JP5503071B1 - Flame retardant polyolefin resin composition, molded product, and method for producing flame retardant polyolefin resin composition - Google Patents

Abstract

[PROBLEMS] To provide a flame retardant polyolefin resin composition, a molded article, and a flame retardant polyolefin resin composition having excellent flame retardancy and excellent appearance, tracking resistance, electrical insulation and chemical resistance. A manufacturing method is provided.
The flame-retardant polyolefin resin composition of the present invention contains the following components (A), (B), (C) and (D) in a predetermined ratio. The component (A) is a polyolefin resin, the component (B) is an amine phosphate, the component (C) is a master batch obtained by melting and kneading PTFE, and the component (D) is represented by the following general formula (1). A phosphate ester compound.
[Selection figure] None

Description

  The present invention relates to a flame retardant polyolefin resin composition, a molded article, and a method for producing the flame retardant polyolefin resin composition.

Brominated flame retardant polyolefin resin composition has good electrical properties such as tracking resistance and electrical insulation and chemical resistance, and also has excellent flame resistance, so chemical resistance is required. It is often used for electrically insulating flame retardant sheets. However, in recent years, environmental problems such as dioxins are concerned about the environmental impact of brominated flame retardants, and substitution of brominated flame retardants with non-halogen flame retardants is required.
In addition, the electrical insulating flame retardant sheet is required to have a thin sheet for the purpose of downsizing and cost reduction of electronic devices. In particular, an electrically insulative flame retardant sheet having a thickness of 0.2 mm and having flame retardancy that passes UL94 V-0 and excellent in chemical resistance and tracking resistance is required depending on the use environment. Yes. However, there is no report that an electrically insulating flame retardant sheet using a non-halogen flame retardant satisfying these conditions has been obtained.

For example, as a non-halogen flame retardant, a polyolefin flame retardant resin composition in which a predetermined amount of a flame retardant containing a phosphate and a fluorine drip agent is blended is disclosed (see Patent Document 1). The flame retardant performance of the flame retardant resin composition of Patent Document 1 is V-0 determination at a thickness of 0.3 mm, and there is no description that the flame retardant performance of V-0 is achieved at a thickness of 0.2 mm.
In addition, a sheet made of a flame retardant resin composition of a styrenic thermoplastic elastomer containing a predetermined amount of a metal hydroxide such as aluminum hydroxide is disclosed (see Patent Document 2). The flame retardancy performance of the flame retardant resin composition of Patent Document 2 is V-0 determination at a thickness of 0.3 mm, and there is no description that the flame retardancy performance of V-0 is achieved at a thickness of 0.2 mm.

Moreover, the sheet | seat which consists of a flame-retardant polycarbonate resin composition which mix | blended a small amount of perfluorobutanesulfonic-acid potassium salt is disclosed (refer patent document 3). The flame retardant performance of the resin composition of Patent Document 3 is V-0 determination at a thickness of 0.4 mm, and there is no description that the flame retardant performance of V-0 is achieved at a thickness of 0.2 mm.
Further disclosed is a sheet comprising a flame retardant resin composition of 2,6-dimethyl-1,4-phenylene ether / styrene-based thermoplastic elastomer in which a predetermined amount of a triaryl phosphate such as resorcinol bis (diphenyl phosphate) is blended. (See Patent Document 4). The flame retardant performance of the flame retardant resin composition of Patent Document 4 is V-0 determination at a thickness of 0.2 mm, but since 2,6-dimethyl-1,4-phenylene ether is the main component, it is chemically resistant. There is a problem that the nature is low.

  Also disclosed is a flame retardant synthetic resin composition comprising a synthetic resin and a predetermined amount of a phosphate compound and an anti-drip agent (polytetrafluoroethylene (hereinafter referred to as PTFE)) (patent). Reference 5). In the flame-retardant synthetic resin composition of Patent Document 5, although V-0 determination is obtained at a thickness of 1.6 mm, there is no description that the flame-retardant performance of V-0 is achieved at a thickness of 0.2 mm. Moreover, the flame retardant polyolefin resin composition which contains the specific (poly) phosphate compound as a flame retardant component with respect to polyolefin resin and satisfies the standard of UL94 5VA is disclosed ( (See Patent Document 6). The flame retardant performance of the flame retardant polyolefin-based resin composition of Patent Document 6 is 1.6 mm or 3.2 mm, and UL94 5VA is obtained, but the thickness is 0.2 mm and V-0 flame retardant performance. There is no description that it was achieved.

Moreover, the flame retardant polyolefin resin film which consists of a polyolefin resin composition and a phosphate compound is disclosed (refer patent document 7). In the flame-retardant polyolefin-based resin composition film of Patent Document 7, since a large amount of amine phosphate is blended, a high flame retardance with an oxygen index of 27 is achieved at a thickness of 0.1 mm. However, there is no description that the flame retardancy performance of V-0 was achieved at a thickness of 0.2 mm.
Moreover, the flame-retardant thermoplastic resin composition which contains a phosphate compound in a thermoplastic resin component is disclosed (refer patent document 8). The flame retardant performance of the flame retardant thermoplastic resin composition of Patent Document 8 is a level that passes the flame retardant evaluation UL1581 for electric wires. However, there is no description that the flame retardancy performance of V-0 was achieved at a thickness of 0.2 mm.

Also disclosed is a flame retardant elastomer composition comprising a hydrogenated block copolymer, a non-aromatic rubber softener, a polypropylene resin, a phosphate flame retardant, a fluorine resin, and a metal soap ( (See Patent Document 9). The flame retardancy performance of the flame retardant elastomer composition of Patent Document 9 is V-0 determination at a thickness of 1.5 mm, and V at a thickness of 0.2 mm, even though the amount of the phosphate flame retardant is large. There is no description that the flame retardant performance of −0 was achieved.
A flame retardant comprising a hydrogenated block copolymer, a non-aromatic rubber softener, a polypropylene resin, a polyphenylene ale resin, a hydrogenated petroleum resin, a phosphate flame retardant, a fluorine resin, and a dispersant. An elastomer composition is disclosed (see Patent Document 10). The flame retardant performance of the flame retardant elastomer composition of Patent Document 10 is V-0 determination at a thickness of 3.0 mm, even though the amount of the phosphate flame retardant is large, and V at a thickness of 0.2 mm. There is no description that the flame retardant performance of −0 was achieved.

Further, a flame-retardant synthetic resin film containing piperazine pyrophosphate and melamine cyanurate and formed into a film having a thickness of 0.1 to 0.3 mm is disclosed with respect to polypropylene resin (see Patent Document 11). ). The flame retardant performance of the flame retardant synthetic resin film of Patent Document 11 is a level that passes UL94 VTM-0 with a thickness of 0.1 mm. However, a large amount of flame retardant composed of piperazine pyrophosphate and melamine cyanurate is blended, and PTFE is also blended as an anti-drip agent. There is no.
In addition, PTFE has low compatibility with thermoplastic resins, so it is difficult to uniformly disperse, and aggregates tend to be formed. PTFE aggregates cause poor appearance of molded products, reduce flame retardancy, and It has been disclosed that mechanical properties are likely to deteriorate (see Patent Document 12). In this regard, Patent Document 12 includes a (meth) acrylic acid alkyl ester-based polymer containing 70% by mass or more of a structural unit composed of PTFE and a (meth) acrylic acid alkyl ester having an alkyl group having 1 to 4 carbon atoms. By blending the thermoplastic resin modifier as an anti-drip agent, PTFE agglomerates are reduced and a molded product having a good appearance is obtained. Although there is a large amount of magnesium hydroxide as a flame retardant, there is no description that the flame retardancy of V-0 is achieved at a thickness of 1.6 mm and V-0 at a thickness of 0.2 mm. In addition, there is no example in which a phosphate compound, which is considered to have a flame retardant effect higher than that of magnesium hydroxide, is blended with polypropylene resin, and a PTFE dispersion effect is similarly obtained for a composition containing a phosphate compound. It is unclear whether it will be done.

Japanese Patent No. 5243653 International Publication No. 2009/133930 International Publication No. 2005/103155 Special table 2010-519389 JP 2003-26935 A JP2013-119575A JP 2007-84681 A JP 2008-63458 A JP 2010-180326 A JP 2010-180325 A JP 2013-124340 A International Publication No. 2002/090440

  As described above, in an electrical insulating sheet comprising a flame retardant polyolefin resin composition comprising a polyolefin having excellent tracking resistance, electrical insulation and chemical resistance as a main component and blended with a non-halogen flame retardant, the thickness is 0. There is no report that a high flame retardant performance that passes V-0 at 2 mm and excellent in appearance has been obtained.

  In view of such circumstances, the present invention has a flame retardant polyolefin resin composition, a molded article and a flame retardant having excellent flame retardancy and excellent appearance, tracking resistance, electrical insulation and chemical resistance. An object of the present invention is to provide a method for producing a conductive polyolefin resin composition.

The flame retardant polyolefin resin composition of the present invention is a flame retardant polyolefin resin composition containing at least the following components (A), (B), (C) and (D): The component (A) is a polyolefin resin, the component (B) is a phosphoric acid amine salt composed of the component (B-1) and the component (B-2), and the component (B-1) is , At least one of piperazine pyrophosphate and piperazine polyphosphate, and the component (B-2) is at least one melamine compound selected from dimelamine pyrophosphate, melamine pyrophosphate and melamine polyphosphate, The component (C) is a master batch obtained by melting and kneading PTFE, the component (D) is a phosphate ester compound represented by the following general formula (1), the component (A) and the former (B) when the total amount of the components is 100 mass%, satisfies the following formula (F1) and the following formula (F2),
45% by mass ≦ (A) component ≦ 58% by mass (F1)
42% by mass ≦ (B) component ≦ 55% by mass (F2)
The component (B) satisfies the following formula (F3) and the following formula (F4),
55 mass% ≦ (B-1) component ≦ 65 mass% (F3)
35% by mass ≦ (B-2) component ≦ 45% by mass (F4)
PTFE in the component (C) satisfies the following mathematical formula (F5) with respect to 100 parts by mass of the total amount of the component (A) and the component (B),
0.08 part by mass ≦ PTFE in component (C) ≦ 0.16 part by mass (F5)
The ratio of PTFE in the component (C) of the formula (F5) to the component (B) of the formula (F2) satisfies the following formula (F6),
0.00145 ≦ [PTFE / component (B) in component (C)] ≦ 0.00381 (F6)
With respect to 100 parts by mass of the total amount of the component (A) and the component (B), the component (D) satisfies the following mathematical formula (F7): 0.5 part by mass ≦ (D) component ≦ 3 parts by mass ( F7)
A flame retardant polyolefin-based resin composition characterized by the above.

(However, in the said General formula (1), R < ¹ >, R < ² >, R < ⁴ > and R < ⁵ > may be same or different, and are C1-C10 alkyl groups or following General formula (2). R ³ represents a divalent aromatic group represented by the following general formula (3) or the following general formula (4), and s is a number from 0 to 30.

(However, the general formulas above general formula (2) in (4), ^{A 1} and ^{A 2} each independently represent a hydrogen atom, ^.A 3 representing a hydroxy group or an alkyl group having 1 to 10 carbon atoms, A ⁴ , A ⁵ , A ⁶ , A ⁷ and A ⁸ are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a cycloalkyl group, an aryl group, an alkoxy group, a nitro group, a halogen atom or a cyano group. G represents a direct bond, a divalent sulfur atom, a sulfone group, an alkylidene group having 1 to 5 carbon atoms, or an alkylene group.

  In the flame-retardant polyolefin resin composition of the present invention, the polyolefin resin as the component (A) is preferably a polypropylene resin.

  In the flame-retardant polyolefin resin composition of the present invention, the component (A) preferably has a polypropylene resin having an isotactic pentad fraction of less than 0.97.

  In the flame-retardant polyolefin resin composition of the present invention, the component (A) has a polypropylene content of 35% by mass or more and 57.5% by mass or less, and an ethylene homopolymer or a copolymer mainly composed of ethylene is 0.5%. It is preferable that they are 10 mass% or less.

  In the flame-retardant polyolefin resin composition of the present invention, the matrix resin of the masterbatch obtained by melt-kneading the PTFE in the component (C) is preferably a polyolefin resin.

  The molded article of the present invention is formed by molding a flame retardant polyolefin resin composition.

  The method for producing a flame retardant polyolefin resin composition of the present invention is a premix obtained by mixing at least the component (A), the component (B), the component (C) and the component (D). Is melt-kneaded.

  According to the present invention, a flame retardant polyolefin resin composition, a molded article, and a flame retardant polyolefin series having excellent flame retardancy and excellent appearance, tracking resistance, electrical insulation and chemical resistance. A method for producing a resin composition can be provided.

  The flame retardant polyolefin resin composition of the present embodiment contains at least the following components (A), (B), (C) and (D).

[(A) component]
In the flame retardant polyolefin resin composition of this embodiment, a polyolefin resin is used as the component (A).
Examples of polyolefin resins include polypropylene resins, polyethylene resins, polybutene resins, polypentene resins, and thermoplastic elastomers.
Examples of the polypropylene resin include a homopolymer of propylene (homopolypropylene), a copolymer mainly composed of propylene, and a mixture obtained by mixing two or more of these.
Copolymers mainly composed of propylene include random copolymers of propylene and ethylene or other α-olefins (random polypropylene), block copolymers (block polypropylene), block copolymers containing rubber components Or a graft copolymer and the mixture which mixed 2 or more types etc. are mentioned. Examples of other α-olefin copolymerizable with propylene include ethylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 4-methyl-1-pentene, 1-decene, and the like. These 1 type, or 2 or more types of mixtures are used.

The polypropylene resin preferably has an isotactic pentad fraction of less than 0.97. When the main component is an isotactic pentad fraction of less than 0.97 (30% by mass or more), the dispersibility of (B) component phosphoric acid amine salt and (C) component PTFE described later is good. Become. As a result, since the aggregates of amine phosphate and PTFE are reduced, the appearance of the molded product produced from the flame retardant polyolefin resin composition is improved. Furthermore, since the dispersibility of the phosphoric acid amine salt and PTFE is good, the flame retardancy is extremely good.
On the other hand, when the main component is an isotactic pentad fraction of 0.97 or more (30% by mass or more), an aggregate of phosphoric acid amine salt or an aggregate of PTFE is generated, or flame retardant It may cause a decrease.
The isotactic pentad fraction ([mmmm]) in the present invention is an isotactic fraction of pentad units in a polypropylene molecular chain measured by a method using ¹³ C-NMR (Macromolecules, 6 Vol., Page 925 (1973)).

  Examples of the polyethylene resin include ethylene homopolymers, copolymers containing ethylene as a main component, and those polymerized using a metallocene catalyst thereof. Examples of the copolymer containing ethylene as a main component include an ethylene / α-olefin copolymer. Examples of the α-olefin used in the ethylene / α-olefin copolymer include 1-butene, 1-pentene, 1-hexene, 1-octene, 4-methyl-1-pentene, and 1-decene. It is done. Moreover, the polyethylene-type resin which has a polar group, for example, ethylene vinyl acetate copolymer (EVA), ethylene ethyl acrylate copolymer (EEA), etc. are mentioned.

[Other resins and processing aid ingredients]
In the flame-retardant polyolefin resin composition of the present embodiment, conventionally known resins and processing aid components can be added as necessary within a range not impairing the object of the present invention.
For the purpose of imparting impact resistance, an appropriate amount of polyolefin thermoplastic elastomer (TPO) or styrene-based thermoplastic elastomer can be used as necessary within a range where flame retardancy does not decrease (about 5% by mass or less). .
For example, SBR [polystyrene-polybutadiene rubber], SBS [polystyrene-polybutadiene block-polystyrene], SEBS [polystyrene-poly (ethylene / butylene) block-polystyrene], SIR [polystyrene-polyisoprene rubber], SIS [polystyrene-polyisoprene]. Block-polystyrene], SEEPS [polystyrene-poly (ethylene-ethylene / propylene) block-polystyrene], SEP [polystyrene-poly (ethylene / propylene) block], SEPS [polystyrene-poly (ethylene / propylene) block-polystyrene], etc. May be added. Of these, hydrogenated butadiene block copolymers and blocks TPO, SEBS, and SEPS are particularly preferably used.
Examples of commercially available products include Clayton series such as Dynalon 6200 manufactured by JSR, R-110MP manufactured by Prime Polymer, Clayton G1651 manufactured by Shell Chemical Co., and Septon Series such as Septon 2104 manufactured by Kuraray, Asahi Kasei Chemicals The Tuftec H series manufactured by the company is listed.

  In addition, for the purpose of increasing strength and rigidity, polypropylene resin, polyethylene resin, polybutene resin, polypentene resin, thermoplastic elastomer, etc. modified with maleic anhydride, etc., as necessary, have flame retardancy. An appropriate amount can be used within a range where it does not decrease (about 5% by mass or less).

Further, for the purpose of improving flame retardancy, an appropriate amount of a flame retardant resin can be added as necessary within a range in which workability and physical properties do not deteriorate (about 20% by mass or less).
Examples of the flame-retardant resin include Noryl PPO640 manufactured by SABIC, which is polyphenylene ether, and A1020LP manufactured by Unitika, which is nylon 6.

In addition, for the purpose of improving processability and impact resistance, a mineral oil softener can be added in an appropriate amount within a range where flame retardancy does not decrease (about 5% by mass or less), if necessary.
Mineral oil-based softeners are high-boiling petroleum fractions, with paraffin chain carbon number accounting for 50% or more of the total carbon number, paraffin type, naphthene ring carbon number of 30-40% naphthenic, Those having an aromatic carbon number of 30% or more are called aromatic mineral oil softeners.
As the mineral oil softener, a mineral oil softener for rubber used for rubber is preferable. The mineral oil softener for rubber is a mixture in which an aromatic ring, a naphthene ring, and a paraffin chain are combined. As this mineral oil softener for rubber becomes more pollutant when the aromatic component increases, the weather resistance also decreases, so that the non-aromatic paraffinic and naphthenic rubber mineral oil softener, In particular, the mineral oil softener for paraffin rubber is preferable because it is colorless and transparent. Also, a liquid or low molecular weight synthetic softener can be used together with the mineral oil softener.
Examples of commercially available products include process oils PW90, PW100, and PW380 manufactured by Idemitsu Kosan Co., Ltd.

[Component (B)]
In the flame retardant polyolefin resin composition of the present embodiment, an amine phosphate is used as the component (B). The component (B) acts as a flame retardant. (B) component is comprised from the (B-1) component and the (B-2) component.

[(B-1) component]
The component (B-1) constituting the component (B) is at least one of piperazine pyrophosphate and piperazine polyphosphate.
Piperazine pyrophosphate can be synthesized according to a known method. For example, piperazine pyrophosphate is obtained by dehydrating and condensing piperazine diphosphate at a temperature of 120 to 320 ° C. for 0.5 to 3 hours. The piperazine diphosphate is obtained by heating and reacting 2 equivalents of orthophosphoric acid and 1 equivalent of piperazine in a solvent such as water or methanol at 200 to 250 ° C. for 0.5 to 1 hour.
A commercially available piperazine polyphosphate can be used.
Piperazine pyrophosphate and piperazine polyphosphate may be used alone or in combination of two or more.
Piperazine phosphate and dipiperazine pyrophosphate are difficult to use because they decompose and foam during kneading.

[(B-2) component]
The component (B-2) constituting the component (B) is at least one melamine compound selected from dimelamine pyrophosphate, melamine pyrophosphate and melamine polyphosphate.
A commercial item can be used for these melamine compounds.
Note that melamine phosphate and dimelamine phosphate are difficult to use because they decompose and foam during kneading.

[Composition of component (B-1) and component (B-2)]
The component (B) is blended so that the component (B-1) and the component (B-2) satisfy the following formula (F3) and the following formula (F4).
55 mass% ≦ (B-1) component ≦ 65 mass% (F3)
35% by mass ≦ (B-2) component ≦ 45% by mass (F4)
Of the proportion represented by the formula (F3), the component (B-1) is preferably 56% by mass or more and 64% by mass or less, and particularly preferably 57% by mass or more and 63% by mass or less. When the component (B-1) is less than 55% by mass or exceeds 65% by mass, sufficient flame retardancy cannot be obtained.
Of the proportion represented by the formula (F4), the component (B-2) is preferably 36% by mass or more and 44% by mass or less, and particularly preferably 37% by mass or more and 43% by mass or less. When the component (B-2) is less than 35% by mass or exceeds 45% by mass, sufficient flame retardancy cannot be obtained.
Examples of commercially available products of component (B) include FP2050, FP2100J, FP2100JC, FP2200S, FP2200S and FP2400 manufactured by ADEKA with piperazine pyrophosphate / melamine pyrophosphate = 60/40 (mass ratio).

[Composition of component (A) and component (B)]
In the flame retardant polyolefin resin composition of the present embodiment, when the total amount of the component (A) and the component (B) is 100% by mass, the following formula (F1) and the following formula (F2) are satisfied. Has been.
45% by mass ≦ (A) component ≦ 58% by mass (F1)
42% by mass ≦ (B) component ≦ 55% by mass (F2)
Of the proportion represented by the formula (F1), the component (A) is preferably 46% by mass or more and 57% by mass or less, and particularly preferably 48% by mass or more and 55% by mass or less.
Of the proportion represented by the formula (F2), the component (B) is preferably 43% by mass or more and 54% by mass or less, and particularly preferably 45% by mass or more and 52% by mass or less.
When the proportion of the component (A) is less than 45% by mass and the proportion of the component (B) exceeds 55% by mass, the amount of the flame retardant contained in the flame retardant polyolefin resin composition increases. In particular, mechanical characteristics and impact characteristics are lowered, and the cost is further increased. Further, when the proportion of the component (B) is less than 42% by mass and the proportion of the component (A) exceeds 58% by mass, the composition amount of the flame retardant contained in the flame retardant polyolefin-based resin composition is reduced. Flame retardant performance is reduced.

In the flame-retardant polyolefin resin composition of the present embodiment, the component (B), which is a flame retardant, is often blended in an amount of 42% by mass to 55% by mass. At the above ratio, the physical properties of the flame retardant polyolefin resin composition, particularly the impact strength, may be lowered. For this reason, as the component (A), it is preferable to use a block copolymer of propylene having good impact resistance.
For example, in order to improve the impact strength, an ethylene homopolymer (may be polymerized using a metallocene catalyst) or an ethylene-based copolymer (polymerized using a metallocene catalyst) may be used. ) Is more preferable.
Specifically, the block copolymer of propylene is 35% by mass or more and 57.5% by mass or less, and the ethylene homopolymer or ethylene-based copolymer is 0.5% by mass or more and 10% by mass or less. It is preferable. Among these, it is more preferable that the block copolymer of propylene is 37 mass% or more and 57 mass% or less, and the ethylene homopolymer or the copolymer mainly composed of ethylene is 1 mass% or more and 8 mass% or less. More preferably, the propylene block copolymer is 40% by mass or more and 56% by mass or less, and the ethylene homopolymer or ethylene-based copolymer is 1% by mass or more and 5% by mass or less.
The blending ratio of the propylene block copolymer and the ethylene homopolymer or ethylene-based copolymer is preferably within the above range from the viewpoint of the balance of rigidity, strength and impact strength.
In addition, when an ethylene homopolymer or a copolymer mainly composed of ethylene exceeds 10% by mass, flame retardancy may be reduced.

[Component (C)]
In the flame retardant polyolefin resin composition of the present embodiment, a master batch obtained by melting and kneading PTFE with a matrix resin is used as the component (C).
The reason why the component (C) is in the form of a master batch obtained by melting and kneading PTFE is from the viewpoint of flame retardancy and dispersibility of PTFE (suppression of aggregate generation).
The PTFE in the masterbatch of the present invention may be referred to as PTFE particles or a mixed powder of PTFE particles and particles selected from organic polymer particles and talc (hereinafter referred to as “PTFE-containing mixed powder”). ).

[PTFE particles]
Commercially available PTFE particles can be used. For example, a homopolymer of tetrafluoroethylene or a copolymer containing tetrafluoroethylene as a main component can be used.
Conomers that copolymerize with tetrafluoroethylene include fluorine-containing olefins such as difluoroethylene, trifluoroethylene, hexafluoropropylene, chlorotrifluoroethylene, fluoroalkylethylene, perfluoroalkyl vinyl ether, and perfluoroalkyl (meth) acrylate. The fluorine-containing alkyl (meth) acrylate can be used. The content of the copolymer component is preferably 10% by mass or less with respect to tetrafluoroethylene.
As commercial products of PTFE particles, AGC Asahi Glass Co., Ltd. Fullon CD1, CD076, CD123, Daikin Industries, Ltd. Polyflon PTFE Fine Powder F-201, F-104, Polyflon MPAFA-500, F-500H, Mitsui DuPont Typical examples include Teflon 6CJ, 6J, 62-J, and 640-J (Teflon is a registered trademark) manufactured by Fluorochemical Co., Ltd.

[PTFE-containing mixed powder]
A commercially available powder can be used as the PTFE-containing mixed powder. The morphology of the PTFE-containing mixed powder varies depending on the mixing ratio, particle diameter, etc. of the PTFE particles, the organic polymer particles and talc, and there is no particular limitation. For example, PTFE particles are surrounded by organic polymer particles and talc particles, and conversely, organic polymer particles and talc are surrounded by PTFE particles. There are forms in which individual particles are aggregated.

  The PTFE-containing mixed powder is composed of PTFE particles having an average particle diameter of 10 μm or less, organic polymer particles, and talc, and the PTFE particles in the mixed powder are not aggregates exceeding the average particle diameter of 10 μm. preferable. As such a PTFE-containing mixed powder, a PTFE particle aqueous dispersion having a particle diameter of about 0.05 μm to 1.0 μm and an organic polymer particle aqueous dispersion and / or an aqueous talc dispersion are mixed. Those obtained by pulverization by coagulation or spray drying are preferred. Further, those obtained by polymerizing the monomer constituting the organic polymer in the presence of an aqueous PTFE particle dispersion having a particle size of about 0.05 μm to 1.0 μm and then pulverizing by solidification or spray drying are preferable. . Furthermore, an ethylenically unsaturated bond is formed in a dispersion obtained by mixing an aqueous PTFE particle dispersion having a particle diameter of about 0.05 μm to 1.0 μm with an aqueous organic polymer particle dispersion and / or an aqueous talc dispersion. What is obtained by emulsion polymerization of the monomer having it and then pulverizing by coagulation or spray drying is preferable.

An aqueous PTFE particle dispersion having a particle size of about 0.05 μm to 1.0 μm can be obtained by polymerizing a tetrafluoroethylene monomer by emulsion polymerization using a fluorine-containing surfactant. In the emulsion polymerization, PTFE is copolymerized with fluorine-containing olefins such as hexafluoropropylene, chlorotrifluoroethylene, fluoroalkylethylene and perfluoroalkyl vinyl ether, and fluorine-containing alkyl (meta) such as perfluoroalkyl (meth) acrylate ) Acrylate can be used. These copolymer components are preferably 10% by mass or less with respect to tetrafluoroethylene.
Commercially available raw materials for PTFE particle aqueous dispersions include AGC Asahi Glass's Fullon AD-1, AD-911L, AD-936, AD-938L, Daikin Industries' Polyflon D-1, D-2, Mitsui DuPont Fluoro Typical examples include Teflon 30-J, 31-JR, and 34-JR manufactured by Chemical Corporation.

  The organic polymer constituting the organic polymer particles is not particularly limited, and for example, the following commercially available products can be used. Polycarbonate (PC), polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, 6-nylon, 6,6-nylon, polyarylate, polyphenylene ether, modified polyphenylene ether, polyphenylene sulfide, polyether ketone, polyether Ether ketone, polysulfone, polyethersulfone, polyamideimide, polyetherimide, polypropylene, polyethylene, polystyrene, high impact polystyrene, polyalkyl (meth) acrylate, polyacetal, copolymer of aromatic alkenyl compound and vinyl cyanide compound, Phenolic resin, urea resin, melamine resin, unsaturated polyester resin, alkyd resin, epoxy resin, silicon Fat, polyurethane, ethylene-propylene copolymer, styrene-butadiene block copolymer, polybutadiene, polyisoprene, random copolymer or block copolymer of styrene-butadiene, water additive of this block copolymer, acrylonitrile Diene rubber such as butadiene copolymer, butadiene-isoprene copolymer, random copolymer or block copolymer of ethylene-propylene, random copolymer or block copolymer of ethylene-butene, ethylene and α-olefin Copolymer, maleic anhydride modified polypropylene, acrylic acid modified polypropylene, maleic anhydride modified polyethylene, acrylic acid modified polyethylene, maleic anhydride modified ethylene-propylene random copolymer or block copolymer, poly Propylene wax, polyethylene wax, oxidized polypropylene wax, oxidized polyethylene wax, acrylic acid-modified ethylene-propylene random copolymer or block copolymer, ethylene-unsaturated carboxylic acid ester such as ethylene-methacrylate, ethylene-butyl acrylate Copolymer, acrylic ester-butadiene copolymer, acrylic elastic polymer such as butyl acrylate-butadiene, ethylene-vinyl acetate copolymer, ethylene-propylene-ethylidene norbornene copolymer, ethylene-propylene-hexadiene copolymer Ethylene-propylene non-conjugated diene terpolymer such as polymer, butylene-isoprene copolymer, chlorinated polyethylene, polyorganosiloxane, polyalkyl (meth) acrylate Rubber polymer such as, composite rubber containing polyorganosiloxane and polyalkyl (meth) acrylate, graft copolymer obtained by graft polymerization of aromatic vinyl monomer and vinyl cyanide monomer to rubber polymer, 50% by mass or less of a composite rubber-based graft copolymer obtained by grafting a vinyl monomer to a composite rubber containing polyorganosiloxane and polyalkyl (meth) acrylate, and a component copolymerizable therewith. And a polymer to be contained. These may be used alone or in combination of two or more, but are preferably those having an affinity for the polyolefin resin from the viewpoint of dispersibility of PTFE when blended with the polyolefin resin. More preferred are polyalkyl (meth) acrylates having a polyalkyl (meth) acrylate having 4 or more alkyl groups, polypropylene wax, polyethylene wax, and rubbery polymer.

  Talc is not particularly limited, and for example, a commercial product of talc having an average particle diameter of 0.5 μm to 100 μm can be used. When the average particle size is less than 0.5 μm, the talc particles are easily aggregated. As a result, the mixed powder of PTFE and talc is aggregated, and when a master batch is prepared by melt-kneading with a polyolefin resin. , PTFE may aggregate and the flame retardancy improving effect may be insufficient. When the average particle diameter exceeds 100 μm, PTFE tends to aggregate, and the flame retardancy improving effect may be insufficient.

  The mixing ratio of PTFE particles and organic polymer particles and talc in the PTFE-containing mixed powder is not particularly limited, but the ratio of PTFE particles in the PTFE-containing mixed powder is 0.1% by mass or more and 90% by mass or less. Is preferable, and 10 mass% or more and 70 mass% is especially preferable. If the proportion of PTFE particles in the PTFE-containing mixed powder is less than 0.1% by mass, the flame retardancy improving effect may be insufficient. Further, if the ratio of PTFE particles in the PTFE-containing mixed powder exceeds 90% by mass, agglomeration of the forming raw material occurs in the raw material supply line during continuous production of the melt-kneading of the master batch, and the raw material supply line is likely to be blocked. There is a case. As a result, stable raw material supply may be hindered, the composition discharge amount may become unstable, and productivity may decrease.

  Commercially available products of PTFE-containing mixed powder include METABRENE A3000 manufactured by Mitsubishi Rayon Co., Ltd. [PTFE / mixed powder of polyalkyl (meth) acrylate having an alkyl group having 4 or more carbon atoms = 1/5 (mass ratio)], metabrene A3800 [PTFE / mixed powder of polyalkyl (meth) acrylate having an alkyl group having 4 or more carbon atoms = 1/1 (mass ratio)], methabrene A3300 [PTFE / polyalkyl having an alkyl group having 4 or more carbon atoms ( (Meth) acrylate = 1/1 (mass ratio) mixed powder], Shamrock X-6901 [PTFE / polypropylene wax = 1/1 (mass ratio) powder], Shamrock Powertex 61 [PTFE / Talc = 1/2 (mass ratio) mixed powder].

[Master batch in which PTFE is melt-kneaded]
The master batch obtained by melting and kneading PTFE, which is the component (C), can be produced by melt-kneading a mixture obtained by mixing PTFE and a matrix resin by an arbitrary method.
As the master batch obtained by melt-kneading PTFE, a commercially available product can be used. The matrix resin is not particularly limited, but a polyolefin resin is preferably used.
In particular, when the polyolefin resin used for the component (A) is used as the matrix resin, the resin is uniformly mixed during melt-kneading with the component (A), the component (B), and the component (D), and PTFE. The dispersibility of the resin becomes good, and as a result, the flame retardancy becomes high, which is preferable.
Moreover, when PTFE mixed powder is used as PTFE in the master batch, the dispersibility of PTFE in the master batch is improved, and as a result, melt kneading with the component (A), the component (B) and the component (D) In this case, the dispersibility of PTFE is further improved, and the flame retardancy is further increased, which is preferable.
In particular, a masterbatch using a polyolefin resin as a matrix resin and a PTFE mixed powder as a PTFE is compared with a non-masterbatch PTFE powder or a PTFE mixed powder as compared with the component (A), component (B) and component (D ) And melt kneaded to form a composition, the dispersibility of PTFE is good, and the flame retardancy is further increased, which is more preferable.

  The proportion of PTFE in the composition of the master batch is preferably 0.05% by mass or more and 20% by mass or less, and more preferably 1% by mass or more and 10% by mass or less. When the proportion of PTFE is less than 0.05% by mass, the dispersibility of PTFE is good, but since the blending amount of PTFE is small, the flame retardancy of V-0 is exhibited at a thickness of 0.2 mm. Needs to increase the amount of component (C), which may be expensive and uneconomical. Moreover, when the ratio of PTFE exceeds 10 mass%, the productivity at the time of melt kneading of the master batch may be lowered.

Master batches are mixed with a suitable amount of PTFE or PTFE mixed powder in a matrix resin such as polypropylene resin, mixed with a tumbler mixer or Henschel mixer, and then pelletized under appropriate melting conditions using a twin screw extruder or the like. It is manufactured by doing.
In addition, in the production of a masterbatch, various additives such as an antioxidant, a lubricant, and a light stabilizer can be blended in addition to the above blending components.
Examples of commercially available masterbatches include MZX4 (Homo PP / Metabrene A3000 = 5/1 mass ratio) manufactured by Mitsubishi Rayon Co., Ltd.

[Composition of component (C)]
In the flame-retardant polyolefin resin composition of the present embodiment, the PTFE in the component (C) satisfies the following formula (F5) with respect to 100 parts by mass of the total amount of the component (A) and the component (B). It is blended.
0.08 part by mass ≦ PTFE in component (C) ≦ 0.16 part by mass (F5)
In the flame-retardant polyolefin resin composition of the present embodiment, the ratio of PTFE in the component (C) of the formula (F5) to the component (B) of the formula (F2) satisfies the following formula (F6). It is blended.
0.00145 ≦ [PTFE / component (B) in component (C)] ≦ 0.00381 (F6)
By satisfying the formula (F5) and the formula (F6), a composition having good flame retardancy can be obtained. Moreover, when an extruded sheet (width 12 cm × length 10 m) having a thickness of 0.2 mm is produced using this composition, the appearance of PTFE aggregates is reduced and the appearance is improved.

Of the proportion represented by the formula (F5), the PTFE in the component (C) is preferably 0.090 parts by mass or more and 0.155 parts by mass or less, particularly 0.100 parts by mass or more and 0.150 parts by mass or less. preferable.
Further, in the ratio represented by the formula (F6), the ratio of PTFE in the component (C) of the formula (F5) to the component (B) of the formula (F2) is preferably 0.00164 or more and 0.00369 or less. 0.00182 to 0.00357 is particularly preferable.
If it is less than the lower limit of the above formula (F5), in the UL94 flame retardancy test with a sheet thickness of 0.2 mm, there is a problem that the flame retardancy decreases due to melt dripping (drip).
Moreover, when the upper limit value of the mathematical formula (F5) is exceeded, in the UL94 flame retardancy test with a sheet thickness of 0.2 mm, the test piece contracts and burns to the clamp, resulting in a problem that the flame retardancy decreases. Further, in the extruded sheet having a sheet thickness of 0.2 mm (width 12 cm × length 10 m), many PTFE aggregates are generated, resulting in poor appearance.
If it is less than the lower limit of the above formula (F6), in the UL94 flame retardancy test with a sheet thickness of 0.2 mm, there is a problem that the flame retardancy is lowered by melting and dripping (drip).
Moreover, when the upper limit of the said numerical formula (F6) is exceeded, in the UL94 flame retardant test of sheet thickness 0.2mm, a test piece will shrink | contract and burn to a clamp, and the malfunction which a flame retardance will fall will arise. Further, in the extruded sheet having a sheet thickness of 0.2 mm (width 12 cm × length 10 m), many PTFE aggregates are generated, resulting in poor appearance.

[(D) component]
In the flame-retardant polyolefin resin composition of the present embodiment, a phosphate ester compound is used as the component (D). The component (D) has a function of improving dispersibility in the composition of the component (B) and the component (C) and improving flame retardancy. (D) The phosphoric acid ester compound of a component is represented by following General formula (1).

(However, in the said General formula (1), R < ¹ >, R < ² >, R < ⁴ > and R < ⁵ > may be same or different, and are C1-C10 alkyl groups or following General formula (2). R ³ represents a divalent aromatic group represented by the following general formula (3) or the following general formula (4), and s is a number from 0 to 30.

(However, the general formulas above general formula (2) in (4), ^{A 1} and ^{A 2} each independently represent a hydrogen atom, ^.A 3 representing a hydroxy group or an alkyl group having 1 to 10 carbon atoms, A ⁴ , A ⁵ , A ⁶ , A ⁷ and A ⁸ are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a cycloalkyl group, an aryl group, an alkoxy group, a nitro group, a halogen atom or a cyano group. G represents a direct bond, a divalent sulfur atom, a sulfone group, an alkylidene group having 1 to 5 carbon atoms, or an alkylene group.

Examples of the alkyl group having 1 to 10 carbon atoms represented by R ¹ , R ² , R ^4, R ⁵ , A ¹ , and A ² in the general formula (1) to the general formula (4) include methyl, ethyl Propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, amyl, tert-amyl, hexyl, 2-ethylhexyl, n-octyl, nonyl, decyl and the like. Examples of the alkyl group having 1 to 4 carbon atoms represented by A ³ , A ⁴ , A ⁵ , A ⁶ , A ⁷ and A ⁸ include methyl, ethyl, propyl, butyl, isobutyl, secondary butyl and tertiary butyl. And examples of the cycloalkyl group include cyclohexyl. Examples of the aryl group include phenyl, cresyl, xylyl, 2,6-xylyl, 2,4,6-trimethylphenyl, butylphenyl, nonylphenyl and the like. Examples of the alkoxy group include methoxy, ethoxy, propoxy, butoxy and the like. Examples of the halogen atom include a fluorine atom, a chlorine atom, and a bromine atom.
Examples of the aromatic group represented by the general formula (2) include phenyl, cresyl, xylyl, 2,6-xylyl, butylphenyl, nonylphenyl, and the like. Examples of the alkylidene group having 1 to 5 carbon atoms represented by G include ethylidene and isopropylidene, and examples of the alkylene group having 1 to 5 carbon atoms include methylene, ethylene, trimethylene and tetramethylene. .
In addition, s in the said General formula (1) showing the phosphate ester compound which is (D) component is a number of 0-30, Preferably it is a number of 1-10.
Specific examples of the phosphoric acid ester compound used as the component (D) in the flame retardant polyolefin resin composition of the present invention include the following compound Nos. 1-Compound No. 1 6 can be mentioned. In particular, from the viewpoint that the effect of improving the dispersibility of the component (B) and the component (C) is high, the compound No. 1 is used. 1, compound no. 2 and compound no. 5 is preferably used.

Specific examples of commercially available products include Compound No. No. 1 PX-200, Compound No. 2 ADE-KA FP-600, Compound No. 5 ADEKA FP-800 and the like.
These phosphate ester compounds may be used alone or in combination of two or more.

[Composition of component (D)]
In the flame-retardant polyolefin resin composition of the present invention, the (D) component is blended so as to satisfy the following formula (F7) with respect to 100 parts by mass of the total amount of the (A) component and the (B) component. .
0.5 parts by mass ≦ (D) component ≦ 3 parts by mass (F7)
Among the proportions represented by the formula (F7), 0.7 parts by mass or more and 2.5 parts by mass or less are preferable, and 1 part by mass or more and 2 parts by mass or less are particularly preferable.
When the proportion of the component (D) is less than 0.5 parts by mass, the flame retardancy effect due to the improvement in dispersibility cannot be obtained. Moreover, when the ratio of (D) component exceeds 3 mass parts, a juicing phenomenon will occur at the time of kneading | mixing and productivity will fall. The juicing phenomenon refers to a phenomenon in which when a phosphate ester component having a low compatibility with a polyolefin and having a low melting point is contained at the time of kneading, the polyolefin and the phosphate ester undergo phase separation and cannot be uniformly kneaded. . Moreover, since the compatibility with polyolefin is low, there is a problem that bleed out occurs from a molded product.

[Other additive components]
In the present invention, in addition to the above-described components, conventionally known flame retardants, flame retardant aids, additives, processing aids, and the like can be added as necessary within a range that does not impair the purpose of the present invention. .

[Flame retardants]
Examples of the flame retardant include halogen flame retardant, metal phosphinate, ammonium polyphosphate, red phosphorus, magnesium hydroxide, aluminum hydroxide, and expanded graphite.

[Flame retardant aid]
As the flame retardant aid, both inorganic flame retardant aid and organic flame retardant aid can be added.

[Inorganic flame retardant aid]
Inorganic flame retardant aids include magnesium hydroxide, hydrotalcite, talc, magnesium bicarbonate, zinc oxide, titanium oxide, aluminum oxide, magnesium oxide, silicon oxide, zirconium oxide, vanadium oxide, molybdenum oxide and their surface treatment Goods. Of these, magnesium bicarbonate, zinc oxide, titanium oxide, magnesium oxide and silicon oxide are preferably used from the viewpoint of the effect as a flame retardant aid.
Specifically, magnesium bicarbonate (decomposition start temperature 210 ° C., magnesium carbonate having an average particle size of 15 μm: manufactured by Kamishima Chemical Co., Ltd.), one type of zinc oxide (manufactured by Mitsui Kinzoku Kogyo Co., Ltd.), partially coated zinc oxide (Mitsui Metal Industries, Ltd.) Manufactured), Nanofine 50 (ultrafine zinc oxide having an average particle size of 0.02 μm: manufactured by Sakai Chemical Industry Co., Ltd.), Nanofine K (ultrafine zinc oxide coated with a zinc silicate having an average particle size of 0.02 μm: Sakai Chemical Industry Co., Ltd.) TIPAQUE R-680 (titanium oxide: manufactured by Ishihara Sangyo Co., Ltd.), Kyowa Mag 150 (magnesium oxide: manufactured by Kyowa Chemical Industry Co., Ltd.), Toxeal NP (silicon oxide, manufactured by Tokuyama Co., Ltd.), and the like.

[Organic flame retardant aid]
Examples of the organic flame retardant aid include melamine, melamine cyanurate, pentaerythritol, dipentaerythritol, tripentaerythritol, monopentaerythritol, tris (2-hydroxyethyl) isocyanurate, PTFE and the like.
Various flame retardant aids may be used alone or in combination of two or more. Addition of flame retardant aids can reduce the amount of flame retardant blended, or flame retardancy that cannot be obtained with a flame retardant alone can be obtained, so use in combination as appropriate depending on the type and application of the resin blended with the flame retardant It is preferable. The particle size, melting point, viscosity, etc. of the flame retardant aid are selected so as to be excellent in flame retardancy and powder characteristics.

[Additive]
As additives and processing aids, antioxidants, weathering agents, lubricants, antistatic agents, nucleating agents, metal deactivators, fillers, and the like can be used.

[Antioxidant]
Examples of the antioxidant include phenolic compounds, phosphorus compounds, and thioether compounds.

[Phenolic antioxidant]
Examples of phenolic antioxidants include 2,6-ditert-butyl-p-cresol, 2,6-diphenyl-4-octadecyloxyphenol, distearyl (3,5-ditert-butyl-4- Hydroxybenzyl) phosphonate, 1,6-hexamethylenebis [(3,5-ditert-butyl-4-hydroxyphenyl) propionic acid amide], 4,4′-thiobis (6-tert-butyl-m-cresol) 2,2'-methylenebis (4-methyl-6-tert-butylphenol), 2,2'-methylenebis (4-ethyl-6-tert-butylphenol), 4,4'-butylidenebis (6-tert-butyl- m-cresol), 2,2′-ethylidenebis (4,6-ditert-butylphenol), 2,2′-ethylidenebis (4-secondarybutyl-6-tert-butylphenol), , 1,3-Tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 1,3,5-tris (2,6-dimethyl-3-hydroxy-4-tert-butylbenzyl) isocyanate Nurate, 1,3,5-tris (3,5-ditert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris (3,5-ditert-butyl-4-hydroxybenzyl)- 2,4,6-trimethylbenzene, 2-tert-butyl-4-methyl-6- (2-acryloyloxy-3-tert-butyl-5-methylbenzyl) phenol, stearyl (3,5-ditert-butyl) -4-hydroxyphenyl) propionate, tetrakis [3- (3,5-ditert-butyl-4-hydroxyphenyl) propionate methyl] methane, thiodiethylene glycol bis [(3 5-di-tert-butyl-4-hydroxyphenyl) propionate], 1,6-hexamethylene bis [(3,5-di-tert-butyl-4-hydroxyphenyl) propionate], bis [3,3-bis (4 -Hydroxy-3-tert-butylphenyl) butyric acid] glycol ester, bis [2-tert-butyl-4-methyl-6- (2-hydroxy-3-tert-butyl-5-methylbenzyl) phenyl] terephthalate 1,3,5-tris [(3,5-ditert-butyl-4-hydroxyphenyl) propionyloxyethyl] isocyanurate, 3,9-bis [1,1-dimethyl-2-{(3-t Tributyl-4-hydroxy-5-methylphenyl) propionyloxy} ethyl] -2,4,8,10-tetraoxaspiro [5,5] undecane, And reethylene glycol bis [(3-tert-butyl-4-hydroxy-5-methylphenyl) propionate]. These may be used singly or in combination of two or more.

[Phosphorus antioxidant]
Examples of phosphorus antioxidants include trisnonylphenyl phosphite, tris [2-tert-butyl-4- (3-tert-butyl-4-hydroxy-5-methylphenylthio) -5-methylphenyl] phos. Phyto, tridecyl phosphite, octyl diphenyl phosphite, di (decyl) monophenyl phosphite, di (tridecyl) pentaerythritol diphosphite, di (nonylphenyl) pentaerythritol diphosphite, bis (2,4-di-tertiary) Tributylphenyl) pentaerythritol diphosphite, bis (2,6-ditert-butyl-4-methylphenyl) pentaerythritol diphosphite, bis (2,4,6-tritert-butylphenyl) pentaerythritol diphosphite Phyto, bis (2,4-dicumylphenyl) pentae Thritol diphosphite, tetra (tridecyl) isopropylidene diphenol diphosphite, tetra (tridecyl) -4,4'-n-butylidenebis (2-tert-butyl-5-methylphenol) diphosphite, hexa (tridecyl)- 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane triphosphite, tetrakis (2,4-ditert-butylphenyl) biphenylene diphosphonite, 9,10-dihydro- 9-oxa-10-phosphaphenanthrene-10-oxide, 2,2′-methylenebis (4,6-tert-butylphenyl) -2-ethylhexyl phosphite, 2,2′-methylenebis (4,6- Tert-butylphenyl) -octadecyl phosphite, 2,2′-ethylidenebis (4,6-ditertiary) Butylphenyl) fluorophosphite, tris (2-[(2,4,8,10-tetrakis tert-butyldibenzo [d, f] [1,3,2] dioxaphosphin-6-yl) oxy] Ethyl) amine, 2-ethyl-2-butylpropylene glycol and 2,4,6-tritert-butylphenol phosphite. These may be used singly or in combination of two or more.

[Thioether antioxidant]
Examples of the thioether-based antioxidant include dialkylthiodipropionates such as dilauryl thiodipropionate, dimyristyl thiodipropionate, distearyl thiodipropionate, and pentaerythritol tetra (β-alkylmercaptopropionate esters). These may be used alone or in combination of two or more.

[Weatherproofing agent]
As the weathering agent, an ultraviolet absorber, a hindered amine light stabilizer, or the like can be used.

[Ultraviolet absorber]
Examples of the ultraviolet absorber include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, and 5,5′-methylenebis (2-hydroxy-4-methoxybenzophenone). 2-hydroxybenzophenones such as 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-3 ′, 5′-ditert-butylphenyl) -5-chlorobenzo Triazol, 2- (2′-hydroxy-3′-tert-butyl-5′-methylphenyl) -5-chlorobenzotriazole, 2- (2′-hydroxy-5′-tert-octyl) Phenyl) benzotriazole, 2- (2′-hydroxy-3 ′, 5′-dicumylphenyl) benzotriazole, 2,2′-methylenebis (4 2- (2′-hydroxyphenyl) benzo such as tert-octyl-6- (benzotriazolyl) phenol), 2- (2′-hydroxy-3′-tert-butyl-5′-carboxyphenyl) benzotriazole Triazoles; phenyl salicylate, resorcinol monobenzoate, 2,4-ditert-butylphenyl-3,5-ditert-butyl-4-hydroxybenzoate, 2,4-ditert-amylphenyl-3,5-ditert Benzoates such as tributyl-4-hydroxybenzoate, hexadecyl-3,5-ditert-butyl-4-hydroxybenzoate; 2-ethyl-2′-ethoxyoxanilide, 2-ethoxy-4′-dodecyloxani Substituted oxanilides such as Lido; ethyl-α-cyano-β, β-diphenylacrylate, methyl-2-cyano Cyanoacrylates such as 3-methyl-3- (p-methoxyphenyl) acrylate; 2- (2-hydroxy-4-octoxyphenyl) -4,6-bis (2,4-ditert-butylphenyl)- s-triazine, 2- (2-hydroxy-4-methoxyphenyl) -4,6-diphenyl-s-triazine, 2- (2-hydroxy-4-propoxy-5-methylphenyl) -4,6-bis ( And triaryltriazines such as 2,4-ditertiarybutylphenyl) -s-triazine. You may use these in mixture of 2 or more types.

[Hindered amine light stabilizer]
Examples of the hindered amine light stabilizer include 2,2,6,6-tetramethyl-4-piperidyl stearate, 1,2,2,6,6-pentamethyl-4-piperidyl stearate, and 2,2,6. , 6-tetramethyl-4-piperidylbenzoate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-tetramethyl-4-piperidyl) sebacate Bis (1-octoxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) -1,2,3,4 Butanetetracarboxylate, tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, bis (2,2,6, 6-tetramethyl-4-piperidyl) di (tridecyl) -1,2,3,4-butanetetracarboxylate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) di (tridecyl) ) -1,2,3,4-butanetetracarboxylate, bis (1,2,2,4,4-pentamethyl-4-piperidyl) -2-butyl-2- (3,5-ditert-butyl- 4-hydroxybenzyl) malonate, 1- (2-hydroxyethyl) -2,2,6,6-tetramethyl-4-piperidinol / diethyl succinate polycondensate, 1,6-bis (2,2, 6,6-tetramethyl-4-piperidylamino) hexane / 2,4-dichloro-6-morpholino-s-triazine polycondensate, 1,6-bis (2,2,6,6-tetramethyl-4- Piperidylamino) hex 2,4-dichloro-6-tert-octylamino-s-triazine polycondensate, 1,5,8,12-tetrakis [2,4-bis (N-butyl-N- (2,2,6 , 6-tetramethyl-4-piperidyl) amino) -s-triazin-6-yl] -1,5,8,12-tetraazadodecane, 1,5,8,12-tetrakis [2,4-bis ( N-butyl-N- (1,2,2,6,6-pentamethyl-4-piperidyl) amino) -s-triazin-6-yl] -1,5,8-12-tetraazadodecane, 1,6 , 11-tris [2,4-bis (N-butyl-N- (2,2,6,6-tetramethyl-4-piperidyl) amino) -s-triazin-6-yl] aminoundecane, 1,6 , 11-tris [2,4-bis (N-butyl-N- (1,2,2,6 6-pentamethyl-4-piperidyl) amino) -s-triazin-6-yl] hindered amine compounds such as aminoundecanoic the like. These may be used singly or in combination of two or more.

[Lubricant]
As the lubricant, fatty acid amide, fatty acid ester, fatty acid, fatty acid metal salt, and the like can be used.

[Aliphatic amide lubricant]
Examples of aliphatic amide lubricants include stearic acid amide, oleic acid amide, erucic acid amide, behenic acid amide, ethylene bis stearic acid amide, ethylene bis oleic acid amide, ethylene biserucic acid amide, and ethylene bis lauric acid amide. It is done. These may be used singly or in combination of two or more.

[Aliphatic ester lubricant]
Aliphatic ester lubricants include methyl laurate, methyl myristate, methyl palmitate, methyl stearate, methyl oleate, methyl erucate, methyl behenate, butyl laurate, butyl stearate, isopropyl myristate, palmitic acid Isopropyl, octyl palmitate, octyl palm fatty acid, octyl stearate, beef tallow fatty acid octyl ester, lauryl lauryl, stearyl stearate, behenyl behenate, cetyl myristate, 28-30 carbon linear and unbranched saturated Monocarboxylic acid (hereinafter abbreviated as montanic acid) and ethylene glycol ester, montanic acid and glycerol ester, montanic acid and butylene glycol ester, montanic acid and trimethylolethane ester Esters of montanic acid and trimethylolpropane, esters of montanic acid and pentaerythritol, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan sesquilate, sorbitan trioleate, polyoxyethylene sorbitan mono Examples thereof include laurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan monooleate, and polyoxyethylene sorbitan trioleate. These may be used singly or in combination of two or more.

[Fatty acid lubricant]
Among the fatty acid lubricants, specific examples of saturated fatty acids include lauric acid (dodecanoic acid), isodecanoic acid, tridecylic acid, myristic acid (tetradecanoic acid), pentadecylic acid, palmitic acid (hexadecanoic acid), margaric acid (heptadecanoic acid) ), Stearic acid (octadecanoic acid), isostearic acid, tuberculostearic acid (nonadecanoic acid), 2-hydroxystearic acid, arachidic acid (icosanoic acid), behenic acid (docosanoic acid), lignoceric acid (tetradocosanoic acid), serotic acid (Hexadocosanoic acid), montanic acid (octadocosanoic acid), melicic acid and the like can be mentioned, and in particular, lauric acid, palmitic acid, stearic acid, behenic acid, 12-hydroxystearic acid, and montanic acid.
Among the fatty acid lubricants, as the unsaturated fatty acid, specifically, myristoleic acid (tetradecenoic acid), palmitoleic acid (hexadecenoic acid), oleic acid (cis-9-octadecenoic acid), elaidic acid (trans-9-octadecenoic acid) ), Ricinoleic acid (octadecadienoic acid), vaccenic acid (cis-11-octadecenoic acid), linoleic acid (octadecadienoic acid), linolenic acid (9,11,13-octadecatrienoic acid), elestearic acid ( 9,11,13-octadecatrienoic acid), gadoleic acid (icosanoic acid), erucic acid (docosanoic acid), nervonic acid (tetradocosanoic acid), and the like. These may be used singly or in combination of two or more.

[Fatty acid metal salt lubricant]
Examples of the fatty acid metal salt lubricant include lithium salt, calcium salt, magnesium salt and aluminum salt of the fatty acid of the above fatty acid lubricant. These may be used singly or in combination of two or more.

[Antistatic agent]
Examples of the antistatic agent include cationic, anionic, nonionic, amphoteric, and fatty acid partial esters such as glycerin fatty acid monoester.
Specifically, alkyltrimethylammonium salt, dialkyldimethylammonium salt, benzalkonium salt, N, N-bis (2-hydroxyethyl) -N- (3-dodecyloxy-2-hydroxypropyl) methylammonium mesosulfate , (3-laurylamidopropyl) trimethylammonium methylsulfate, stearoamidopropyldimethyl-2-hydroxyethylammonium nitrate, stearoamidopropyldimethyl-2-hydroxyethylammonium phosphate, cationic polymer, alkylsulfonate Alkyl benzene sulfonate, sodium alkyl diphenyl ether disulfonate, alkyl nitrate ester salt, alkyl phosphate ester salt, alkyl phosphate amine salt, monoglyceride stearate , Pentaerythritol fatty acid ester, sorbitan monopalmitate, sorbitan monostearate, diglycerin fatty acid ester, alkyldiethanolamine, alkyldiethanolamine fatty acid monoester, alkyldiethanolamide, polyoxyethylene dodecyl ether, polyoxyethylene alkylphenyl ether, polyethylene glycol Examples thereof include monolaurate, polyoxyethylene alkylamine, polyoxyethylene alkylamide, polyether block copolymer, cetyl betaine, and hydroxyethyl imidazoline sulfate. These may be used singly or in combination of two or more.

[Nuclear agent]
As the nucleating agent, sorbitols, phosphorus-based, rosins, petroleum resins and the like can be used.

[Sorbitol nucleating agents]
Examples of sorbitols such as alkyl-substituted benzylidene sorbitol include 1,3,2,4-dibenzylidene sorbitol, 1,3,2,4-di- (p-methylbenzylidene) sorbitol, and 1,3-o-methyl. Benzylidene 2,4-p-methylbenzylidene sorbitol, 1,3,2,4-di- (p-ethylbenzylidene) sorbitol, 1,3,2,4-di- (2 ′, 4′-dimethylbenzylidene) sorbitol Etc.

[Phosphorus nucleating agent]
Examples of phosphorus-based compounds include bis (4-t-butylphenyl) sodium phosphate, 2,2′-ethylidene-bis (4,6-di-t-butylphenyl) sodium phosphate, and organic phosphate-based composite products. Is mentioned.
In addition, sodium benzoate, pt-butyl aluminum benzoate, sodium montanate, calcium montanate, aluminum oxide, kaolin clay, talc, rosins, petroleum resins and the like can be mentioned. These may be used singly or in combination of two or more.

[Metal deactivator]
As the metal deactivator, triazines, phosphones, epoxies, triazoles, hydrazides, oxamides, and the like can be used.
Specifically, N, N′-bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyl] hydrazine, bis (2-phenoxypropionylhydrazide) isophthalate, decanedicarboxylic acid disali Tyroylbidazide, bisbenzylidenehydrazide oxalate, N, N′-bis {2- [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyloxyl] ethyl} oxamide, 3- (N -Salicyloyl) amino-1,2,4, -triazole, acid amide, melamine, tris [2-t-butyl-4-thio (2'-methyl-4'-hydroxy-5-t-butyl) phenyl- 5-methyl] phosphite. These may be used singly or in combination of two or more.

[filler]
As the filler, talc, calcium carbonate, barium sulfate, carbon fiber, mica, wollastonite, whisker and the like can be used.
In addition, a coloring agent, an anti-blooming agent, a surface treatment agent, an antibacterial agent, an anti-spotting agent (a silicone oil described in JP 2009-120717 A, a monoamide compound of a higher aliphatic carboxylic acid, and a higher aliphatic carboxylic acid) An anti-smudge agent such as a monoester compound obtained by reacting a monovalent to trivalent alcohol compound) may be added.

[Method for Producing Flame Retardant Polyolefin Resin Composition]
The flame retardant polyolefin-based resin composition of the present embodiment is prepared by mixing a preliminary mixture obtained by mixing at least the component (A), the component (B), the component (C), and the component (D) by any method. It can be manufactured by melt-kneading.
For example, the method of using a uniaxial or biaxial continuous kneader, a roll mixer, etc. alone or in combination thereof may be mentioned.
In particular, the kneading extruder described in Japanese Patent No. 3964314 is preferably used. The kneading and extruding machine includes a biaxial kneading portion having a screw having a biaxial portion L / D (length / diameter) of 12 or more and having a damming structure at the end of the biaxial portion; And the screw diameter D (mm) and the length Lf (mm) of the raw material supply unit are kneading extruders having a relationship of (Lf / D) /D=0.12 to 0.33 mm ⁻¹ .
In the above kneading extruder, (1) since the dispersibility of the flame retardant is remarkably improved, a high level of flame retardancy is exhibited with a small amount of flame retardant, and the mechanical properties are remarkably improved. (2) No surging occurs In addition, there is an advantage that the flame retardant is not ejected from the open vent, the productivity is improved, and (3) the extrusion performance (discharge amount) of the melt-kneading is improved.

[Molding method of molded product obtained by molding flame retardant polyolefin resin composition]
As a method for obtaining a molded article using the flame retardant polyolefin resin composition of the present invention, conventionally known molding methods can be employed. Examples of such a molding method include injection molding, sheet molding, extrusion molding, profile extrusion molding, and hot press molding. Among these, the method of forming a sheet using a melt extruder is preferable from the viewpoint of excellent appearance of the obtained molded product and economical efficiency. These molding conditions are not particularly limited.

[Molded product using flame retardant polyolefin resin composition]
Molded articles using the flame-retardant polyolefin resin composition have flame retardancy that passes UL94 V-0 at a thickness of 0.2 mm or more.
Molded articles having such properties have UL94 V-0 performance at a thickness of 0.2 mm or more, and are required to have the tracking resistance, electrical insulation and chemical resistance, which are the characteristics of polyolefin. It is suitable to be used for an application.
Specifically, among the molded articles of the present invention, for example, the thin molded body is used for computer parts such as desktop personal computers and notebook personal computers, mobile phone parts, electrical / electronic devices, personal digital assistants, home appliance parts, etc. It is preferred that
In particular, the thin molded body is preferably an insulating film or an insulating sheet. Furthermore, battery cases, plastic frames, and the like, for which demands for thin molded articles have been increasing in recent years, can also be mentioned as suitable applications.

[Effect of the embodiment]
According to the above-described embodiment, the following effects can be achieved.
According to the flame retardant polyolefin resin composition of the present embodiment, since the polyolefin resin is used as the component (A) in place of the conventionally used polycarbonate, tracking resistance, electrical insulation and resistance Chemical properties can be imparted at a high level.
As the component (C), a master batch obtained by melting and kneading PTFE is used, so that the dispersibility of PTFE is high and the generation of aggregates is suppressed, so that flame retardancy can be improved.
Since the phosphate ester compound represented by the above general formula (1) is used as the component (D), the dispersibility in the composition of the component (B) and the component (C) is improved. Aggregates and PTFE aggregates are reduced, and the appearance of the molded article is improved. Moreover, since the dispersibility of the phosphoric acid amine salt and PTFE becomes good, the flame retardancy can be further improved.
Moreover, since a polypropylene resin is used as the polyolefin resin, impact resistance can be improved.
In addition, since the polyolefin-based resin having an isotactic pentad fraction of less than 0.97 is used, the dispersibility of the (B) component phosphoric acid amine salt and the (C) component PTFE is improved. Further, the aggregates of amine phosphate and PTFE are reduced, and the appearance of the molded article is improved. Moreover, since the dispersibility of the phosphoric acid amine salt and PTFE becomes good, the flame retardancy can be further improved.

In addition, this invention is not limited to the above-mentioned embodiment, The change in the range which can achieve the objective of this invention, improvement, etc. are included in this invention.
In addition, specific materials and configurations in the implementation of the present invention may be other materials and configurations as long as the object of the present invention can be achieved.

  Next, the present invention will be described in more detail with reference to examples and comparative examples. In addition, this invention is not restrict | limited to the description content of these Examples at all.

  Substances used in the following examples and comparative examples are as follows.

[(A) Group]
Homopolypropylene A (density = 0.905 g / cm ³ , MFR = 6.8 g / 10 min (230 ° C., 2.16 kg), isotactic pentad fraction = 0.94, commercially available product)
-Ethylene-propylene block copolymer A (density = 0.898 g / cm ³ , MFR = 3.0 g / 10 min (230 ° C., 2.16 kg), isotactic pentad fraction = 0.94, commercially available product )
-Ethylene-propylene block copolymer B (density = 0.903 g / cm ³ , MFR = 13 g / 10 min (230 ° C., 2.16 kg), isotactic pentad fraction = 0.97, commercially available product)
-Ethylene-octene copolymer A (ENGAGE8452 manufactured by Dow Chemical Company)
-Ethylene-octene copolymer B (ENGAGE 8200 manufactured by Dow Chemical Company)
・ Ethylene-butene copolymer (ENGAGE7467 manufactured by Dow Chemical Company)

[(B) Group]
-Phosphoric acid amine salt A (a flame retardant comprising 40/60 mass ratio of dimelamine pyrophosphate component (A) / piperazine pyrophosphate component (B), FP2100JC manufactured by ADEKA)
-Phosphoric acid amine salt B (a flame retardant having a mass ratio of dimelamine pyrophosphate component (A) / piperazine pyrophosphate component (B) of 40/60, FP2050 manufactured by ADEKA)

[(C) Group]
-PTFE powder (Daikin Industries, Ltd. Polyflon MPA FA-500H)
PTFE-containing mixed powder (PTFE and polyalkyl (meth) acrylate having an alkyl group having 4 or more carbon atoms mixed in a mass ratio of 5/1, Mitsubishi Rayon Metablene A3000)
-PTFE melt-kneaded master batch (PTFE-containing mixed powder methabrene A3000 and ethylene-propylene block copolymer A are mixed at a mass ratio of 1/5 and melt-kneaded PTFE master batch)

[(D) Group]
-Phosphate ester A (PX-200 manufactured by Daihachi Chemical Industry Co., Ltd.)
・ Phosphate ester B (FP-600 manufactured by ADEKA)
・ Phosphate ester C (FP-800 manufactured by ADEKA)

[Other additives]
・ Dispersant / Lubricant (saturated aliphatic carbon number 30 montanic acid ester, Clariant Ricolb WE40)
Phenol antioxidant (3,9-bis [1,1-dimethyl-2- [β- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] ethyl] 2,4,8 , 10-tetraoxaspiro [5,5] -undecane, ADEKA ADK STAB AO80)
Phosphorus antioxidant (Tris (2,4-di-t-butylphenyl) phosphite, ADEKA ADEKA STAB 2112)
Thio antioxidant (2,2-bis {[3- (dodecylthio) -1-oxopropyl] methyl} propane-1,3-diylbis [3- (dodecylthio) propionate], ADEKA ADK STAB AO412S)
・ Mineral oil softener (Diana Process Oil PW90 manufactured by Idemitsu Kosan Co., Ltd.)

[Examples 1-9, Comparative Examples 1-13]
[1] Production Each component was mixed and melt-kneaded by an extruder to obtain a pellet-like flame-retardant polyolefin resin composition. Hereinafter, each process will be described in detail.
(1) Pre-mixing It mix | blended with the composition of each group shown in the following Table 1-Table 5, and pre-mixed with the tumbler mixer.
Moreover, about an additive, with respect to 100 mass parts of total amounts of (A) group and (B) group, as other additives, 0.3 mass part of dispersing agents and lubricants, 0.5 mass part of phenolic antioxidants , 0.5 parts by mass of a thio antioxidant, 0.2 parts by mass of a phosphorus antioxidant, and 0.3 parts by mass of a mineral oil softener were added.

In addition, 1) in Table 1 is a blending ratio (% by mass) of the (A) group and the (B) group when the total amount of the (A) group and the (B) group is 100% by mass. Moreover, 2) in Table 1 is the number of parts (parts by mass) of the (C) group and (D) group with respect to 100 parts by mass of the total amount of the (A) group and (B) group. The same applies to mass% and parts by mass in Examples 2 to 9 and Comparative Examples 1 to 13 in Tables 1 to 5.
Moreover, 3) of Table 1-Table 5 made the polypropylene component amount contained in the substance of (C) group the compounding ratio (mass%) of a component (A).

(2) Melt kneading The premix obtained by the above premixing was melt kneaded by the following kneading extruder.
HTM type biaxial continuous kneading and extruding machine HTM38 manufactured by CTE Co., Ltd. [screw diameter = 38 mm, L / D = 28 (biaxial part)]
In the HTM kneading extruder, the biaxial kneading section and the single-shaft kneading section have an integral structure.
Further, the screw is of a non-meshing opposite direction type, the screw structure of the screw is a double thread, the first kneading part has a mixing grotter in the first kneading part and the second kneading part of the biaxial kneading part, There is an open vent between the second kneading section and the end of the biaxial kneading section has a damming structure and an orifice adjusting function for adjusting the resin flow rate. From the orifice adjusting function part to the die is a uniaxial kneading part, and has a vacuum vent between them.
The discharge amount of the flame retardant resin composition was adjusted by the damming structure and the orifice adjusting function. The orifice opening was fully open.
The screw size of the kneading machine is as follows: screw diameter D = 38 mm, L _{1 of} the first kneading part (mixin grouter length mm) / D = 12, L _{2 of} the second kneading part (mminx grouter length mm) / D = 3. The operating conditions were a discharge rate of 40 to 80 kg / h, a cylinder set temperature of 200 to 240 ° C., and a screw rotation speed of 300 to 500 rpm.

[2] Molding Extruded sheets were manufactured by using an extruder equipped with a Toyo Seiki Seisakusho T150C (die width 150 mm) as a T-die on a Toyo Seiki Seisakusho lab plast mill 4M150 (full flight screw, screw diameter 25 mm). Using.
The pellet obtained by the above melt-kneading was introduced into the hopper of an extruder, and melt-extruded from the T die under the following extrusion conditions. The extrusion conditions were an extrusion temperature of 200 to 240 ° C., a screw rotation speed of 10 to 50 rpm, and a lip opening of 0.1 to 0.8 mm.
The extruded resin was cooled and solidified and wound by a winder equipped with a cooling roll to obtain an extruded sheet having a desired thickness (0.2 mm). The winding conditions were a roll temperature of 50 to 60 ° C. and a take-up speed of 0.9 to 1.5 m / min.

[3] Evaluation The following evaluation tests were performed on the extruded sheets obtained in the examples and comparative examples. The results are shown in Tables 1 to 5 below.
(1) Flame retardance An extruded sheet having a thickness of 0.2 mm obtained by extrusion molding was cut to a width of 12.7 mm and a length of 127 mm (however, the sheet extrusion direction was defined as the length direction) to prepare a sample. . The produced sample was subjected to a 20 mm vertical combustion test according to the UL94V test standard. About five samples, the combustion rank was given according to UL-94 specification from the combustion time of the 1st time and the 2nd time, the presence or absence of the ignition of cotton, etc., respectively. V-0 has the highest combustion rank, and the flame retardance decreases as V-1 and V-2. However, those not corresponding to any of the ranks V-0 to V-2 were set to not-V.
(2) Number of Aggregates of PTFE and Amine Phosphate Salt An extruded sheet having a thickness of 0.2 mm obtained by extrusion molding was cut into a width of 12 cm and a length of 10 m to prepare a sample. About the produced sample, the number of 0.3 mm or more of PTFE and phosphoric acid amine salt aggregates on the sheet surface was counted. As for the number of each aggregate, 0-10 were evaluated as “◯” and 11 or more as “x”.
In addition, how to distinguish the aggregate of PTFE and an amine phosphate salt was performed by elemental analysis. In the case of PTFE aggregates, fluorine atoms were detected, and in the case of phosphoric acid amine salt aggregates, phosphorus atoms were detected.

(3) Chemical resistance A sample was prepared by cutting an extruded sheet having a thickness of 0.2 mm obtained by extrusion molding into a width of 5 cm and a length of 5 cm. The prepared sample was immersed in a solvent at room temperature for 48 hours, and the appearance of the sample after the solvent immersion was evaluated. As the solvent, acetone, methyl ethyl ketone (MEK), methanol and n-heptane were used, respectively. The case where the appearance of the sample after the solvent immersion was unchanged was evaluated as “◯”, the case where rough skin was generated was evaluated as “Δ”, and the case where the solvent crack was generated, dissolved or swollen was evaluated as “X”.
(4) Tracking resistance An extruded sheet having a thickness of 0.2 mm obtained by extrusion molding was cut into 10 cm × 10 cm, and 15 sheets thereof were stacked to prepare a sample having a thickness of 3 mm. About the produced sample, the relative tracking index (CTI value) was calculated | required according to the test method shown by IEC Publication112 specification. The CTI value is better as the applied voltage during the test is larger, and is measured at an applied voltage in the range of 0V to 600V.

(5) Dielectric breakdown voltage An extruded sheet having a thickness of 0.2 mm obtained by extrusion molding was cut into a size of 10 cm × 10 cm, and 5 sheets thereof were stacked to prepare a sample having a thickness of 1 mm. About the produced sample, the dielectric breakdown voltage was calculated | required according to the test method shown by ASTM D149 specification.
(6) Tensile properties A 0.2 mm thick extruded sheet obtained by extrusion molding was cut into a width of 25 mm to prepare a test piece. In addition, the test piece prepared two types, when the sheet extrusion direction is the length direction (MD) and when the direction perpendicular to the extrusion direction is the length direction (TD). About the produced sample piece, according to JIS-K7161 (ISO527-1), the breaking stress (unit: MPa) and elongation at break at a distance of 30 mm between chucks and a pulling speed of 100 mm / min in an environment of 23 ° C. and 50% RH ( Unit:%) was measured.

  As is clear from Tables 1 and 2, Examples 1 to 9 passed V-0 at a thickness of 0.2 mm, there were few aggregates of PTFE and phosphate amine salt, and the sheet appearance was also good. . Moreover, in chemical resistance, the result was rough skin with n-heptane, but good results were obtained with other solvents. The tracking resistance and dielectric breakdown voltage were also good, and the tensile breaking stress and elongation were good. In Example 9, since the ethylene-propylene block copolymer B having an isotactic pentad fraction of 0.97 is used, the flame retardancy is the lowest within the range of the effect of the present invention. In addition, the number of aggregates of PTFE and amine phosphate was large.

As is clear from Table 3, Comparative Example 1 is an example that is 59% by mass for the (A) group and 41% by mass for the (B) group, and is outside the range of the above formulas (F1) and (F2). . In Comparative Example 1, since the compounding amount of the phosphate amine salt was small, in the flame retardance evaluation of thickness 0.2 mm, drip cotton was ignited to V-2, and V-0 was rejected.
The comparative example 2 is an example outside the range of the said numerical formula (F1) and the said numerical formula (F2) as (A) group 44 mass% and (B) group 56 mass%. In Comparative Example 2, the flame retardancy evaluation with a thickness of 0.2 mm is V-0 pass and there are few aggregates of PTFE and amine phosphate, but there is a large amount of phosphate amine salt. The physical properties are remarkably lowered, and the results are not practical.
Comparative Example 3 is an example in which PTFE in the group (C) is 0.070 parts by mass and out of the range of the formula (F5). In Comparative Example 3, since the blending amount of PTFE was small, in the flame retardance evaluation of thickness 0.2 mm, drip cotton was ignited to V-2, and V-0 was rejected.
Comparative Example 4 is an example in which PTFE in the group (C) is 0.170 parts by mass and out of the range of the above formula (F5). In Comparative Example 4, since the blending amount of PTFE is large, the test piece contracts and burns to the clamp in the flame retardance evaluation of 0.2 mm in thickness to become not-V, and the flame retardancy of V-0 is It was rejected. Further, many PTFE aggregates were generated, resulting in poor appearance.

As is apparent from Table 4, Comparative Example 5 is 42% by mass for the (A) group and 58% by mass for the (B) group, which is outside the range of the above formula (F1) and the above formula (F2). (C) The ratio of PTFE / (B) group in the group is 0.00138, which is an example out of the range of the formula (F6). In Comparative Example 5, since the ratio of PTFE / (B) group in group (C) is as low as 0.00138, PTFE aggregates are small, but in the flame retardance evaluation of thickness 0.2 mm, drip cotton It ignited and became V-2, and V-0 was rejected. Moreover, since the compounding quantity of the phosphoric acid amine salt was large, the tensile physical properties were remarkably lowered, and the results were not practical.
In Comparative Example 6, the (A) group is 59% by mass and the (B) group is 41% by mass, which is outside the range of the above formula (F1) and the above formula (F2), and (C) PTFE in the group. / (B) Group ratio is 0.00390, which is an example outside the range of the above formula (F6). In Comparative Example 6, since the ratio of PTFE / (B) group in group (C) is as high as 0.00390, the test piece contracted and burned to the clamp in the flame retardance evaluation of 0.2 mm thickness. It became not-V, V-0 was rejected, and a large amount of PTFE aggregates were generated, resulting in poor appearance.
In Comparative Example 7, the PTFE in the (C) group was 0.070 parts by mass and out of the range of the above formula (F5), and the ratio of the PTFE / (B) group in the (C) group was 0.00. This is an example outside the range of 00143 and the above formula (F6). In Comparative Example 7, since the blending amount of PTFE is small and the ratio of the PTFE / (B) group in the (C) group is low, the drip cotton ignites in the flame retardance evaluation of 0.2 mm thickness. V-2 and V-0 failed.

In Comparative Example 8, the PTFE in the (C) group is 0.170 parts by mass and out of the range of the formula (F5), and the ratio of the PTFE / (B) group in the (C) group is 0.00. This is an example out of the range of the above formula (F6). In Comparative Example 8, since the amount of PTFE is large and the ratio of PTFE / (B) group in group (C) is high, the test piece was evaluated in the flame retardancy evaluation of thickness 0.2 mm. It contracted and burned to the clamp, became not-V, and failed V-0. Further, many PTFE aggregates were generated, resulting in poor appearance.
As is apparent from Table 5, Comparative Example 9 is an example in which the phosphate ester of group (D) is not blended. In Comparative Example 9, since phosphate ester is not blended, in the flame retardance evaluation of thickness 0.2 mm, there is a test piece having a single combustion time exceeding 10 seconds, and thus V-1 evaluation is performed. V-0 was rejected. Moreover, since phosphate ester was not mix | blended, many aggregates of PTFE and a phosphoric acid amine salt generate | occur | produced, and it became the appearance defect.
Comparative Example 10 is an example in which an ethylene-propylene block copolymer B having an isotactic pentad fraction of group (A) of 0.97 is blended, and a phosphate ester of group (D) is not blended. It is. In this comparative example 10, in addition to the example in which the phosphate ester of comparative example 9 is not blended, the ethylene-propylene block copolymer B having an isotactic pentad fraction of 0.97 is blended, In the flame retardance evaluation with a thickness of 0.2 mm, the V-1 evaluation is the same as that of Comparative Example 9, but the total combustion time is 25 to 50 seconds longer than that of Comparative Example 9, and compared with Comparative Example 9. As a result, flame retardancy decreased. In addition, for the same reason, PTFE and phosphoric acid amine salt aggregates also increased, and the appearance deteriorated.
Comparative Example 11 (D) A group of phosphate ester is 4 parts by mass and is an example outside the range of the above formula (F7). In Comparative Example 11, since the amount of the phosphate ester was large, a large amount of the phosphate ester melted during kneading, making it difficult for the resin component pellets to melt (juicing phenomenon). As a result, melt kneading became difficult and the composition could not be obtained, and thus could not be evaluated.

Comparative Example 12 is an example in which PTFE powder was used as group (C). In Comparative Example 12, in the flame retardancy evaluation with a thickness of 0.2 mm, since there was a test piece having one burning time exceeding 10 seconds, it was evaluated as V-1 and was V-0 rejected. Further, many PTFE aggregates were generated, resulting in poor appearance.
Comparative Example 13 is an example in which a mixed powder of organic polymer particles and PTFE particles was used as group (C). In Comparative Example 13, in the flame retardancy evaluation with a thickness of 0.2 mm, since there was a test piece with one burning time exceeding 10 seconds, it was evaluated as V-1 and was V-0 rejected. Further, many PTFE aggregates were generated, resulting in poor appearance.

  The flame-retardant polyolefin-based resin composition of the present invention is excellent in tracking resistance, electrical insulation, chemical resistance, tensile properties, and appearance, and is particularly difficult because UL94 is V-0 at a thickness of 0.2 mm or more. Shows flammability. In particular, it can be suitably used in the field of electrical insulating flame retardant sheets that require electrical characteristics such as tracking resistance and electrical insulation, and chemical resistance.

Claims (7)

A flame-retardant polyolefin resin composition containing at least the following component (A), component (B), component (C) and component (D),
The component (A) is a polyolefin resin,
The component (B) is a phosphate amine salt composed of the component (B-1) and the component (B-2).
The component (B-1) is at least one of piperazine pyrophosphate and piperazine polyphosphate,
The component (B-2) is at least one melamine compound selected from dimelamine pyrophosphate, melamine pyrophosphate and melamine polyphosphate,
The component (C) is a master batch obtained by melt-kneading polytetrafluoroethylene,
The component (D) is a phosphate ester compound represented by the following general formula (1),
When the total amount of the component (A) and the component (B) is 100% by mass, the following formula (F1) and the following formula (F2) are satisfied,
45% by mass ≦ (A) component ≦ 58% by mass (F1)
42% by mass ≦ (B) component ≦ 55% by mass (F2)
The component (B) satisfies the following formula (F3) and the following formula (F4),
55 mass% ≦ (B-1) component ≦ 65 mass% (F3)
35% by mass ≦ (B-2) component ≦ 45% by mass (F4)
With respect to 100 parts by mass of the total amount of the component (A) and the component (B), the polytetrafluoroethylene in the component (C) satisfies the following formula (F5),
0.08 parts by mass ≦ (C) Polytetrafluoroethylene in component ≦ 0.16 parts by mass (F5)
The ratio of polytetrafluoroethylene in the component (C) of the formula (F5) to the component (B) of the formula (F2) satisfies the following formula (F6),
0.00145 ≦ [Polytetrafluoroethylene / component (B) in component (C)] ≦ 0.00381 (F6)
With respect to 100 parts by mass of the total amount of the component (A) and the component (B), the component (D) satisfies the following mathematical formula (F7): 0.5 part by mass ≦ (D) component ≦ 3 parts by mass ( F7)
A flame retardant polyolefin-based resin composition characterized by the above.

(However, in the said General formula (1), R < ¹ >, R < ² >, R < ⁴ > and R < ⁵ > may be same or different, and are C1-C10 alkyl groups or following General formula (2). R ³ represents a divalent aromatic group represented by the following general formula (3) or the following general formula (4), and s is a number from 0 to 30.

(However, the general formulas above general formula (2) in (4), ^{A 1} and ^{A 2} each independently represent a hydrogen atom, ^.A 3 representing a hydroxy group or an alkyl group having 1 to 10 carbon atoms, A ⁴ , A ⁵ , A ⁶ , A ⁷ and A ⁸ are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a cycloalkyl group, an aryl group, an alkoxy group, a nitro group, a halogen atom or a cyano group. G represents a direct bond, a divalent sulfur atom, a sulfone group, an alkylidene group having 1 to 5 carbon atoms, or an alkylene group. In the flame-retardant polyolefin resin composition according to claim 1,
The flame retardant polyolefin resin composition, wherein the polyolefin resin of the component (A) is a polypropylene resin. In the flame-retardant polyolefin resin composition according to claim 2,
The flame retardant polyolefin resin composition, wherein the component (A) has a polypropylene resin having an isotactic pentad fraction of less than 0.97. In the flame-retardant polyolefin resin composition according to any one of claims 1 to 3,
The component (A) is 35% by mass or more and 57.5% by mass or less of polypropylene, and the ethylene homopolymer or the copolymer mainly composed of ethylene is 0.5% by mass or more and 10% by mass or less. A flame retardant polyolefin resin composition. In the flame-retardant polyolefin resin composition according to any one of claims 1 to 4,
The flame retardant polyolefin resin composition, wherein the matrix resin of the master batch in which the polytetrafluoroethylene is melt-kneaded in the component (C) is a polyolefin resin.   A molded product obtained by molding the flame-retardant polyolefin resin composition according to any one of claims 1 to 5. A method for producing a flame retardant polyolefin resin composition according to any one of claims 1 to 5,
A flame retardant polyolefin resin characterized by melting and kneading at least a premix obtained by mixing each of the component (A), the component (B), the component (C) and the component (D). A method for producing the composition.