, an electron donating compound can be used as an internal donor component or an external donor component as the third component in order to increase the isotacticity and polymerization activity of the resulting polypropylene. These electron-donating compounds are not particularly limited, and specifically, ester compounds such as ε-caprolactone, methyl methacrylate, ethyl benzoate, methyl toluate; triphenyl phosphite, tributyl phosphite, etc. Phosphorous acid esters of phosphoric acid; phosphoric acid derivatives such as hexamethylphosphoric triamide; alkoxy ester compounds; aromatic monocarboxylic acid esters; alkoxysilane compounds such as aromatic alkylalkoxysilanes and aliphatic hydrocarbon alkoxysilanes; various ether compounds Various alcohols; and / or various phenols.

  In addition, (a) polypropylene resin used in this embodiment is the above-mentioned polypropylene resin grafted and / or added with α, β-unsaturated carboxylic acid and / or its derivative (including acid anhydride and ester). It may be a modified polypropylene resin. Such a modified polypropylene resin is not particularly limited. Specifically, the above-described polypropylene is used in the presence or absence of a radical generator, in a molten state, a solution state, or a slurry state at a temperature of 30 to 350 ° C. It is obtained by reacting a resin with an α, β-unsaturated carboxylic acid and / or a derivative thereof. Further, the (a) polypropylene resin used in the present embodiment may be a mixture of the above-described polypropylene resin and the modified polypropylene resin in an arbitrary ratio. In addition, although it does not specifically limit as a modified polypropylene resin, Specifically, it is preferable that (alpha), (beta) -unsaturated carboxylic acid and / or its derivative are 0.01-10 mass% grafting or addition. .

  The (a) polypropylene resin in the present embodiment can be obtained by the above method. Further, it can be used even when it is a polypropylene resin having any crystallinity and melting point. Furthermore, (a) polypropylene resin may be used independently and may use 2 or more types together.

<(B) component>
(B) The polyphenylene ether resin will be described in detail.
The (b) polyphenylene ether resin (hereinafter also abbreviated as “component (b)” or “PPE”) used in the present embodiment is not particularly limited, but specifically, it is a repeat represented by the following formula (1). A homopolymer and / or copolymer having a unit structure is preferred. Although the reduced viscosity (0.5 g / dL chloroform solution, 30 degreeC measurement) of (b) component is not specifically limited, Preferably it is 0.15-0.7, More preferably, it is 0.2-0.6. Range.

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 a halohydrocarbonoxy group in which at least two carbon atoms separate a halogen atom and an oxygen atom.

  The (b) polyphenylene ether resin used in the present embodiment is not particularly limited. Specifically, poly (2,6-dimethyl-1,4-phenylene ether), poly (2-methyl-6-ethyl-) is used. 1,4-phenylene ether), poly (2-methyl-6-phenyl-1,4-phenylene ether), poly (2,6-dichloro-1,4-phenylene ether) and other polymers; A polyphenylene ether copolymer of dimethylphenol and other phenols (for example, 2,3,6-trimethylphenol or 2-methyl-6-butylphenol) can also be used. Among these, poly (2,6-dimethyl-1,4-phenylene ether) and a copolymer of 2,6-dimethylphenol and 2,3,6-trimethylphenol are preferable, and poly (2,6-trimethylphenol) is more preferable. 6-dimethyl-1,4-phenylene ether).

  (B) The manufacturing method of polyphenylene ether resin is not specifically limited, A conventionally well-known thing can be used. For example, it can be easily produced by, for example, 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. Alternatively, U.S. Pat. No. 3,306,875, U.S. Pat. No. 3,257,357, U.S. Pat. No. 3,257,358, JP-B-52-17880, JP-A-50-51197, JP-A-63-152628. It can be manufactured by a method described in a gazette or the like.

  Further, (b) the polyphenylene ether resin may be a modified polyphenylene ether resin obtained by grafting and / or adding the above polyphenylene ether resin with a styrene monomer and / or a derivative thereof. Such a modified polyphenylene ether resin is not particularly limited. Specifically, in the presence or absence of a radical generator, in the molten state, the solution state or the slurry state, at 80 to 350 ° C. It can be obtained by reacting an ether resin with a styrene monomer and / or a derivative thereof.

  Such a modified polyphenylene ether resin is not particularly limited, and examples thereof include a polyphenylene ether resin obtained by grafting and / or adding 0.01 to 10% by mass of a styrene monomer and / or a derivative thereof.

  When the polyphenylene ether resin and the modified polyphenylene ether resin are used in combination, the mixing ratio is not limited and can be mixed at an arbitrary ratio.

  As the (b) polyphenylene ether resin, a mixture of the above-described polyphenylene ether resin and polystyrene, syndiotactic polystyrene or high impact polystyrene can also be suitably used. More preferably, 100 parts by mass of the polyphenylene ether resin described above is a mixture of polystyrene, syndiotactic polystyrene or high impact polystyrene within a range not exceeding 400 parts by mass.

<(C) component>
The (c) hydrogenated block copolymer used in this embodiment is a polymer block A mainly composed of vinyl aromatic compound units, and the total amount of 1,2-vinyl bonds and 3,4-vinyl bonds. 30 to 90%, and at least a part of a block copolymer containing a copolymer block B mainly composed of a conjugated diene compound unit is hydrogenated.

(Polymer block A)
The polymer block A mainly composed of a vinyl aromatic compound unit is preferably a homopolymer block of a vinyl aromatic compound or a copolymer block of a vinyl aromatic compound and a conjugated diene compound.

  In the polymer block A, “consisting mainly of a vinyl aromatic compound unit” means that the polymer block A contains a vinyl aromatic compound unit in an amount exceeding 50 mass%. And it is preferable to contain 60 mass% or more of vinyl aromatic compound units in the polymer block A, and it is more preferable to contain 70 mass% or more. Thereby, more excellent fluidity, impact resistance, weld, and appearance can be obtained.

  Although it does not specifically limit as a vinyl aromatic compound which comprises the polymer block A, Specifically, styrene, (alpha) -methylstyrene, vinyl toluene, p-tert- butyl styrene, diphenylethylene etc. are mentioned. These may be used alone or in combination of two or more. Of these, styrene is preferred. Further, the conjugated diene compound copolymerizable with the vinyl aromatic compound is not particularly limited, and specifically, those used in the polymer block B described later can be used.

  The number average molecular weight of the polymer block A is not particularly limited, but is preferably 15,000 or more. Thereby, the heat-resistant creep property of the resin composition of this embodiment can be made more excellent. The number average molecular weight of the polymer block A can be measured by gel permeation chromatography (GPC, moving layer: tetrahydrofuran, standard material: polystyrene).

(Polymer block B)
The polymer block B mainly composed of a conjugated diene compound unit is preferably a homopolymer block of a conjugated diene compound or a random copolymer block of a conjugated diene compound and a vinyl aromatic compound.

  In the polymer block B, “consisting mainly of a conjugated diene compound unit” means that the polymer block B contains a conjugated diene compound in an amount exceeding 50 mass%. And it is preferable to contain 60 mass% or more of conjugated diene compounds in the polymer block B from a viewpoint of the outstanding fluidity | liquidity, impact resistance, weld, and external appearance, and it is more preferable to contain 70 mass% or more.

  Although it does not specifically limit as a conjugated diene compound which comprises the polymer block B, Specifically, butadiene, isoprene, 1,3-pentadiene, 2,3-dimethyl-1,3-butadiene, etc. are mentioned. These may be used alone or in combination of two or more. Of these, butadiene, isoprene, and combinations thereof are preferred. Further, the vinyl aromatic compound copolymerizable with the conjugated diene compound is not particularly limited, and specifically, those used in the polymer block A described above can be used.

  And about the microstructure (bonding form of a conjugated diene compound) of the polymer block B, the total amount of 1,2-vinyl bond amount and 3,4-vinyl bond amount (henceforth "total vinyl bond amount"). Is 30 to 90%, preferably 45 to 90%, more preferably 65 to 90%. Here, the term “total amount of 1,2-vinyl bond and 3,4-vinyl bond” refers to 1,2-addition, 3,4-addition, and 1,4-vinyl bond in polymer block B. This refers to the number% of 1,2-added or 3,4-added conjugated diene compound units among the conjugated diene compound units added. By setting the total vinyl bond content of the conjugated diene compound in the polymer block B within the above range, the fluidity, impact resistance, weld and appearance are excellent.

  In particular, when the polymer block B is a polymer mainly composed of butadiene units, the total vinyl bond content of the butadiene units in the polymer block B is 65 to 65 from the viewpoints of fluidity, impact resistance, weld, and appearance. 90% is preferable.

  In the present embodiment, the total vinyl bond amount can be measured by an infrared spectrophotometer. The calculation method is described in Analytical Chemistry, Volume 21, No. 8, according to the method described in August 1949.

The component (c) is a hydrogenated block copolymer of a block copolymer containing at least a polymer block A and at least a polymer block B. When the block polymer A is “A” and the block polymer B is “B”, as the component (c), for example, AB, ABA, BABA, (A -B-) ₄ Si, vinyl aromatic compounds having a structure such as a-B-a-B- a - hydrogenated product of a conjugated diene compound block copolymer. (A-B-) ₄ Si is a reaction residue of a polyfunctional coupling agent such as silicon tetrachloride or tin tetrachloride, or a residue of an initiator such as a polyfunctional organolithium compound.

  The molecular structure of the block copolymer including the block polymer A and the block polymer B is not particularly limited, and may be, for example, linear, branched, radial, or any combination thereof.

  In the polymer block A and the polymer block B, the distribution of the vinyl aromatic compound or conjugated diene compound in the molecular chain in each polymer block is random, tapered (the monomer component increases or decreases along the molecular chain) ), Partially blocky or any combination thereof.

  When there are two or more polymer blocks A or polymer blocks B in the block copolymer, each polymer block may have the same structure or a different structure. .

  In the hydrogenated block copolymer of component (c), the content of the vinyl aromatic compound unit bonded to the block copolymer before hydrogenation is preferably from the viewpoint of fluidity, impact resistance, weld, and appearance. Is 20 to 95 mass%, more preferably 30 to 80 mass%. In the present embodiment, the content of the vinyl aromatic compound unit can be measured with an ultraviolet spectrophotometer.

  Further, the number average molecular weight of the block copolymer before hydrogenation is not particularly limited, but specifically, 5,000 to 1,000,000 is preferable, 10,000 to 800,000 is more preferable, and 30,000. More preferably, ˜500,000. The number average molecular weight can be measured by gel permeation chromatography (GPC, solvent: tetrahydrofuran, standard material: polystyrene).

  The molecular weight distribution of the block copolymer before hydrogenation is not particularly limited, but specifically, 10 or less is preferable. The molecular weight distribution can be calculated by the ratio (Mw / Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) measured by gel permeation chromatography (GPC, solvent: tetrahydrofuran, standard material: polystyrene).

  Further, the hydrogenation rate with respect to the conjugated diene compound unit in the component (c) is not particularly limited, but specifically, from the viewpoint of heat resistance, preferably 50% or more of the double bond derived from the conjugated diene compound unit. More preferably, it is 80% or more, more preferably 90% or more. In this embodiment, the hydrogenation rate can be measured by NMR.

  (C) The manufacturing method of the hydrogenated block copolymer of a component is not specifically limited, For example, it can obtain with a well-known manufacturing method. For example, Japanese Patent Application Laid-Open Nos. 47-11486, 49-66743, 50-75651, 54-126255, and 56-10542 are disclosed. No. 5, JP-A 56-62847, JP-A 56-100900, JP-A 2-300218, British Patent 1130770, US Pat. No. 3,281,383, US Pat. No. 3639517 The methods described in the specification, British Patent No. 1020720, US Pat. No. 3,333,024 and US Pat. No. 4,501,857 can be used.

  Further, the hydrogenated block copolymer of component (c) is obtained by grafting the above hydrogenated block copolymer with α, β-unsaturated carboxylic acid and / or a derivative thereof (ester compound or acid anhydride compound). It may be a modified hydrogenated block copolymer which has been converted and / or added. Such a modified hydrogenated block copolymer is not particularly limited, and specifically, in the presence or absence of a radical generator, in a molten state, a solution state or a slurry state, at 80 to 350 ° C., It can be obtained by reacting the above hydrogenated block copolymer with an α, β-unsaturated carboxylic acid and / or a derivative thereof. Furthermore, the component (c) may be a mixture of any proportion of the above hydrogenated block copolymer and the modified hydrogenated block copolymer.

  In the present embodiment, the component (c) is preferably a hydrogenated block copolymer having a segment chain highly compatible with the polyphenylene ether resin and a segment chain highly compatible with the polypropylene resin. The component (c) serves as an admixture for mixing the polypropylene resin and the polyphenylene ether resin. The compounding quantity is 1-20 mass parts, it is preferable that it is 3-18 mass parts, and it is more preferable that it is 5-15 mass parts. When the blending amount of the component (c) is within the above range, the obtained resin composition is excellent in impact resistance, bending elastic modulus and the like.

<(D) component>
The (d) phosphate ester flame retardant used in the present embodiment refers to all phosphate ester compounds effective for improving flame retardancy. The component (d) is not particularly limited, and specifically includes trimethyl phosphate, triethyl phosphate, tripropyl phosphate, tributyl phosphate, tripentyl phosphate, trihexyl phosphate, tricyclohexyl phosphate, triphenyl phosphate, triphenyl phosphate, Phosphate esters such as cresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, dicresyl phenyl phosphate, dimethyl ethyl phosphate, methyl dibutyl phosphate, ethyl dipropyl phosphate, hydroxyphenyl diphenyl phosphate; these were modified with various substituents Compound: Examples of various condensation-type condensed phosphate ester flame retardants.

  Among these, what has as a main component at least 1 sort (s) chosen from the group which consists of condensed phosphate ester shown by following formula (2) and following formula (3) is more preferable. Here, the “main component” means that the component is contained in 90% by mass or more in the component (d).

In the formula, Q ¹ , Q ² , Q ³ , and Q ⁴ are each a substituent and each independently represent an alkyl group having 1 to 6 carbon atoms, and R ⁵ and R ⁶ are each a substituent and are methyl R ⁷ and R ⁸ each independently represents a hydrogen atom or a methyl group. n represents an integer of 0 or more, n ¹ and n ² each independently represents an integer of 0 to 2, and m ¹ , m ² , m ³ and m ⁴ each independently represents an integer of 0 to 3.
The condensed phosphate ester represented by the above formulas (2) and (3) is composed of a plurality of molecular chains. For each molecule, n is an integer of 0 or more, preferably an integer of 1 to 3. As a whole, n preferably has an average value of 1 or more.

In this, m ^1, m ^2, m ³ in the formula ^{(2), m 4, n} 1, n 2 is 0, condensed phosphoric acid ester R ^7, R ⁸ is a methyl group; Formula (2 Q ¹ , Q ² , Q ³ , Q ⁴ , R ⁷ and R 8 are methyl groups, n ¹ and n ² are 0, and m ¹ , m ² , m ³ and m ⁴ are 1 to 3 It is a condensed phosphate ester that is an integer, and the range of n is preferably an integer of 1 to 3, particularly 50% by mass or more of the phosphate ester in which n is 1. The condensed phosphate ester is preferable because it has low volatility during molding.

  In this embodiment, the blending amount of the (d) phosphate ester flame retardant is 25 to 45 parts by mass, preferably 30 to 45 parts by mass, from the viewpoint of flame retardancy and heat resistance balance, 35 More preferably, it is -45 mass parts.

<(E) component>
(E) The metal oxide that can be used in the present embodiment is not particularly limited, but specifically, zinc oxide, iron oxide, tin oxide, calcium oxide, magnesium oxide, aluminum oxide, copper oxide, titanium oxide Etc. Among these, iron oxide is preferable from the viewpoint of flame retardancy.

  The particle size of the metal oxide suitably used in the present invention is not particularly limited, and conventionally known ones can be suitably used. Among these, from the viewpoint of impact resistance and appearance, it is preferably 100 μm or less, more preferably 50 μm or less, further preferably 10 μm or less, still more preferably 5 μm or less, and even more preferably 1 μm or less.

  Each metal oxide may be used alone or as a mixture of two or more. Further, these metal oxides may be used after being coated with an arbitrary inorganic and / or organic substance.

  In this embodiment, the compounding amount of the metal oxide (e) is 0.5 to 10 parts by mass, preferably 1 to 8 parts by mass, and 1 to 5 parts by mass from the viewpoint of flame retardancy. More preferably. (E) When the compounding quantity of a component exists in the said range, the obtained resin composition shows the more outstanding flame retardance.

<Additives>
In the resin composition according to this embodiment, non-halogen and non-antimony flame retardants can be used in combination. Such a flame retardant is not particularly limited, and specifically, metal hydroxides such as magnesium hydroxide, aluminum hydroxide, calcium hydroxide, calcium aluminate; melamine, melam, melem, melon, methylene diene Melamine, ethylene dimelamine, decamethylene dimelamine, 1,3-cyclohexyl dimelamine, 4,4'-diethylene dimelamine, diethylenetrimelamine, benzoguanamine, dibenzoguanamine, succinoguanamine, methylguanamine, acetoguanamine, melamine resin, etc. Cyanurate, sulfate, phosphate, borate of the above compound; 2-dibutylamino-4,6-dimercapto-S-triazine, 2-N-phenylamino-4,6-dimercapto-S-triazine, 2,4,6-trimercapto-S-triazine, Triazine compounds such as triallyl cyanurate and trimethallyl isocyanurate; boron-containing compounds such as boric acid and zinc borate compounds; silicon-containing compounds such as polyorganosiloxane, silsesquioxane and silicon resin; silica, kaolin clay and talc Further, the flame retardancy can be further improved by adding an inorganic silicon compound such as wollastonite.

  Moreover, a filler can be mix | blended with the resin composition which concerns on this embodiment in order to improve a mechanical physical property. Such filler is not particularly limited, and specifically, silica, kaolin clay, talc, wollastonite, titanium oxide, glass beads, glass flakes, glass fiber, calcium carbonate, barium carbonate, calcium sulfate, Examples thereof include barium sulfate, calcium silicate, potassium titanate, aluminum borate, magnesium borate; fibrous reinforcing agents such as kenaf fibers, carbon fibers, silica fibers, alumina fibers, and quartz fibers; non-fibrous reinforcing agents. These may be covered with an organic substance, an inorganic substance, or the like.

  Furthermore, other additives such as plasticizers, antioxidants, and ultraviolet absorbers are added to impart other characteristics such as rigidity and dimensional stability to the resin composition and / or molded product thereof according to this embodiment. , Stabilizers such as light stabilizers, curing agents, curing accelerators, antistatic agents, conductivity imparting agents, stress relaxation agents, mold release agents, crystallization accelerators, hydrolysis inhibitors, lubricants, impact imparting agents, Sliding property improving agents, compatibilizing agents, nucleating agents, reinforcing agents, reinforcing agents, flow control agents, dyes, sensitizers, coloring pigments, rubbery polymers, conductive polymers and the like can be added.

〔Flame retardance〕
The flame retardancy of the resin composition of the present embodiment is V-1 or higher, and preferably V-0 or higher. In this embodiment, UL94 is used as a measure of flame retardancy. Flame retardant grades are referred to as V-0, V-1. This determination of flame retardancy is performed by a combustion test in which a flame of a gas burner is applied to a test piece of a prescribed size to check the degree of combustion of the test piece. As a flame retardancy grade of a general material based on UL94, there are 5VA, 5VB, V-0, V-1, V-2, and HB in descending order of flame retardancy. Here, the term “V-1 or higher” refers to a grade of 5VA, 5VB, and V-0, which has higher flame retardancy than V-1. As a specific method for evaluating flame retardancy, those listed in <Flame retardance> in the examples can be used.

[Method for producing resin composition]
Although the manufacturing method of the resin composition of this embodiment is not specifically limited, Specifically, a twin screw extruder can be used. Specific examples of such a twin screw extruder include the ZSK series manufactured by Coperion, the TEM series manufactured by Toshiba Machine Co., Ltd., and the TEX series manufactured by Nippon Steel Works.

  In this case, the melt kneading temperature and the screw rotation speed are not particularly limited, but can be appropriately selected from a melt kneading temperature of 200 to 370 ° C. and a screw rotation speed of 100 to 1200 rpm.

  Although the raw material supply apparatus for supplying a raw material to this twin-screw extruder is not specifically limited, Specifically, a single screw feeder, a twin screw feeder, a table feeder, a rotary feeder, etc. can be used. Of these, the loss-in-weight feeder is preferable because of less fluctuation error in the raw material supply.

  Moreover, when supplying a liquid raw material, it can knead | mix by sending a liquid raw material directly into a cylinder system using a liquid addition pump etc. to an extruder cylinder part. At this time, as a method for feeding the liquid raw material, a method using a liquid pump is preferable, and the liquid pump includes a gear pump, a flange type pump, and the like, and a gear pump is preferable. Furthermore, in order to feed the liquid raw material, the tank that stores the liquid raw material used for the liquid pump, the pipe between the tank and the pump, the pipe between the pump and the extruder cylinder, etc. If it is used after heating and heating, etc., to reduce the viscosity of the liquid raw material slightly, the load applied to the liquid pump is reduced, which is preferable in terms of operability.

It is preferable that the manufacturing method of the resin composition which concerns on this embodiment is a manufacturing method containing the following processes 1 and 2 from a flame-retardant viewpoint.
(Step 1): Polymer block A mainly composed of (a) polypropylene resin, less than 50% of required amount, (b) polyphenylene ether resin, (c) vinyl aromatic compound, and 1,2-vinyl Hydrogenation in which at least a part of a block copolymer comprising a block B containing a conjugated diene compound mainly comprising 30 to 90% of the total amount of bonds and 3,4-vinyl bonds is hydrogenated A step of melt-kneading the block copolymer and (e) a metal oxide.
(Step 2): (a) A step of adding the remainder of the polypropylene resin to the melt-kneaded product obtained in (Step 1) and melt-kneading.
In addition, the order in which (d) the phosphate ester flame retardant is melt-kneaded is not particularly limited, and the phosphate ester flame retardant is melt-kneaded where it is a manufacturing method including (Step 1) and (Step 2). May be.

〔Molding〕
The molded article of this embodiment contains the above-mentioned resin composition, and can be obtained by molding this. 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 OA equipment, electronic equipment, battery electrical equipment materials, and the like. Although it does not specifically limit as a shaping | molding method, For example, well-known shaping | molding methods, such as injection molding, hollow shaping | molding, extrusion molding, sheet shaping | molding, film shaping | molding, can be used.

  EXAMPLES Hereinafter, although an Example demonstrates embodiment of this invention, this invention is not limited by these Examples. In addition, the used raw material is as follows.

(A) Polypropylene resin MA4AHB (manufactured by Nippon Polypro)
Melt flow rate (230 ° C., load 2.16 kg) = 5.9 g / 10 min
Here, the melt flow rate was measured by the same method as described later.

(B) Polyphenylene ether resin Polyphenylene ether having a reduced viscosity (0.5 g / dL chloroform solution, measured at 30 ° C.) = 0.3, obtained by oxidative polymerization of 2,6-xylenol.

(C) Hydrogenated block copolymer Polystyrene (polymer block A) -hydrogenated polybutadiene (polymer block B) -polystyrene (polymer block A), with a bound styrene content of 43% by mass, polybutadiene The total amount of 1,2-vinyl bonds and 3,4-vinyl bonds in the part (polymer block B) is 75%, the number average molecular weight of polystyrene chains is 20,000, and the hydrogenation rate of the polybutadiene part is 99.9% hydrogenated block copolymer.

(Measurement method of vinyl bond amount)
The amount of vinyl bonds in the polybutadiene moiety was measured with an infrared spectrophotometer, and the calculation method was Analytical Chemistry, Volume 21, No. 8, according to the method described in August 1949. The amount of bound styrene was measured with an ultraviolet spectrophotometer. Furthermore, the number average molecular weight of the polystyrene chain was measured by GPC (moving layer: tetrahydrofuran, standard material: polystyrene). Furthermore, the hydrogenation rate of the polybutadiene portion was measured by NMR.

(D) Phosphate ester flame retardant (d-1) Condensed phosphate ester: E890 (manufactured by Daihachi Chemical Industry)
(D-2) Phosphate ester: TPP (manufactured by Daihachi Chemical Industry)

(E) Metal oxide (e-1) Iron oxide: Iron trioxide (Fe ₂ O ₃ : Wako Pure Chemical Industries)
(E-2) Zinc oxide: Zinc oxide (ZnO: Wako Pure Chemical Industries, Ltd.)

(F) Phenoxyphosphazene: Rabitle FP110 (Fushimi Pharmaceutical)

<Example 1>
As a resin composition production apparatus, a twin screw extruder ZSK-25 (manufactured by Coperion) was used. In the twin-screw extruder, a first raw material supply port is provided upstream of the raw material flow direction, a second raw material supply port is provided downstream of the first raw material supply port, and a liquid feed pump is provided further downstream. A vacuum vent was provided between the supply ports and downstream of the liquid pump. 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.

  To the twin-screw extruder set as described above, the components (a) to (e) are supplied in the composition shown in Table 1, conditions of extrusion temperature 270 to 320 ° C., screw rotation speed 300 rpm, discharge rate 15 kg / hour And kneaded to obtain pellets of the resin composition.

<Examples 2 to 6>
Resin composition pellets were obtained in the same manner as in Example 1 except that the components (a) to (e) were supplied to the twin-screw extruder at the composition shown in Table 1.

<Comparative Examples 1-5>
Resin composition pellets were obtained in the same manner as in Example 1 except that the components (a) to (f) were supplied to the twin-screw extruder at the compositions shown in Table 1.

  The characteristics of the pellets of the resin compositions obtained in Examples and Comparative Examples were evaluated as follows. The results are shown in Table 1.

<Flame retardance>
Based on the UL-94 vertical combustion test, flame retardancy was evaluated using an injection molded test piece having a thickness of 1.6 mm.

<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.

<Load deflection temperature (DTUL)>
The resin composition pellets obtained in the examples and comparative examples were supplied to a screw in-line injection molding machine set at 240 to 220 ° C., and injection molded under the conditions of a mold temperature of 60 ° C. Molded pieces were molded. The obtained molded piece was left to stand in an environment of 80 ° C. for 24 hours using a gear oven and subjected to heat history treatment. The molded piece after the heat history treatment was cut into 80 mm × 10 mm × 4 mm, and the deflection temperature under load (DTUL) was measured at 1.80 MPa according to ISO 75.

  The results are shown in Table 1.

  The resin composition pellets obtained in Examples 1 to 6 were all excellent in the balance of flame retardancy, heat resistance, and fluidity. Comparative Examples 1, 3, and 5 were incombustible, Comparative Example 2 was heat resistant, and Comparative Example 4 was inferior in fluidity. As mentioned above, it was shown that the resin composition which concerns on this embodiment is excellent in a flame retardance, fluidity | liquidity, and heat resistance balance.

  The flame-retardant resin composition according to the present invention has an excellent balance of flame retardancy, fluidity, and heat resistance, and can be suitably used for various applications that require these characteristics. It is optimally used for electronic equipment, battery electrical equipment materials, etc.

Claims (7)

(A) 40-20 parts by mass of polypropylene resin;
(B) including 60 to 80 parts by mass of a polyphenylene ether resin,
For a total amount of 100 parts by mass of the component (a) and the component (b),
(C) The polymer block A mainly composed of vinyl aromatic compound units, the total amount of 1,2-vinyl bonds and 3,4-vinyl bonds is 30 to 90%, and conjugated diene compound units 1 to 20 parts by mass of a hydrogenated block copolymer in which at least a part of a block copolymer including the polymer block B as a main component is hydrogenated;
(D) 25 to 45 parts by mass of a phosphate ester flame retardant;
(E) 0.5 to 10 parts by mass of a metal oxide,
A resin composition having flame retardancy of V-1 or higher. In a total of 100 parts by mass of the component (a) and the component (b),
35 to 25 parts by mass of the component (a),
The resin composition according to claim 1, comprising 65 to 75 parts by mass of the component (b).   The resin composition according to claim 1 or 2, wherein a total amount of the 1,2-vinyl bond amount and the 3,4-vinyl bond amount is 65 to 90%.   The resin composition according to any one of claims 1 to 3, wherein the component (d) is a condensed phosphate ester flame retardant.   The resin composition according to any one of claims 1 to 4, wherein the component (e) is iron oxide.   The resin composition according to any one of claims 1 to 5, wherein the flame retardancy is V-0 or more.   The molded article containing the resin composition of any one of Claims 1-6.