JP2014210839A - Flame-retardant resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composition excellent in balance among flame retardancy, fluidity and heat resistance.SOLUTION: The resin composition comprises: (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 hydrogenated block copolymer in which at least a part of a block copolymer containing a block copolymer A composed mainly of 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 composed mainly of a conjugated diene compound unit is subjected to hydrogenation based on the total 100 pts.mass of the (a) component and the (b) component; (d) 5 to 25 pts.mass of a phosphate ester-based flame retardant; (e) 0.1 to 12 pts.mass of a phosphinic acid salt; and (f) 0.1 to 5 pts.mass of a metal oxide.

Description

  The present invention relates to a flame retardant resin composition.

  Polyphenylene ether (hereinafter referred to as “PPE”) is known as an engineering plastic, and polypropylene is known as a general-purpose plastic widely used in the fields of automobile parts, electrical / electronic equipment parts, home appliances, and the like. Yes. Therefore, if these two resins are blended to complement each other's disadvantages and bring out the advantages, it is possible to further provide an excellent resin material in a wide field of use, and its industrial significance is very large.

  However, blending with polypropylene has a problem that the excellent flame retardancy inherent to PPE is impaired. For example, Patent Document 1 describes a resin composition containing a metal oxide and a pentavalent phosphorus compound as a flame retardant.

JP 2006-016587 A

  However, in order to solve the above-described problems related to the reduction in flame retardancy of blend compositions of PPE and polypropylene, conventionally, a method of adding a halogen compound or antimony trioxide has been used. There is still room for improvement. Furthermore, from the viewpoint of environmental hygiene, there is a demand to reduce the addition of halogen compounds and antimony trioxide as much as possible. Furthermore, regarding the technique of Patent Document 1, etc., the present inventors examined a resin composition obtained by adding a metal oxide and a pentavalent phosphorus compound to a blend composition of PPE and polypropylene. Even if it could be improved, it was found that there was a problem that the fluidity and heat resistance were not satisfactory.

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

  As a result of intensive studies to solve the above problems, the present inventors have found that a blend ratio of a polypropylene resin and a polyphenylene ether resin includes a specific proportion of a phosphate ester flame retardant, a phosphinate, and a metal oxide. When it mix | blended with, it acquired knowledge that it was excellent in the balance of a flame retardance, fluidity | liquidity, and heat resistance, and came to make this invention.

That is, the present invention is as follows.
[1]
(A) 40-20 parts by mass of polypropylene resin;
(B) 60-80 parts by mass of a polyphenylene ether resin,
Including
For 100 parts by mass of the total amount 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 mainly composed of conjugated diene compound units 1 to 20 parts by mass of a hydrogenated block copolymer obtained by hydrogenating at least a part of a block copolymer comprising
(D) 5 to 25 parts by mass of a phosphate ester flame retardant,
(E) 0.1-12 parts by mass of a phosphinate,
(F) 0.1 to 5 parts by mass of a metal oxide,
A resin composition comprising:
[2]
The resin composition according to [1], wherein the component (f) is iron oxide.
[3]
With respect to 100 parts by mass of the total amount of the component (a) and the component (b),
The content of the component (a) is 35 to 25 parts by mass,
The resin composition according to [1] or [2], wherein the content of the component (b) is 65 to 75 parts by mass.
[4]
Any one of [1] to [3], wherein the total amount of the 1,2-vinyl bond and 3,4-vinyl bond in the polymer block B of the component (c) is 65 to 90%. 2. The resin composition according to item 1.
[5]
The resin composition according to any one of [1] to [4], wherein the component (d) is a condensed phosphate ester flame retardant.
[6]
The resin composition according to any one of [1] to [5], wherein the component (e) is an aluminum dialkylphosphinate.
[7]
[1] A molded article comprising the resin composition according to any one of [6].

  ADVANTAGE OF THE INVENTION According to this invention, the resin composition excellent in the flame retardance, fluidity | liquidity, and heat 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, this invention is not limited to the following embodiment, It can implement by changing variously within the range of the summary.

  Further, in the following, unless otherwise specified, a structural unit constituting a polymer is described as “˜unit”, and a monomer component before polymerization is described by a compound name.

(Resin composition)
The resin composition of the present 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 component (a) and 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 obtained by hydrogenating at least a part of a block copolymer including a polymer block B as a main component,
(D) 5 to 25 parts by mass of a phosphate ester flame retardant,
(E) 0.1-12 parts by mass of a phosphinate,
(F) A resin composition containing 0.1 to 5 parts by mass of a metal oxide. The resin composition of this embodiment is excellent in the balance of flame retardancy, fluidity, and heat resistance.

In the resin composition of the present embodiment, in 100 parts by mass of the total amount of the component (a) and the component (b), the content of the component (a) is 40 to 20 parts by mass, and the content of the component (b) is 60. It is -80 mass parts, Preferably content of (a) component is 35-25 mass parts, and content of (b) component is 65-75 mass parts.
When the content of the component (a) and the component (b) is within these ranges, the flame retardancy, heat resistance, solvent resistance, and gas barrier properties of the resin composition are further improved.

<(A) component>
(A) The polypropylene resin (hereinafter sometimes abbreviated as “PP”) is not particularly limited, and may be, for example, a propylene homopolymer (polypropylene homopolymer) or a combination of propylene and another monomer. It may be a copolymer (propylene copolymer). Among these, a crystalline polypropylene homopolymer and a crystalline propylene-ethylene block copolymer are preferable. Here, the “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 other in the second and subsequent steps of polymerization. And a propylene-ethylene random copolymer portion obtained by copolymerizing an α-olefin (for example, butene-1, hexene-1, etc.).

  The manufacturing method of (a) component is not specifically limited, A well-known thing can also be used. For example, a method of polymerizing under conditions of a polymerization temperature of 0 to 100 ° C. and a polymerization pressure of 3 to 100 atm 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. Etc. At this time, a chain transfer agent such as hydrogen can be added in order to adjust the molecular weight of the polymer. The polymerization method is not particularly limited, and for example, either a batch method or a continuous method is possible. The polymerization method is not particularly limited, and examples thereof include solution polymerization under a solvent such as butane, pentane, hexane, heptane, and octane, and slurry polymerization. Furthermore, bulk polymerization without a solvent in a monomer, a gas phase polymerization method without a solvent in a gaseous monomer, and the like are also included.

  In order to increase the isotacticity and polymerization activity of the resulting polypropylene, in addition to the polymerization catalyst described above, an electron donating compound can be further used as an internal donor component or an external donor component. These electron-donating compounds are not particularly limited, and include, for example, ester compounds such as ε-caprolactone, methyl methacrylate, ethyl benzoate, and methyl toluate; phosphorus phosphites such as triphenyl phosphite and tributyl phosphite. Acid esters; 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 various phenols.

  Component (a) is a modified polypropylene resin obtained by grafting and / or adding an α, β-unsaturated carboxylic acid and / or a derivative thereof (for example, acid anhydride or ester) to the above-described polypropylene resin. May be. Such a modified polypropylene resin is not particularly limited, and may be, for example, the above-described polypropylene resin and an α, β-unsaturated carboxylic acid and / or at a temperature of 30 to 350 ° C. in a molten state, a solution state, or a slurry state. Or it is obtained by making it react with the derivative (s). These may be in the presence or absence of a radical generator. The modified polypropylene resin is not particularly limited, but is preferably a modified polypropylene resin having an α, β-unsaturated carboxylic acid and / or derivative thereof grafted or added in an amount of 0.01 to 10% by mass relative to the whole. is there. Such a modified polypropylene resin may be used in combination with an unmodified polypropylene resin.

  The crystal state of the component (a) is not particularly limited. Further, the melting point of the component (a) is not particularly limited. As the component (a), these may be used alone or in combination of two or more.

  (A) A component can be identified and quantified by solvent extraction and infrared absorption analysis (IR) described later.

<(B) component>
(B) The polyphenylene ether resin (hereinafter sometimes abbreviated as “PPE”) is not particularly limited, and may be a phenylene ether homopolymer (polyphenylene ether homopolymer), or phenylene ether and other monomers. And 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. 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. It is.

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.

  The component (b) is not particularly limited, and examples thereof include poly (2,6-dimethyl-1,4-phenylene ether), poly (2-methyl-6-ethyl-1,4-phenylene ether), and poly ( Homopolymers such as 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, , 2,3,6-trimethylphenol, 2-methyl-6-butylphenol) and the like. 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).

  The manufacturing method of (b) component is not specifically limited, A conventionally well-known thing can also be used. For example, it can be easily produced by, for example, a method of oxidative polymerization of 2,6-xylenol using a complex of cuprous salt and amine described in US Pat. No. 3,306,874 as a catalyst. Alternatively, U.S. Pat. No. 3,306,875, U.S. Pat. No. 3,257,357, U.S. Pat. No. 3,257,358, Japanese Examined Patent Publication No. 52-017808, Japanese Laid-Open Patent Publication No. 50-051197, Japanese Laid-Open Patent Publication No. 63-152628. It can be produced by a method described in a publication or the like.

  Further, the component (b) may be a modified polyphenylene ether resin obtained by grafting and / or adding a styrene monomer and / or a derivative thereof to the above polyphenylene ether resin. Such a modified polyphenylene ether resin is not particularly limited. For example, the polyphenylene ether resin and the styrenic monomer and / or derivative thereof at 80 to 350 ° C. in a molten state, a solution state, or a slurry state. It can be obtained by reacting. These may be in the presence or absence of a radical generator. Although it does not specifically limit as modified polyphenylene ether resin, Preferably, the modified polyphenylene ether resin etc. which the styrene-type monomer and / or its derivative grafted and / or added 0.01 to 10 mass% with respect to the whole are mentioned. . Such a modified polyphenylene ether resin may be used in combination with an unmodified polyphenylene ether resin. When the above-mentioned polyphenylene ether resin and modified polyphenylene ether resin are used in combination, the mixing ratio thereof is not limited and can be mixed at an arbitrary ratio.

  (B) The component can be identified and quantified by solvent extraction and infrared absorption analysis (IR), which will be described later.

  It is preferable that the resin composition of this embodiment further contains any one selected from the group consisting of polystyrene, syndiotactic polystyrene, and high impact polystyrene as the other component. By using the component (b) and these resins in combination, the moldability can be further improved. From this viewpoint, it is more preferable that polystyrene, syndiotactic polystyrene, and high-impact polystyrene are included in a total amount of 400 parts by mass or less with respect to 100 parts by mass of the component (b).

<(C) component>
(C) The hydrogenated block copolymer has 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 is 30 to 90%. And a hydrogenated block copolymer in which 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)
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%. The ratio of the vinyl aromatic compound unit in the polymer block A is preferably 60% by mass or more, more preferably 70% by mass or more, still more preferably 90% by mass or more, and still more preferably 100% by mass. %. By making the ratio of a vinyl aromatic compound unit into the said range, fluidity | liquidity, impact resistance, weld, and an external appearance improve further.

  The polymer block A preferably includes a homopolymer block of a vinyl aromatic compound and / or a copolymer block of a vinyl aromatic compound and a conjugated diene compound.

  The vinyl aromatic compound constituting the polymer block A is not particularly limited, and examples thereof include styrene, α-methylstyrene, vinyltoluene, p-tert-butylstyrene, diphenylethylene and the like. Of these, styrene is preferred. These may be used alone or in combination of two or more.

  The conjugated diene compound copolymerizable with the vinyl aromatic compound is not particularly limited. For example, a conjugated diene compound that can be used in the polymer block B described later can also be used in the polymer block A.

  The number average molecular weight of the polymer block A is not particularly limited, but is preferably 15,000 or more, more preferably 15,000 or more and 30,000 or less. When the number average molecular weight is in the above range, the heat resistant creep resistance of the resin composition is further improved. The number average molecular weight of the polymer block A can be measured by gel permeation chromatography (GPC, mobile phase: tetrahydrofuran, standard material: polystyrene).

(Polymer block B)
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%. The ratio of the conjugated diene compound unit in the polymer block B is preferably 60% by mass or more, more preferably 70% by mass or more, still more preferably 90% by mass, and still more preferably 100% by mass. is there. By setting the ratio of the conjugated diene compound unit within the above range, the fluidity, impact resistance, weld, and appearance are further improved.

  The polymer block B mainly composed of a conjugated diene compound unit preferably includes a homopolymer block of a conjugated diene compound and / or a random copolymer block of a conjugated diene compound and a vinyl aromatic compound.

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

  Regarding the microstructure of the polymer block B (bonded form of the conjugated diene compound), the total amount of 1,2-vinyl bonds and 3,4-vinyl bonds (hereinafter referred to as “total vinyl bond amount”) is 30 to 30. 90%, preferably 45 to 90%, more preferably 65 to 90%. Here, “total amount of 1,2-vinyl bond and 3,4-vinyl bond” refers to 1,2-addition, 3,4-addition, and 1,4-addition in polymer block B. Among the conjugated diene compound units being used, it means the mol% of the 1,2-added or 3,4-added conjugated diene compound units. 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 further improved.

  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 from the viewpoint of fluidity, impact resistance, weld, and appearance. It is preferable that it is -90%.

  In the present embodiment, the total vinyl bond amount can be measured by infrared absorption analysis (IR). In addition, the calculation method of total vinyl bond amount is 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. Examples of (A-B-) ₄ Si include a reaction residue of a polyfunctional coupling agent such as silicon tetrachloride and 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 the conjugated diene compound in the molecular chain in each polymer block is not particularly limited. For example, random, tapered (monomer along the molecular chain) The component is increased or decreased), partially in a block form, 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 component (c), the content of the vinyl aromatic compound unit bonded to the block copolymer before hydrogenation is not particularly limited, but is preferably 20 from the viewpoint of fluidity, impact resistance, weld, and appearance. It is -95 mass%, More preferably, it is 30-80 mass%. In the present embodiment, the content of the vinyl aromatic compound unit can be measured with an ultraviolet spectrophotometer.

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

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

  (C) Although the hydrogenation rate with respect to the conjugated diene compound unit in a component is not specifically limited, From a heat resistant viewpoint, Preferably it is 50% or more of the double bond derived from a conjugated diene compound unit, More preferably, 80 % Or more, more preferably 90% or more. The hydrogenation rate can be measured by a nuclear magnetic resonance apparatus (NMR).

  (C) The manufacturing method of a component is not specifically limited, For example, it can obtain with a well-known manufacturing method. Examples of such devices include JP-A-47-011486, JP-A-49-066743, JP-A-50-075651, JP-A-54-126255, JP-A-56- No. 010542, JP 56-062847, JP 56-1000084, JP 02-300188, British Patent 1130770, US Pat. No. 3,281,383, US Pat. No. 3639517 No. 1, British Patent No. 1020720, US Pat. No. 3,333,024, US Pat. No. 4,501,857, and the like can be used.

  As the component (c), α, β-unsaturated carboxylic acid and / or a derivative thereof (for example, an ester compound or an acid anhydride compound) is grafted and / or added to the hydrogenated block copolymer. A modified hydrogenated block copolymer may also be used. Such a modified hydrogenated block copolymer is not particularly limited, and for example, in the molten state, the solution state or the slurry state, at 80 to 350 ° C., the above-mentioned hydrogenated block copolymer and α, β-unsaturated copolymer. It can be obtained by reacting with a saturated carboxylic acid and / or a derivative thereof. These may be in the presence or absence of a radical generator. Such a modified hydrogenated block copolymer may be used in combination with an unmodified hydrogenated block copolymer. Component (c) may be a mixture in any proportion of the hydrogenated block copolymer and the modified hydrogenated block copolymer.

  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 content of the component (c) is 1 to 20 parts by mass, preferably 3 to 18 parts by mass, more preferably 5 to 15 parts per 100 parts by mass of the total amount of the components (a) and (b). Part by mass. (C) The impact resistance of a resin composition, a bending elastic modulus, etc. improve further because the compounding quantity of a component exists in the said range.

  (C) The component can be identified and quantified by solvent extraction and infrared absorption analysis (IR) described later.

<(D) component>
(D) The phosphate ester flame retardant is not particularly limited, and for example, trimethyl phosphate, triethyl phosphate, tripropyl phosphate, tributyl phosphate, tripentyl phosphate, trihexyl phosphate, tricyclohexyl phosphate, triphenyl phosphate, tricres Phosphate ester compounds such as dil 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 Modified phosphoric acid ester compounds; various condensed phosphoric acid ester-based flame retardants. 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 the formula, Q ¹ , Q ² , Q ³ , and Q ⁴ each independently represent an alkyl group having 1 to 6 carbon atoms, 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 It is an integer of 0-3.

  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.

In which 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; 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 phosphate ester having n of 1 in a total amount of 50% by mass or more. preferable. By using these condensed phosphate esters, the volatility during the molding process of the resin composition can be further reduced.

  (D) A commercial item can also be used as a component. Examples of such commercially available products include “TPP” (produced by Daihachi Chemical Industry Co., Ltd.) which is a phosphate ester, “E890”, “PX-200” and “CR-733S” which are condensed phosphate esters (any Also manufactured by Daihachi Chemical Industry Co., Ltd.). Note that these commercially available products may contain surplus components other than the above-described components as long as the effects of the present embodiment are not impaired.

  The content of the component (d) with respect to 100 parts by mass of the total amount of the components (a) and (b) is 5 to 25 parts by mass, preferably 6 to 20 from the viewpoint of flame retardancy and heat resistance balance. It is a mass part, More preferably, it is 10-20 mass parts, More preferably, it is 15-20 mass parts.

(D) The component can be identified and quantified by solvent extraction, ¹ H-NMR, and ³¹ P-NMR, which will be described later.

<(E) component>
(E) The phosphinic acid salt is not particularly limited. For example, the phosphinic acid salt represented by the following formula (4), the phosphinic acid salt represented by the following formula (5), and the group consisting of these polymers. There may be mentioned at least one selected.

(In Formula (4), Q ⁵ and Q ⁶ each independently represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aryl group, or an aryloxy group. , N are each independently an integer of 1 to 3. M is any one selected from the group consisting of metal atoms, amide groups, ammonium groups, and melamine derivatives after the fourth period of the periodic table. Represents a group of species, and when n is 2, they may be the same group or different groups.)

(In Formula (5), Q < ⁷ > and Q < ⁸ > respectively independently represent a hydrogen atom, a C1-C12 alkyl group, a C1-C12 alkoxy group, an aryl group, or an aryloxy group. Q ⁹ represents any one group selected from the group consisting of alkylene having 1 to 18 carbon atoms, arylalkylene, arylene, alkylarylene, and diarylene, and n and m are each independently 1 And x is an integer of 1 to 2. M is any one selected from the group consisting of a metal atom, an amide group, an ammonium group, and a melamine derivative after the fourth period of the periodic table. A group of a species, and when x is 2, they may be the same group or different groups.)

  Examples of the phosphinic acid salts include phosphinic acid metal salts produced in an aqueous solution using phosphinic acid and metal carbonates, metal hydroxides or metal oxides. Depending on the reaction conditions, these may be polymeric phosphinates having a degree of condensation of 1 to 3 depending on the environment.

  The phosphinic acid is not particularly limited. For example, dimethylphosphinic acid, ethylmethylphosphinic acid, diethylphosphinic acid, methyl-n-propylphosphinic acid, methandi (methylphosphinic acid), benzene-1,4- (dimethylphosphinic acid) ), Methylphenylphosphinic acid, diphenylphosphinic acid and the like.

  In addition, the metal component as M in the formula (4) and the formula (5) is not particularly limited as the metal atoms after the fourth period of the periodic table, but preferably the periodic table excluding alkali metals such as potassium and cesium. A metal element after the fourth period, more preferably, a metal carbonate, metal hydroxide, or magnesium, calcium, aluminum, tin, germanium, titanium, iron, zirconium, zinc, bismuth, strontium, or manganese, or It is a metal oxide, More preferably, a metal carbonate, a metal hydroxide, or a metal oxide containing calcium, magnesium, aluminum, titanium, or zinc is mentioned.

  Such phosphinates are not particularly limited, and examples thereof include dimethylphosphinates such as calcium dimethylphosphinate, magnesium dimethylphosphinate, aluminum dimethylphosphinate, zinc dimethylphosphinate; calcium ethylmethylphosphinate, ethylmethyl Ethyl methylphosphinates such as magnesium phosphinate, aluminum ethylmethylphosphinate, zinc ethylmethylphosphinate; diethyl such as calcium diethylphosphinate, magnesium diethylphosphinate, aluminum diethylphosphinate, zinc diethylphosphinate, titanium diethylphosphinate Phosphinates; calcium methyl-n-propylphosphinate, magnesium methyl-n-propylphosphinate, methyl-n-propyl Methyl-n-propylphosphinates such as aluminum pyrphosphinate, zinc methyl-n-propylphosphinate, titanium methyl-n-propylphosphinate; methandi (methylphosphinic acid) calcium, methandi (methylphosphinic acid) magnesium, methandi Methanodi (methylphosphinic acid) salts such as (methylphosphinic acid) aluminum, methanedi (methylphosphinic acid) zinc, methandi (methylphosphinic acid) titanium; benzene-1,4- (dimethylphosphinic acid) calcium, benzene-1,4 -Benzene such as (dimethylphosphinic acid) magnesium, benzene-1,4- (dimethylphosphinic acid) aluminum, benzene-1,4- (dimethylphosphinic acid) zinc, benzene-1,4- (dimethylphosphinic acid) titanium; 1 4- (dimethylphosphinic acid) salt; methylphenylphosphinic acid calcium such as calcium methylphenylphosphinate, magnesium methylphenylphosphinate, aluminum methylphenylphosphinate, zinc methylphenylphosphinate, titanium methylphenylphosphinate; calcium diphenylphosphinate, etc. And diphenylphosphinates such as magnesium diphenylphosphinate, aluminum diphenylphosphinate, zinc diphenylphosphinate and titanium diphenylphosphinate.

  Of these, aluminum dialkylphosphinate is particularly preferable from the viewpoint of flame retardancy. Examples of the aluminum dialkylphosphinate include aluminum diethylphosphinate, aluminum dimethylphosphinate, aluminum ethylmethylphosphinate, and aluminum methyl-n-propylphosphinate. Among these, from the viewpoint of flame retardancy, aluminum diethylphosphinate, aluminum dimethylphosphinate, aluminum ethylmethylphosphinate and the like are preferable.

  The content of the component (e) is 0.1 to 12 parts by mass, preferably 0.1 to 15 parts by mass with respect to 100 parts by mass of the total amount of the component (a) and the component (b). From a viewpoint of property and fluidity | liquidity, More preferably, it is 3-10 mass parts.

  (E) A component can be identified and quantified by solvent extraction, X-ray fluorescence analysis (XRF), and X-ray diffraction (XRD), which will be described later.

<Component (f)>
(F) The metal oxide is not particularly limited, and examples thereof include zinc oxide, iron oxide, tin oxide, calcium oxide, magnesium oxide, aluminum oxide, copper oxide, and titanium oxide. Among these, iron oxide is preferable from the viewpoint of flame retardancy. These may be used alone or in combination of two or more. Further, these metal oxides may be used after being coated with an arbitrary inorganic and / or organic substance.

  The number average particle size of the component (f) is preferably 100 μm or less, more preferably 50 μm or less, still more preferably 10 μm or less, and even more preferably 5 μm or less, from the viewpoint of impact resistance and appearance. More preferably, it is 1 μm or less, but is not limited thereto. The number average particle size can be measured by dispersing the component (f) in water using a laser diffraction particle size distribution analyzer (for example, trade name “SALD-2000” manufactured by Shimadzu Corporation). . The dispersion liquid of the component (f) in water can be prepared by using a stirring tank equipped with an ultrasonic diffuser and / or a stirrer. The prepared dispersion is fed to a measurement cell, and the particle diameter is measured by laser diffraction. The number average particle size can be calculated from the obtained particle size and the frequency distribution of the number of particles.

  From the viewpoint of flame retardancy, the content of component (f) with respect to 100 parts by mass of component (a) and component (b) is 0.1 to 5 parts by mass, preferably 0.5 to 4 parts. It is a mass part, More preferably, it is 1-3 mass parts. When the content of the component (f) is in the above range, the obtained resin composition exhibits more excellent flame retardancy.

  (F) The component can be identified and quantified by solvent extraction, X-ray fluorescence analysis (XRF), and X-ray diffraction (XRD), which will be described later.

<Identification and quantification method of each component>
Each component can be identified and quantified by the following method. The sample is subjected to solvent extraction with chloroform, and the weight ratio of soluble and insoluble components is determined. Here, the soluble component contains the component (b), the component (c), and the component (d), and the insoluble component contains the component (a), the component (e), and the component (f). With respect to the chloroform-soluble component, each component is separated by GPC (solvent: chloroform) and dried to obtain the weight ratio of each component. Further, the component (b) and the component (c) can be identified by IR, and the component (d) can be identified by ¹ H-NMR and ³¹ P-NMR. The chloroform insoluble matter is extracted with HFIP (1,1,1,3,3,3-hexafluoro-2-propanol). HFIP solubles contain component (e) and can be identified by XRF and XRD. The HFIP-insoluble component is put into a filtration filter and immersed in xylene at a temperature of 150 ° C., so that the HFIP-insoluble component is divided into a hot xylene-soluble (a) component and an insoluble (f) component. The component (a) can be identified by IR, and the component (f) can be identified by XRF and XRD. Moreover, the above-mentioned HFIP soluble component, hot xylene soluble component, and hot xylene insoluble component can be dried, and the weight of these components can be measured to determine the weight ratio of each component. Based on the above results, the weight ratio of each component can be calculated.

<Additives>
In the resin composition of this embodiment, you may further contain other flame retardants other than (d) component. Such other flame retardants include non-halogen or non-antimony flame retardants. Specific examples of such flame retardants are not particularly limited, for example, metal hydroxides such as magnesium hydroxide, aluminum hydroxide, calcium hydroxide, calcium aluminate; melamine, melam, melem, melon, polyphosphoric acid Melamine, methylene dimelamine, ethylene dimelamine, decamethylene dimelamine, 1,3-cyclohexyl dimelamine, 4,4'-diethylene dimelamine, diethylene trimelamine, benzoguanamine, dibenzoguanamine, succinoguanamine, methylguanamine, acetoguanamine Melamine resin, etc .; cyanurate, sulfate, 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-to Triazine compounds such as lyazine, 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 and kaolin clay And inorganic silicon compounds such as talc and wollastonite. It is possible to further improve the flame retardancy by adding these.

  In the resin composition of this embodiment, a filler can be blended for the purpose of improving the mechanical properties. Such filler is not particularly limited, for example, silica, kaolin clay, talc, wollastonite, titanium oxide, glass beads, glass flakes, glass fiber, calcium carbonate, barium carbonate, calcium sulfate, barium sulfate, Examples thereof include calcium silicate, potassium titanate, aluminum borate, magnesium borate; fibrous reinforcing agents such as kenaf fiber, carbon fiber, silica fiber, alumina fiber, and quartz fiber; non-fibrous reinforcing agent. These may be covered with an organic substance, an inorganic substance, or the like.

  The resin composition of the present embodiment provides other properties such as rigidity and dimensional stability, so other additives such as plasticizers, antioxidants, and stabilizers such as ultraviolet absorbers and light stabilizers, Curing agent, curing accelerator, antistatic agent, conductivity imparting agent, stress relaxation agent, mold release agent, crystallization accelerator, hydrolysis inhibitor, lubricant, impact imparting agent, slidability improving agent, compatibilizing agent , A nucleating agent, a reinforcing agent, a reinforcing agent, a flow regulator, a dye, a sensitizer, a coloring pigment, a rubbery polymer, a conductive polymer, and the like.

[Method for producing resin composition]
The manufacturing method of the resin composition of this embodiment is not specifically limited, For example, the method of melt-kneading each above-mentioned component using a twin-screw extruder is mentioned. Specific examples of such a twin screw extruder are not particularly limited, and examples thereof include a ZSK series manufactured by Coperion, a TEM series manufactured by Toshiba Machine, a TEX series manufactured by Nippon Steel Works, and the like.

  The 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.

The method for producing a resin composition of the present embodiment includes the following step 1 and step 2 from the viewpoint of flame retardancy, and the component (d) is added in step 1, step 2, or both steps thereof. A production method is preferred.
(Step 1): Step of melt-kneading component (a) less than 50% by mass of the total amount, component (b), component (c), and component (f) of the total amount;
(Step 2): Step of adding the remainder of component (a) and the total amount of component (e) to the melt-kneaded product obtained in (Step 1), and melt-kneading.

  In addition, the order which melt-kneads (d) component is not specifically limited, What is necessary is just the manufacturing method containing (process 1) and (process 2), and (d) component may melt-knead anywhere.

〔Molding〕
The resin composition of this embodiment can be formed into a molded product by molding it. Although it does not specifically limit as a shaping | molding method, For example, well-known shaping | molding methods, such as injection molding, hollow shaping | molding, extrusion molding, sheet shaping | molding, film shaping | molding, can also be used. Molded articles obtained by molding the above-described resin composition can be used as various molded articles, and in particular, can be suitably used for OA equipment, electronic equipment, battery electrical equipment 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 40 to 100 ° C. It is not limited to these.

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

(A) Polypropylene resin Propylene homopolymer (manufactured by Nippon Polypro, "MA4AHB")
Melt flow rate (MFR; 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 (b-1) Reduced viscosity (0.5 g / dL chloroform solution, measured at 30 ° C.) 0.3 poly (2,6-dimethyl-1,4-phenylene ether)
(B-2) Reduced viscosity (0.5 g / dL chloroform solution, measured at 30 ° C.) 0.4 poly (2,6-dimethyl-1,4-phenylene ether)
(B-3) Reduced viscosity (0.5 g / dL chloroform solution, measured at 30 ° C.) 0.5 poly (2,6-dimethyl-1,4-phenylene ether)

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

(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. Further, the number average molecular weight of the polystyrene chain was measured by GPC (mobile phase: tetrahydrofuran, standard substance: polystyrene). Furthermore, the hydrogenation rate of the polybutadiene portion was measured by NMR.

(D) Phosphate ester flame retardant (d-1) Condensed phosphate ester: “E890” (condensed phosphate ester represented by the following formula) manufactured by Daihachi Chemical Industry Co., Ltd.
(D-2) Phosphate ester: “TPP” (phosphate ester represented by the following formula) manufactured by Daihachi Chemical Industry Co., Ltd.

(E) Phosphinate (e-1) “Exolit OP1230” (aluminum dialkylphosphinate represented by the following formula) manufactured by Clariant

(E-2) “Exolit OP1312” manufactured by Clariant

(F) Metal oxide (f-1) Iron (III) oxide (Fe ₂ O ₃ : Wako Pure Chemical Industries, Ltd.)
(F-2) Aluminum oxide (Al ₂ O ₃ : Wako Pure Chemical Industries, Ltd.)
(F-3) Calcium oxide (CaO: Wako Pure Chemical Industries, Ltd.)
(F-4) Zinc oxide (ZnO: Wako Pure Chemical Industries, Ltd.)

<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 was provided upstream of the raw material flow direction. A second raw material supply port was provided downstream of the first raw material supply port. A liquid pump was provided downstream of the second raw material supply port. A first vacuum vent was provided between the first raw material supply port and the second raw material supply port. A second vacuum vent was provided 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 (f) are supplied in the composition shown in Table 1, conditions of extrusion temperature of 270 to 320 ° C., screw rotation speed of 300 rpm, and discharge rate of 15 kg / hour. And kneaded to obtain pellets of the resin composition.

<Examples 2 to 21>
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 with the compositions shown in Tables 1 and 2.

<Comparative Examples 1-7>
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 with the compositions shown in Table 3.

  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. First, the resin compositions obtained in Examples and Comparative Examples were supplied to a screw in-line type injection molding machine (“TOSHIBA Co.,“ IS100GN ”) set at 265 to 245 ° C., and injection was performed at a mold temperature of 60 ° C. By molding, a test piece having a size defined in the standard was prepared. A flame of a gas burner was applied to the prepared test piece, and the degree of combustion was evaluated. As the grade of flame retardancy based on UL94, evaluation was performed based on the criteria of 5VA, 5VB, V-0, V-1, V-2, 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.

<Load deflection temperature (DTUL)>
The pellets of the resin compositions obtained in Examples and Comparative Examples were supplied to a screw in-line type injection molding machine (“TOSHIBA Co.,“ IS100GN ”) set at 265 to 245 ° C., and injection was performed at a mold temperature of 60 ° C. A multi-purpose test piece A-type molded piece was prepared. The obtained molded piece was left to stand in a gear oven set at 80 ° C. for 24 hours to perform a 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.

  Table 1, Table 2, and Table 3 show component compositions and physical property evaluations of the examples and comparative examples.

  It was confirmed that the pellets of the resin composition obtained in each Example were excellent in at least a balance of flame retardancy, heat resistance, and fluidity.

  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) 60-80 parts by mass of a polyphenylene ether resin,
Including
For 100 parts by mass of the total amount 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 mainly composed of conjugated diene compound units 1 to 20 parts by mass of a hydrogenated block copolymer obtained by hydrogenating at least a part of a block copolymer comprising
(D) 5 to 25 parts by mass of a phosphate ester flame retardant,
(E) 0.1-12 parts by mass of a phosphinate,
(F) 0.1 to 5 parts by mass of a metal oxide,
A resin composition comprising:   The resin composition according to claim 1, wherein the component (f) is iron oxide. With respect to 100 parts by mass of the total amount of the component (a) and the component (b),
The content of the component (a) is 35 to 25 parts by mass,
The resin composition according to claim 1 or 2, wherein the content of the component (b) is 65 to 75 parts by mass.   The total amount of the 1,2-vinyl bond amount and 3,4-vinyl bond amount in the polymer block B of the component (c) is 65 to 90%. The resin composition described in 1.   The resin composition according to any one of claims 1 to 4, wherein the component (d) is a condensed phosphate ester flame retardant.   The resin composition according to any one of claims 1 to 5, wherein the component (e) is an aluminum dialkylphosphinate.   The molded article containing the resin composition of any one of Claims 1-6.