JP2016027159A - Flame-retardant polyolefin resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a flame-retardant polyolefin resin composition having excellent flame retardancy even in a thin material.SOLUTION: The flame-retardant polyolefin resin composition contains a component (A): an ethylene-vinyl acetate copolymer and/or an ethylene-(meth)acrylate copolymer, a component (B): a polyolefin resin, a component (C): a (poly)phosphate compound represented by general formula (1), a component (D): a (poly)phosphate compound represented by general formula (3), and a component (E): talc. The content of the component (E) is 1-70 wt.% based on the total amount of the component (C) and the component (D).SELECTED DRAWING: None

Description

  The present invention relates to a flame retardant polyolefin resin composition. Specifically, the present invention relates to a polyolefin resin composition having excellent flame retardancy even in a thin-walled material.

  Polyvinyl chloride resin and its resin composition are excellent in electrical insulation and have self-extinguishing flame retardant properties, so they are widely used in wire coverings, tubes, tapes, building materials, automobile parts, home appliance parts, etc. . However, since polyvinyl chloride resin contains chlorine in its molecular structure, it generates hydrogen chloride gas, which is a corrosive gas during combustion, and may generate toxic gases such as dioxins depending on the combustion conditions. . For this reason, as a part of countermeasures against recent environmental problems, materials that do not contain halogens (hereinafter sometimes referred to as “halogen-free materials”) that hardly generate these toxic gases during combustion are used. Tend to be.

Examples of the halogen-free material include polyolefin resins typified by polypropylene and polyethylene and styrene resins. However, since these resins are easily combustible, they need to be flame retardant depending on the application. As a countermeasure, a method of adding a halogen-based flame retardant has been used for a long time. However, a halogen-based flame retardant also has a problem of generating a toxic gas at the time of combustion. Recently, as a non-halogen-based flame retardant, magnesium hydroxide or water is used. A technique of blending a metal hydroxide such as aluminum oxide is employed.
These flame retardant resin compositions containing magnesium hydroxide, aluminum hydroxide, etc. can prevent the generation of halogen gas during combustion, but in order to obtain the required flame retardant performance, a large amount of flame retardant is filled. There is a problem that the physical properties of the resin composition are inferior and the molding processing properties are inferior due to the influence.

On the other hand, phosphoric ester-based flame retardants such as triphenyl phosphate (TPP) are used as flame retardants that do not contain halogens. However, these are highly volatile, and gold is added to the resin when it is extruded. There are problems such as contamination of the mold and oozing out on the surface of the molded product, thereby impairing the appearance. Therefore, the use of condensed phosphoric esters having low volatility has been proposed, but these flame retarding effects are still insufficient.
Therefore, in recent years, in order to meet the above requirements, as a flame retardant mainly composed of a specific phosphate, a surface expansion layer is formed at the time of combustion, and flame retardancy is suppressed by suppressing the diffusion and heat transfer of decomposition products. Intomesent flame retardants have been proposed (Patent Document 1). Although intomescent flame retardants have excellent flame retardancy, they have problems such as poor dispersion in resins due to secondary aggregation and deterioration of hygroscopicity due to hydrolysis, but phosphoric acid having a specific molecular structure. Improvements have been made by co-adding compounds such as ester, silicone oil, polycarbodiimide, etc. (Patent Documents 2 to 4).

JP 2003-26935 A JP 2004-238568 A JP 2009-120717 A JP 2009-292965 A

As described in the above background art, it is possible to obtain a flame retardant polyolefin resin composition having good flame resistance, heat resistance, and water resistance by adding an intumescent flame retardant to a polyolefin resin. . However, in each of the above-mentioned patent documents, a test using a test piece having a thickness of 1.6 mm is performed in the UL94V combustion test, and no evaluation is made when a test piece having a thin thickness is used.
On the other hand, in the electric wire field, flame retardancy is often required for thinner molded products. Therefore, as a result of the inventors confirming the above-mentioned patent document, the test piece having a thickness of about 0.5 to 1.0 mm spreads quickly and it is difficult to maintain high flame retardancy. It has been found that dripping is also likely to occur.

Therefore, a material having good flame retardancy is expected even when a thin test piece having a thickness of about 0.5 to 1.0 mm is used in a combustion test such as UL94V. It has not been clear so far whether this can be achieved.
This invention is made | formed in view of the said situation, The objective is to provide the flame-retardant polyolefin resin composition which has the flame retardance excellent also in the thin-walled material.

  As a result of intensive studies in view of the above problems, the present inventors have formulated and combined the specific resin as the polyolefin resin and combined the specific phosphorus-based flame retardant. The present invention has been completed by finding that it can be solved.

That is, the gist of the present invention is the following [1] to [7].
[1] The following components (A) to (E) are contained, and the content ratio of the component (E) to the total amount of the components (C) and (D) is 1 to 70% by weight. Flame retardant polyolefin resin composition.
Component (A): Ethylene-vinyl acetate copolymer and / or ethylene- (meth) acrylate copolymer Component (B): Polyolefin resin Component (C): Represented by the following general formula (1) ) Phosphate compound Component (D): (Poly) phosphate compound represented by the following general formula (3) Component (E): Talc

但し、（１）式中のｎは１〜１００の数、Ｘ^１はアンモニア又は下記一般式（２）で表されるトリアジン誘導体であり、ｐは関係式０＜ｐ≦ｎ＋２を満たす数である。

However, n in the formula (1) is a number from ^{1 to} 100, X ¹ is ammonia or a triazine derivative represented by the following general formula (2), and p is a number satisfying the relational expression 0 <p ≦ n + 2. .

但し、（２）式中のＺ^１及びＺ^２は同一でも異なっていてもよく、それぞれ独立に、−ＮＲ^５Ｒ^６基（ここでＲ^５及びＲ^６はそれぞれ独立に、水素原子、炭素原子数１〜６の直鎖もしくは分岐のアルキル基又はメチロール基）、水酸基、メルカプト基、炭素原子数１
〜１０の直鎖又は分岐のアルキル基、炭素原子数１〜１０の直鎖又は分岐のアルコキシ基、フェニル基及びビニル基からなる群より選ばれる基である。

However, Z ¹ and Z ² in the formula (2) may be the same or different, and are each independently a —NR ⁵ R ⁶ group (where R ⁵ and R ⁶ are each independently a hydrogen atom, a carbon atom, A linear or branched alkyl group or methylol group of 1 to 6), hydroxyl group, mercapto group, 1 carbon atom
-10 linear or branched alkyl group, a linear or branched alkoxy group having 1 to 10 carbon atoms, a phenyl group and a vinyl group.

但し、（３）式中のｒは１〜１００の数、Ｙ^１は〔Ｒ^１Ｒ^２Ｎ（ＣＨ_２）_ｍＮＲ^３Ｒ^４〕、ピペラジンまたはピペラジン環を含むジアミンであり、Ｒ^１、Ｒ^２、Ｒ^３及びＲ^４はそれぞれ独立に、水素原子、又は炭素原子数１〜５の直鎖もしくは分岐のアルキル基、ｍは１〜１０の整数、ｑは関係式０＜ｑ≦ｒ＋２を満たす数である。

However, in the formula (3), r is a number of 1 to 100, Y ¹ is [R ¹ R ² N (CH ₂ ) _m NR ³ R ⁴ ], a piperazine or a diamine containing a piperazine ring, R ¹ , R ² , R ³ and R ⁴ are each independently a hydrogen atom or a linear or branched alkyl group having 1 to 5 carbon atoms, m is an integer of 1 to 10, and q satisfies the relational expression 0 <q ≦ r + 2. Is a number.

[2] In [1], 5 to 95% by weight of component (A) and 95 to 5% by weight of component (B) are contained with respect to the total amount of component (A) and component (B). Flame retardant polyolefin resin composition.
[3] The flame retardant polyolefin resin composition according to [1] or 2, wherein the vinyl acetate content in the total amount of the component (A) and the component (B) is 1 to 45% by weight.
[4] The flame retardant polyolefin resin composition according to [1] or 2, wherein the (meth) acrylic acid ester content in the total amount of the component (A) and the component (B) is 1 to 45% by weight.
[5] The flame-retardant polyolefin resin composition according to any one of [1] to [4], wherein the total content of the component (C) and the component (D) is 15 to 60% by weight in the resin composition.
[6] A molded article obtained by molding the flame retardant polyolefin resin composition according to any one of [1] to [5].
[7] An electric wire formed by coating the flame retardant polyolefin resin composition according to any one of [1] to [5].

  ADVANTAGE OF THE INVENTION According to this invention, the flame retardant polyolefin resin composition which can hold | maintain high flame retardance also in a thin material is provided.

Hereinafter, the present invention will be described in detail, but the present invention is not limited to the following description, and can be arbitrarily modified and implemented without departing from the gist of the present invention.
The flame-retardant polyolefin resin composition of the present invention contains the following components (A) to (E).
Component (A): Ethylene-vinyl acetate copolymer and / or ethylene- (meth) acrylate copolymer Component (B): Polyolefin resin Component (C): Represented by the following general formula (1) ) Phosphate compound Component (D): (Poly) phosphate compound represented by the following general formula (3) Component (E): Talc

但し、（１）式中のｎは１〜１００の数、Ｘ^１はアンモニア又は下記一般式（２）で表されるトリアジン誘導体であり、ｐは関係式０＜ｐ≦ｎ＋２を満たす数である。

However, n in the formula (1) is a number from ^{1 to} 100, X ¹ is ammonia or a triazine derivative represented by the following general formula (2), and p is a number satisfying the relational expression 0 <p ≦ n + 2. .

但し、（２）式中のＺ^１及びＺ^２は同一でも異なっていてもよく、それぞれ独立に、−ＮＲ^５Ｒ^６基（ここでＲ^５及びＲ^６はそれぞれ独立に、水素原子、炭素原子数１〜６の直鎖もしくは分岐のアルキル基又はメチロール基）、水酸基、メルカプト基、炭素原子数１〜１０の直鎖又は分岐のアルキル基、炭素原子数１〜１０の直鎖又は分岐のアルコキシ基、フェニル基及びビニル基からなる群より選ばれる基である。

However, Z ¹ and Z ² in the formula (2) may be the same or different, and are each independently a —NR ⁵ R ⁶ group (where R ⁵ and R ⁶ are each independently a hydrogen atom, a carbon atom, A linear or branched alkyl group or methylol group having 1 to 6 carbon atoms), a hydroxyl group, a mercapto group, a linear or branched alkyl group having 1 to 10 carbon atoms, a linear or branched alkoxy group having 1 to 10 carbon atoms. And a group selected from the group consisting of a group, a phenyl group and a vinyl group.

但し、（３）式中のｒは１〜１００の数、Ｙ^１は〔Ｒ^１Ｒ^２Ｎ（ＣＨ_２）_ｍＮＲ^３Ｒ^４〕、ピペラジンまたはピペラジン環を含むジアミンであり、Ｒ^１、Ｒ^２、Ｒ^３及びＲ^４はそれぞれ独立に、水素原子、又は炭素原子数１〜５の直鎖もしくは分岐のアルキル基、ｍは１〜１０の整数、ｑは関係式０＜ｑ≦ｒ＋２を満たす数である。

However, in the formula (3), r is a number of 1 to 100, Y ¹ is [R ¹ R ² N (CH ₂ ) _m NR ³ R ⁴ ], a piperazine or a diamine containing a piperazine ring, R ¹ , R ² , R ³ and R ⁴ are each independently a hydrogen atom or a linear or branched alkyl group having 1 to 5 carbon atoms, m is an integer of 1 to 10, and q satisfies the relational expression 0 <q ≦ r + 2. Is a number.

Below, each raw material used for this invention is demonstrated.
<Component (A)>
In the present invention, the component (A) is an ethylene-vinyl acetate copolymer and / or an ethylene- (meth) acrylate copolymer.
[Ethylene-vinyl acetate copolymer]
The ethylene-vinyl acetate copolymer used as the component (A) in the present invention means a copolymer having at least a polymer unit derived from ethylene and a polymer unit derived from vinyl acetate. In the present invention, even if ethylene and vinyl acetate are not used as raw materials, those in which the copolymer after polymerization forms the same chemical structure are included in the ethylene-vinyl acetate copolymer in the present invention.

The vinyl acetate content in the ethylene-vinyl acetate copolymer is not limited, but is preferably 10% by weight or more, more preferably 20% by weight or more, while preferably 55% by weight or less, more preferably 45% by weight. It is as follows.
By using an ethylene-vinyl acetate copolymer having a vinyl acetate content in the above range together with the component (B) described later, the flame retardancy and heat resistance of the flame retardant polyolefin resin composition of the present invention are good. Become. When the vinyl acetate content of the component (A) is less than the above lower limit value, the flame retardancy of the resulting resin composition tends to be insufficient. On the other hand, when the vinyl acetate content of the component (A) exceeds the above upper limit, the affinity with the component (B) decreases, and the tensile fracture stress of the resulting resin composition tends to deteriorate.

  Here, vinyl acetate content means the weight ratio of the monomer derived from vinyl acetate among all the monomer units which comprise an ethylene-vinyl acetate copolymer. In the present invention, the measurement of vinyl acetate content means a value measured according to JIS K7192 (1999) using a Fourier transform infrared spectrophotometer.

  In addition to ethylene and vinyl acetate, the copolymer (A) ethylene-vinyl acetate copolymer may contain other copolymer components. The copolymerizable component is not limited, and examples thereof include propylene, 1-butene, 3-methyl-1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene and 1-decene. And an α-olefin having about 3 to 20 carbon atoms, a copolymer with (meth) acrylic acid, (meth) acrylic acid ester, styrene, and the like. In addition, when it contains (meth) acrylic acid ester as another copolymerization component, it is set as content below vinyl acetate content.

Although the melt flow rate (MFR) of the ethylene-vinyl acetate copolymer of component (A) is not limited, the value measured at 190 ° C. and 21.2 N load is usually 0.2 to 60 g according to JIS K7210 (1999). / 10 minutes, preferably 1 to 35 g / 10 minutes, more preferably 2 to 30 g / 10 minutes. When MFR exceeds the above upper limit, the extrusion moldability of the obtained flame-retardant polyolefin resin composition tends to be lowered. If the MFR is less than the above lower limit, the fluidity is insufficient, so that the moldability of the obtained flame-retardant polyolefin resin composition tends to be lowered.
In the present invention, the ethylene-vinyl acetate copolymer may be used alone or in combination of two or more having different copolymer weight ratios or different MFRs. In addition, the said vinyl acetate content in the case of using together 2 or more types of ethylene-vinyl acetate copolymers means an average value. That is, the average value may be in the numerical range, but it is particularly preferable that each ethylene-vinyl acetate copolymer is in the numerical range.

  Although the manufacturing method of the ethylene-vinyl acetate copolymer of a component (A) is not limited, Usually, well-known manufacturing methods, such as solution combination, latex polymerization, and high pressure method radical polymerization, are mentioned. In particular, when an ethylene-vinyl acetate copolymer having a vinyl acetate content of 45% by weight or less is produced as the component (A), it is preferably produced by high-pressure radical polymerization. Moreover, when producing an ethylene-vinyl acetate copolymer having a vinyl acetate content in the range of 40% by weight or more as the component (A), it is preferably produced by solution polymerization.

  Specific conditions for producing the ethylene-vinyl acetate copolymer of component (A) by high-pressure radical polymerization are not limited, but usually, ethylene and vinyl acetate are used as essential raw materials, and organic peroxide or azo The reaction is performed at a temperature of 150 to 350 ° C. and a pressure of 100 to 300 MPa using a radical initiator such as a compound.

Although the specific conditions at the time of manufacturing the ethylene-vinyl acetate copolymer of a component (A) by solution polymerization are not limited, Usually, ethylene and vinyl acetate are an essential raw material, tert-butanol etc. are used as a solvent, Using a radical initiator such as an organic peroxide or an azo compound, at a temperature of 50 to 150 ° C., preferably 55 to 70 ° C., 10 to 70 MPa (100 to 700 bar), preferably 30 to 40 MPa (300 to 400 bar). ) Under pressure.
Such a production method is disclosed in, for example, JP-A-1-101304, JP-A-7-33829, European Patent Application Publication No. A0341499, European Patent Application Publication No. A051.
No. 0478, etc.

  Examples of the ethylene-vinyl acetate copolymer of component (A) correspond to the above from “Novatech EVA” manufactured by Nippon Polyethylene Co., Ltd., “Evaflex” manufactured by Mitsui DuPont Polychemical Co., “Revaprene” manufactured by LANXESS, etc. You can select and use one.

[Ethylene- (meth) acrylic acid ester copolymer]
The ethylene- (meth) acrylate copolymer used as the component (A) in the present invention is a copolymer having at least a polymer unit derived from ethylene and a polymer unit derived from (meth) acrylate. Means. In the present invention, “(meth) acrylic acid” means acrylic acid or methacrylic acid. In the present invention, even if ethylene and (meth) acrylic acid ester are not used as raw materials, those in which the copolymer after polymerization forms the same chemical structure are those of the ethylene- (meth) acrylic acid ester copolymer in the present invention. Included in coalescence.

  Although the polymer unit derived from the (meth) acrylic acid ester in the ethylene- (meth) acrylic acid ester copolymer is not limited, for example, an ester of (meth) acrylic acid and a hydrocarbon alcohol having about 1 to 20 carbon atoms. A compound. Specifically, acrylic acid esters such as methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, n-hexyl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-hexyl methacrylate, etc. And methacrylic acid esters.

The (meth) acrylic acid ester content in the ethylene- (meth) acrylic acid ester copolymer used as the component (A) in the present invention is not limited, but is preferably 10% by weight or more, more preferably 20% by weight or more. On the other hand, it is preferably 50% by weight or less, more preferably 40% by weight or less.
By using together the ethylene- (meth) acrylic acid ester copolymer whose (meth) acrylic acid ester content is in the above range together with the component (B) described later, it is difficult for the flame-retardant polyolefin resin composition of the present invention. Good flammability and heat resistance. When the (meth) acrylic acid ester content of the component (A) is less than the above lower limit value, the flame retardancy of the resulting resin composition tends to be insufficient. On the other hand, when the (meth) acrylic acid ester content of the component (A) exceeds the above upper limit, the affinity with the component (B) decreases, and the tensile fracture stress of the resulting resin composition tends to deteriorate. It is in.

  Here, (meth) acrylic acid ester content is the weight ratio of the monomer derived from (meth) acrylic acid ester among all monomer units constituting the ethylene- (meth) acrylic acid ester copolymer. Means. In the present invention, the measurement of the (meth) acrylic acid ester content may employ a known measurement method such as measurement with a Fourier transform infrared spectrophotometer.

  The ethylene- (meth) acrylic acid ester copolymer of component (A) may contain other copolymerization components in addition to ethylene and (meth) acrylic acid ester. The copolymerizable component is not limited, and examples thereof include propylene, 1-butene, 3-methyl-1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene and 1-decene. And an α-olefin having about 3 to 20 carbon atoms, a copolymer with (meth) acrylic acid, vinyl acetate, styrene and the like. In addition, when it contains vinyl acetate as another copolymerization component, it is set as content lower than (meth) acrylic acid ester content.

Melt flow rate of ethylene- (meth) acrylate copolymer of component (A) (
MFR) is not limited, but according to JIS K7210 (1999), the value measured at 190 ° C. and 21.2 N load is usually 0.2 to 60 g / 10 minutes, preferably 1 to 35 g / 10 minutes, more preferably, The thing of the range of 2-30 g / 10min is suitable. When MFR exceeds the above upper limit, the extrusion moldability of the obtained flame-retardant polyolefin resin composition tends to be lowered. If the MFR is less than the above lower limit, the fluidity is insufficient, so that the moldability of the obtained flame-retardant polyolefin resin composition tends to be lowered.
In the present invention, the ethylene- (meth) acrylic acid ester copolymer may be used alone or in combination of two or more having different copolymerization ratios or different MFRs. In addition, the said (meth) acrylic acid ester content in the case of using together 2 types of ethylene- (meth) acrylic acid ester copolymers means an average value. That is, the average value may be in the numerical range, but it is particularly preferable that each ethylene- (meth) acrylic acid ester copolymer is in the numerical range.

Although the manufacturing method of the ethylene- (meth) acrylic acid ester copolymer of a component (A) is not limited, Usually, well-known manufacturing methods, such as high pressure method radical polymerization and solution polymerization, are mentioned.
Although the specific conditions at the time of manufacturing the ethylene- (meth) acrylic acid ester copolymer of a component (A) by high pressure method radical polymerization are not limited, Usually, ethylene and a (meth) acrylic acid ester are essential raw materials. And using a radical initiator such as an organic peroxide or an azo compound at a temperature of 150 to 350 ° C. under a pressure of 100 to 300 MPa.

  As an ethylene- (meth) acrylic acid ester copolymer of the component (A), for example, “EEA” manufactured by Nihon Unicar Co., Ltd., “Elvalloy AC” manufactured by Mitsui DuPont Polychemical Co., etc. is selected. Can be used.

<Component (B)>
In the present invention, the component (B) means a polyolefin resin. The polyolefin resin used as the component (B) is not limited. For example, homopolymers such as ethylene, propylene, 1-butene, and the like, or each of them and 3-methyl-1-butene, 1-pentene, 4-methyl-1 -Other α-olefins having about 2 to 20 carbon atoms such as pentene, 1-hexene, 1-octene, 1-decene, vinyl acetate, vinyl alcohol, (meth) acrylic acid, (meth) acrylic acid ester, etc. And the like. Here, (meth) acrylic acid means acrylic acid or methacrylic acid, and the same applies to (meth) acrylate. The component (B) does not include those included in the component (A).

Specific examples of the polyolefin resin include, for example, low, medium and high density polyethylene (branched or linear) ethylene homopolymer, ethylene-propylene copolymer, ethylene-1-butene copolymer, ethylene- 4-methyl-1-pentene copolymer, ethylene-1-hexene copolymer, ethylene-1-octene copolymer, ethylene-vinyl alcohol copolymer (including saponified ethylene-vinyl acetate copolymer), Ethylene-based resin of ethylene- (meth) acrylic acid copolymer; propylene-based resin such as propylene homopolymer, propylene-ethylene copolymer, propylene-ethylene-1-butene copolymer; and 1-butene homopolymer 1-butene resins such as 1-butene-ethylene copolymer and 1-butene-propylene copolymer; ring-opening metathesis of norbornene Coalescence and norbornene derivatives - such as a so-called cyclic polyolefin resins such as ethylene copolymers.
These polyolefin resins may be modified with an unsaturated carboxylic acid such as maleic anhydride, maleic acid or acrylic acid or a derivative thereof, an unsaturated silane compound, or the like. Furthermore, you may have a crosslinked structure partially.

Here, the ethylene-based resin means a polymer containing ethylene as a main component as a raw material monomer, and preferably containing 50% by weight or more of ethylene. The propylene-based resin means a polymer containing propylene as a main component as a raw material monomer, and preferably containing 50% by weight or more of propylene. The same applies to 1-butene resins.

The chain form in the case of using a copolymer as the polyolefin resin is not limited and may be any of a block copolymer, a random copolymer, a graft copolymer, and the like. Moreover, a well-known thing can also be employ | adopted suitably for the polymerization method and the catalyst used for superposition | polymerization.
These polyolefin resins may be used individually by 1 type, or may use 2 or more types together.

  The melt flow rate (MFR) of the polyolefin resin is not limited, but is preferably 0.1 g / 10 min or more, more preferably 0.3 g / 10 min or more, still more preferably 0.5 g / 10 min or more, preferably It is desirable that it is 50 g / 10 min or less, more preferably 30 g / 10 min or less, and still more preferably 10 g / 10 min or less. Here, MFR means a value at 230 ° C. and 21.2 N load when the polyolefin resin is a propylene resin, and when the polyolefin resin is an ethylene resin, a 1-butene resin or other polyolefin resin. Means a value at 190 ° C. and a load of 21.2 N. If the MFR of the polyolefin resin is less than the lower limit value, the fluidity is too low and the load on the extruder tends to increase and the productivity tends to decrease. If the MFR exceeds the upper limit value, the fluidity is too high. It tends to be difficult to form a strand by an extruder.

The flexural modulus of the polyolefin resin is not limited, but the lower limit is usually 500 MPa or more, preferably 800 MPa or more. If the flexural modulus of the polyolefin resin is less than the lower limit, sufficient flame retardancy may not be obtained. This is probably because polyolefin resins having a low flexural modulus generally have a low crystallinity or a low melting point, so that drip is likely to occur during combustion.
The upper limit of the flexural modulus of the polyolefin resin is not limited, but is usually 2200 MPa or less, preferably 2000 MPa or less.
In the present invention, the flexural modulus is measured based on JIS K7171 (propylene resin) or JIS K6922-2 (ethylene resin).
When a plurality of polyolefin resins are used as the component (B), it is preferable that the flexural modulus of at least one component polyolefin resin is in the above range. In particular, 20% by weight or more of the polyolefin resin constituting the component (B) is preferably a polyolefin resin having a flexural modulus in the above range, and more preferably 40% by weight or more.

[Propylene resin]
As the polyolefin resin used as the component (B), a propylene-based resin is suitable. As described above, the propylene-based resin is not limited as long as it is a resin containing propylene as a main component. Usually, the propylene monomer unit is 50% by weight or more, preferably 60% by weight or more, more preferably 70% by weight. % Or more of the polymer is desirable. When the propylene monomer unit constituting the propylene-based resin is set to the lower limit value or more, the expression of flame retardancy of the obtained flame retardant polyolefin resin composition tends to be optimized. In addition, the upper limit of content of a propylene monomer unit is not limited, 100 weight%, ie, a propylene homopolymer, can also be used suitably.

The monomer copolymerized with propylene is not limited as long as it is a copolymerizable compound. Specifically, ethylene; 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4 3 carbon atoms such as methyl-1-pentene, 3-methyl-1-pentene, 1-heptene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicocene Α-olefin of about ˜20; various (meth) acrylic esters such as methyl (meth) acrylate; polar monomers such as (meth) acrylic acid, vinyl acetate, vinyl alcohol, maleic anhydride; styrene such as styrene and styrene derivatives System monomers and the like. These monomers may be used alone or in combination of two or more. Especially, as a monomer copolymerized with propylene, ethylene and an α-olefin having about 3 to 20 carbon atoms are preferable.

Such a copolymer is not limited, and specifically, propylene / ethylene copolymer, propylene / 1-butene copolymer, propylene / ethylene / 1-butene copolymer, propylene / 4-methyl-1 -A pentene copolymer, a copolymer of propylene and other α-olefin, a copolymer of propylene and a polar monomer, and the like.
Among these, as a propylene-type resin, a propylene / ethylene copolymer, a propylene / 1-butene copolymer, and a propylene / ethylene / 1-butene copolymer are preferable.

The chain form in the case of using a copolymer as the propylene-based resin is not limited and may be any of a block copolymer, a random copolymer, a graft copolymer, and the like. Moreover, a well-known thing can also be employ | adopted suitably for the catalyst used for superposition | polymerization.
In addition, as the propylene-based resin, these resins may be modified with an unsaturated carboxylic acid such as maleic anhydride, maleic acid, or acrylic acid or a derivative thereof, an unsaturated silane compound, or the like. Furthermore, you may have a crosslinked structure partially.
These propylene resins may be used alone or in combination of two or more.

  The melt flow rate (MFR) of the propylene-based resin is not limited, but is preferably 0.1 g / 10 min or more, more preferably 0.3 g / 10 min or more, even more preferably as a value at 230 ° C. and 21.2 N load. Is 0.5 g / 10 min or more, preferably 50 g / 10 min or less, more preferably 30 g / 10 min or less, still more preferably 10 g / 10 min or less. If the MFR of the propylene resin is less than the lower limit, the fluidity is too low and molding tends to be difficult. If the MFR exceeds the upper limit, the fluidity is too high and molding tends to be difficult. is there.

  The bending elastic modulus of the propylene-based resin is not limited, but the lower limit is usually 500 MPa or more, preferably 800 MPa or more. If the flexural modulus of the propylene-based resin is less than the lower limit, sufficient flame retardancy may not be obtained. This is probably because propylene-based resins having a low flexural modulus generally have low crystallinity or a low melting point, so that drip is likely to occur during combustion. Moreover, although the upper limit of the bending elastic modulus of propylene-type resin is not limited, Usually, it is 2200 MPa or less, It is desirable that it is 2000 MPa or less.

[Ethylene resin]
As polyolefin resin used as a component (B), ethylene-type resin can also be used suitably. Here, as described above, the ethylene-based resin is not limited as long as it is a resin containing ethylene as a main component, but usually, an ethylene monomer unit is 50% by weight or more, preferably 60% by weight or more, more preferably 70% by weight. % Or more of the polymer is desirable. The direction which makes the ethylene monomer unit which comprises ethylene-type resin more than the said lower limit exists in the tendency for the expression of the flame retardance of the flame-retardant polyolefin resin composition obtained to be optimized. In addition, the upper limit of content of an ethylene monomer unit is not limited, 100 weight%, ie, an ethylene homopolymer can also be used suitably.

The monomer copolymerized with ethylene is not limited as long as it is a copolymerizable compound. Specifically, propylene, 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4 3-methyl-1-pentene, 3-methyl-1-pentene, 1-heptene, 1-octene, 1decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicocene, etc. Α-olefin of about 20; various (meth) acrylic esters such as methyl (meth) acrylate; polar monomers such as (meth) acrylic acid, vinyl acetate, vinyl alcohol, maleic anhydride; styrenes such as styrene and styrene derivatives And monomers. These monomers may be used alone or in combination of two or more. Especially, as a monomer copolymerized with ethylene, a C3-C20 alpha olefin is preferable.

Such a copolymer is not limited, but specifically, ethylene / propylene copolymer, ethylene / 1-butene copolymer, ethylene / propylene / 1-butene copolymer, ethylene / 4-methyl-1 -A pentene copolymer, a copolymer of ethylene and another α-olefin, a copolymer of ethylene and a polar monomer, and the like.
The chain form in the case of using a copolymer as the ethylene-based resin is not limited, and may be any of a block copolymer, a random copolymer, a graft copolymer, and the like. Moreover, a well-known thing can also be employ | adopted suitably for the catalyst used for superposition | polymerization.
Further, as the ethylene-based resin, these resins may be modified with an unsaturated carboxylic acid such as maleic anhydride, maleic acid or acrylic acid, a derivative thereof, an unsaturated silane compound, or the like. Furthermore, you may have a crosslinked structure partially.
These ethylene resins may be used alone or in combination of two or more.

  The melt flow rate (MFR) of the ethylene-based resin is not limited, but the value at 190 ° C. and 21.2 N load is preferably 0.1 g / 10 min or more, more preferably 0.3 g / 10 min or more, still more preferably Is 0.5 g / 10 min or more, preferably 50 g / 10 min or less, more preferably 30 g / 10 min or less, still more preferably 10 g / 10 min or less. If the MFR of the ethylene-based resin is less than the lower limit, the fluidity is too low and molding tends to be difficult. If the MFR exceeds the upper limit, the fluidity is too high and molding tends to be difficult. is there.

  The bending elastic modulus of the ethylene-based resin is not limited, but the lower limit is usually 500 MPa or more, preferably 800 MPa or more. If the flexural modulus of the ethylene resin is less than the lower limit, sufficient flame retardancy may not be obtained. This is probably because ethylene resins having a low flexural modulus generally have a low crystallinity or a low melting point, so that drip is likely to occur during combustion. The upper limit of the flexural modulus of the ethylene-based resin is not limited, but is usually 2000 MPa or less, preferably 1800 MPa or less.

<Ingredient (C)>
In the present invention, component (C) is a salt of phosphoric acid and ammonia or a triazine derivative, and is a (poly) phosphate compound represented by the following general formula (1).

但し、（１）式中のｎは１〜１００の数、Ｘ^１はアンモニア又は下記一般式（２）で表されるトリアジン誘導体であり、ｐは関係式０＜ｐ≦ｎ＋２を満たす数である。

However, n in the formula (1) is a number from ^{1 to} 100, X ¹ is ammonia or a triazine derivative represented by the following general formula (2), and p is a number satisfying the relational expression 0 <p ≦ n + 2. .

但し、（２）式中のＺ^１及びＺ^２は同一でも異なっていてもよく、それぞれ独立に、−ＮＲ^５Ｒ^６基（ここでＲ^５及びＲ^６はそれぞれ独立に、水素原子、炭素原子数１〜６の直鎖もしくは分岐のアルキル基又はメチロール基）、水酸基、メルカプト基、炭素原子数１〜１０の直鎖又は分岐のアルキル基、炭素原子数１〜１０の直鎖又は分岐のアルコキシ基、フェニル基及びビニル基からなる群より選ばれる基である。

However, Z ¹ and Z ² in the formula (2) may be the same or different, and are each independently a —NR ⁵ R ⁶ group (where R ⁵ and R ⁶ are each independently a hydrogen atom, a carbon atom, A linear or branched alkyl group or methylol group having 1 to 6 carbon atoms), a hydroxyl group, a mercapto group, a linear or branched alkyl group having 1 to 10 carbon atoms, a linear or branched alkoxy group having 1 to 10 carbon atoms. And a group selected from the group consisting of a group, a phenyl group and a vinyl group.

Specific examples of the linear or branched alkyl group having 1 to 10 carbon atoms represented by Z ¹ and Z ² in the general formula (2) include methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, Tertiary butyl, isobutyl, amyl, isoamyl, tertiary amyl, hexyl, cyclohexyl, heptyl, isoheptyl BR> A tertiary heptyl, n-octyl, isooctyl, tertiary octyl, 2-ethylhexyl, nonyl, decyl, etc. Examples of the linear or branched alkoxy group having 1 to 10 carbon atoms include groups derived from these alkyl groups.

  Specific examples of the triazine derivative include melamine, acetoguanamine, benzoguanamine, acrylic guanamine, 2,4-diamino-6-nonyl-1,3,5-triazine, 2,4-diamino-6-hydroxy-1,3. , 5-triazine, 2-amino-4,6-dihydroxy-1,3,5-triazine, 2,4-diamino-6-methoxy-1,3,5-triazine, 2,4-diamino-6 Ethoxy-1,3,5-triazine, 2,4-diamino-6-propoxy-1,3,5-triazine, 2,4-diamino-6-isopropoxy-1,3,5-triazine, 2,4 -Diamino-6-mercapto-1,3,5-triazine, 2-amino-4,6-dimercapto-1,3,5-triazine and the like.

As the (poly) phosphate compound represented by the general formula (1) used as the component (C) in the present invention, it is preferable to use a salt of phosphoric acid and melamine. Examples thereof include melamine orthophosphate, melamine pyrophosphate, and melamine polyphosphate. In the present invention, among these, it is particularly preferable to use melamine pyrophosphate in which n in the general formula (1) is 2, p is 2, and X ¹ is melamine.

The salt of melamine phosphoric acid such as melamine pyrophosphate used in the present invention is mixed with sodium pyrophosphate and melamine in an arbitrary reaction ratio, and then reacted with hydrochloric acid to obtain sodium hydroxide. It can be obtained by neutralization.
By using a compound corresponding to such component (C) together with component (D) described later, good flame retardancy can be exhibited.

<Component (D)>
In the present invention, component (D) is a salt of phosphoric acid and diamine or piperazine, and is a (poly) phosphate compound represented by the following general formula (3).

但し、（３）式中のｒは１〜１００の数、Ｙ^１は〔Ｒ^１Ｒ^２Ｎ（ＣＨ_２）_ｍＮＲ^３Ｒ^４〕、ピペラジンまたはピペラジン環を含むジアミンであり、Ｒ^１、Ｒ^２、Ｒ^３及びＲ^４はそれぞれ独立に、水素原子、又は炭素原子数１〜５の直鎖もしくは分岐のアルキル基、ｍは１〜１０の整数、ｑは関係式０＜ｑ≦ｒ＋２を満たす数である。

However, in the formula (3), r is a number of 1 to 100, Y ¹ is [R ¹ R ² N (CH ₂ ) _m NR ³ R ⁴ ], a piperazine or a diamine containing a piperazine ring, R ¹ , R ² , R ³ and R ⁴ are each independently a hydrogen atom or a linear or branched alkyl group having 1 to 5 carbon atoms, m is an integer of 1 to 10, and q satisfies the relational expression 0 <q ≦ r + 2. Is a number.

Specific examples of the diamine represented by Y ¹ in the general formula (3) include N, N, N ′, N′-tetramethyldiaminomethane, ethylenediamine, N, N′-dimethylethylenediamine, N, N′— Diethylethylenediamine, N, N-dimethylethylenediamine, N, N-diethylethylenediamine, N, N, N ′, N′-tetramethylethylenediamine, N, N, N ′, N′-tetraethylethylenediamine, tetramethylenediamine, 1, 2-propanediamine, 1,3-propanediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diamino Decane, piperazine, trans-2,5-dimethylpiperazine, 1, - bis (2-aminoethyl) piperazine, 1,4-bis (3-aminopropyl) piperazine, and the like.

  In the present invention, it is preferable to use a salt of phosphoric acid and piperazine as the (poly) phosphate compound represented by the general formula (3) used as the component (D). Include piperazine orthophosphate, piperazine pyrophosphate, piperazine polyphosphate, and the like. Among these, in the present invention, it is preferable to use piperazine polyphosphate in which q in the above general formula (3) is 1 and Y1 is piperazine, and piperazine pyrophosphate is particularly preferable.

The salt of phosphoric acid and piperazine used in the present invention can be easily obtained as a poorly water-soluble precipitate by reacting piperazine and pyrophosphoric acid in water or an aqueous methanol solution. However, in the case of piperazine polyphosphate, it may be a salt obtained from polyphosphoric acid and piperazine composed of a mixture of orthophosphoric acid, pyrophosphoric acid, tripolyphosphoric acid and other polyphosphoric acids, and the composition of the raw polyphosphoric acid is There is no particular limitation.
By using a compound corresponding to such a component (D) together with the component (C), good flame retardancy can be exhibited.
In addition, as a flame retardant containing a component (C) and a component (D), the product made from ADEKA Co., Ltd., brand name: ADK STAB FP2200 is mentioned, for example (in Unexamined-Japanese-Patent No. 2009-185214, the said product is a component ( C) and a flame retardant containing component (D).

<Ingredient (E)>
The flame retardant polyolefin resin composition of the present invention contains talc as the component (E). By containing talc in the flame retardant polyolefin resin composition of the present invention, the flame retardancy and heat resistance of the resin composition tend to be good. This is considered to be because the generation of drip during combustion is suppressed by containing the component (E). In addition, the combined use of component (C) and component (D) and component (E) can suppress the generation of drip without inhibiting the foaming of the resin during combustion, so the carbonized film blocks air. In addition, it is considered that the foamed heat insulating layer can be efficiently formed and high flame retardancy can be expressed. These components (C)
And a synergistic effect with a component (D) can be notably expressed when talc is used as an additive.

<Other ingredients>
In the flame-retardant polyolefin resin composition of the present invention, additives and resins other than the above-mentioned components (A) to (E) are required as “other components” within a range that does not significantly impair the effects of the present invention. It may be used depending on. Other components may be used alone or in combination of two or more in any combination ratio.

  The resin used as the other component is not limited as long as it is a resin other than component (A) and component (B). Specifically, for example, polyphenylene ether resin; polycarbonate resin; nylon 66, nylon 11, etc. Polyamide resins; Polyester resins such as polyethylene terephthalate and polybutylene terephthalate; (Meth) acrylic resins such as polymethyl methacrylate resins; Thermoplastic resins such as styrene resins such as polystyrene; and various thermoplastic elastomers .

  Additives used as other components are not limited as long as they are other than components (C), (D), and (E). Specifically, various heat stabilizers, antioxidants, ultraviolet absorbers, light Stabilizer, anti-aging agent, nucleating agent, plasticizer, impact modifier, compatibilizer, antifoaming agent, thickener, crosslinking agent, surfactant, lubricant, mold release agent, anti-blocking agent, processing aid , Antistatic agents, flame retardants, flame retardant aids, organic fillers, colorants and the like.

In the flame-retardant polyolefin resin composition of the present invention, flame retardants other than the component (C) and the component (D) may be used in combination as other components. Flame retardants are roughly classified into halogen-based flame retardants and non-halogen-based flame retardants, and non-halogen-based flame retardants are preferred. Non-halogen flame retardants other than component (C) and component (D) include phosphorus flame retardants other than component (C) and component (D), nitrogen-containing compounds (melamine-based and guanidine-based) flame retardants and inorganic-based flame retardants. Compound (magnesium hydroxide, aluminum hydroxide, borate, molybdenum compound) flame retardant and the like.
Examples of the heat stabilizer and the antioxidant include hindered phenols, phosphorus compounds, hindered amines, sulfur compounds, copper compounds, alkali metal halides, and the like.

In the flame-retardant polyolefin resin composition of the present invention, a filler other than the component (E) may be used in combination as the other component. The filler other than the component (E) is not limited, but specifically, clay, whisker, wollastonite, calcium carbonate, zinc carbonate, silica, alumina, zinc borate, magnesium oxide, calcium silicate, sodium aluminate , Inorganic fillers such as calcium aluminate, sodium aluminosilicate, magnesium silicate, glass balloon, carbon black, zinc oxide, antimony trioxide, zeolite, metal fiber, potassium titanate, boron nitride, graphite, carbon fiber, glass fiber, etc. And organic fillers such as naturally occurring polymers such as starch, cellulose fine particles, wood flour, okara, fir shell, bran, and modified products thereof.
As the filler other than the component (E), an inorganic compound having an aspect ratio of 2 or more is preferable, and specifically, clay, whisker, wollastonite, carbon fiber, glass fiber, or the like is preferable.

<Flame-retardant polyolefin resin composition>
The content ratio of the component (A) and the component (B) in the flame-retardant polyolefin resin composition of the present invention is as follows. The component (A): 5 to 95 with respect to the total amount of the component (A) and the component (B). % By weight, component (B): preferably 95 to 5% by weight. When content of a component (A) is less than said lower limit, it exists in the tendency for the flame retardance of the resin composition obtained to deteriorate. On the other hand, when content of a component (A) exceeds said upper limit, it exists in the tendency for the flame retardance and heat resistance of the resin composition obtained to deteriorate.
For the same reason as above, the content ratio of the component (A) and the component (B) is 10% to 90% by weight of the component (A) with respect to the total amount of the component (A) and the component (B). (B): It is preferably 90 to 10% by weight, more preferably component (A): 20 to 80% by weight, and component (B): 80 to 20% by weight.

  In the present invention, by using the component (A) and the component (B) in the above composition range, the obtained flame retardant polyolefin resin composition tends to be able to express good flame retardancy and heat resistance. It is in. Even if the component (B) alone contains the component (C), the component (D) and the component (E), the flame retardance of the obtained resin composition is not sufficiently ensured. On the other hand, even if the component (A) alone contains the component (C), the component (D), and the component (E), the resulting resin composition has insufficient flame retardancy and heat resistance, especially during combustion. The drip resistance deteriorates. The effect of using the component (A) and the component (B) in combination is manifested as a remarkable effect when imparting flame retardancy in a thin molded article.

In the flame-retardant polyolefin resin composition of the present invention, the vinyl acetate content in the total amount of the component (A) and the component (B) is not limited, but is usually 1 to 45% by weight, preferably 8 to 30% by weight. It is desirable to be. By setting the vinyl acetate content within the above range, the flame retardant expression of the obtained flame retardant polyolefin resin composition tends to be optimized.
In the flame-retardant polyolefin resin composition of the present invention, the (meth) acrylic acid ester content in the total amount of the component (A) and the component (B) is not limited, but is usually 1 to 45% by weight, preferably 8 to 30% by weight is desirable. By setting the content of the (meth) acrylic acid ester within the above range, expression of flame retardancy of the obtained flame retardant polyolefin resin composition tends to be optimized.

The vinyl acetate content in the flame retardant polyolefin resin composition of the present invention is not limited, but it is usually 1 to 45% by weight, preferably 2 to 30% by weight. By setting the vinyl acetate content within the above range, the flame retardant expression of the obtained flame retardant polyolefin resin composition tends to be optimized.
The (meth) acrylic acid ester content in the flame retardant polyolefin resin composition of the present invention is not limited, but it is usually 1 to 45% by weight, preferably 2 to 30% by weight. By setting the content of the (meth) acrylic acid ester within the above range, expression of flame retardancy of the obtained flame retardant polyolefin resin composition tends to be optimized.
Here, the vinyl acetate content and the (meth) acrylic acid ester content mean a content derived from a vinyl acetate monomer and a content derived from a (meth) acrylic acid ester monomer, respectively.

Although content of the component (A) in the flame-retardant polyolefin resin composition of this invention is not limited, Usually, 3 to 75 weight%, Preferably it is 5 to 60 weight%, More preferably, it is 10 to 50 weight%. By making content of the component (A) in a resin composition into the said range, there exists a tendency for the flame retardance of the flame-retardant polyolefin resin composition obtained to become favorable.
In the present invention, as component (A), an ethylene-vinyl acetate copolymer and an ethylene- (meth) acrylate copolymer may be used in combination. Content in the resin composition in the case of using these together as a component (A) means the total amount of an ethylene-vinyl acetate copolymer and an ethylene- (meth) acrylic acid ester copolymer.
The blending ratio when using an ethylene-vinyl acetate copolymer and an ethylene- (meth) acrylate copolymer in combination as the component (A) is arbitrary, but the vinyl acetate content or the component ( It is desirable that at least one of the (meth) acrylic acid ester contents in A) is adjusted to be in the above numerical range.

  Although content of the component (B) in the flame-retardant polyolefin resin composition of this invention is not limited, Usually, 3 to 75 weight%, Preferably it is 5 to 60 weight%, More preferably, it is 10 to 50 weight%. By setting the content of the component (B) in the resin composition within the above range, the resulting flame-retardant polyolefin resin composition tends to have good flame resistance and heat resistance, particularly drip resistance during combustion. There is.

In the flame retardant polyolefin resin composition of the present invention, the total content of component (C) and component (D) is not limited, but is usually 15 to 60% by weight, preferably 20 to 50% by weight, more preferably 25. ~ 45 wt%. By setting the total content of component (C) and component (D) in the resin composition within the above range, the flame retardancy and tensile fracture stress of the flame retardant polyolefin resin composition of the present invention tend to be good. There is.
In the present invention, the content ratio of the component (C) and the component (D) is not limited, but the component (C): 1 to 99% by weight, the component (D): 99 to 1% by weight (provided that the component (C) and The total amount with the component (D) is 100 parts by weight. Preferable ranges of the content ratio of the component (C) and the component (D) are the component (C): 20 to 80% by weight, the component (D): 80 to 20% by weight, and the more preferable range is the component (C ): 30 to 70% by weight, component (D): 70 to 30% by weight.

  In the flame-retardant polyolefin resin composition of the present invention, the content of the component (E) is not limited, but is usually 0.5 to 40% by weight, preferably 1 to 30% by weight, more preferably 2 to 20% by weight. It is. By making content of the component (E) in a resin composition into the said range, there exists a tendency for the flame retardance of the flame-retardant polyolefin resin composition of this invention to become favorable.

The content rate of the component (E) with respect to the total amount of the component (C) and the component (D) in the flame-retardant polyolefin resin composition of this invention is 1 to 70 weight%. It is obtained in any case where the content ratio of the component (E) with respect to the total amount of the component (C) and the component (D) is less than the above lower limit value and exceeds the above upper limit value. The flame retardancy of the resin composition deteriorates.
The content ratio of the component (E) with respect to the total amount of the component (C) and the component (D) is preferably 5 to 65% by weight, more preferably 10 to 60% by weight for the same reason as described above.

  In the present invention, by using the components (C) and (D) and the component (E) in the above composition range, the obtained flame retardant polyolefin resin composition exhibits good flame resistance and heat resistance. Is possible. When the content ratio of the component (E) with respect to the total amount of the component (C) and the component (D) is less than the lower limit value, the drip suppression effect is not sufficiently exhibited, so that good flame retardancy cannot be exhibited. On the other hand, when the content ratio of the component (E) exceeds the above upper limit value, it becomes difficult to form a foamed carbonized film by inhibiting foaming of the resin during combustion, which is difficult due to the component (C) and the component (D). Since the flame effect is not sufficiently exhibited, good flame retardancy and heat resistance cannot be exhibited.

In the flame retardant polyolefin resin composition of the present invention, the content in the case of containing a resin as other components is not limited, but is usually 10 to 65% by weight, preferably 15 to 35% by weight in the resin composition. is there. When content of resin exceeds the said upper limit, the flame retardance of the resin composition obtained may become inadequate.
The content of the flame retardant polyolefin resin composition of the present invention when it contains an additive as another component is not limited, but is usually 0.1 to 10% by weight in the resin composition, preferably 0.5. ~ 5% by weight. When content of an additive exceeds the said upper limit, the flame retardance of the resin composition obtained may fall. In addition, when using the flame retardant polyolefin resin composition of the present invention as a master batch, these other components may be contained at a concentration of 2 to 50 times, preferably 3 to 30 times the content described above. it can.

  Although the melt flow rate (MFR) of the flame-retardant polyolefin resin composition of the present invention is not limited, the value measured at 230 ° C. and 21.2 N load is usually 0.2 to 60 g / 10 according to JIS K7210 (1999). Minutes, preferably 0.5 to 30 g / 10 minutes, more preferably 1 to 20 g / 10 minutes. When MFR exceeds the above upper limit, the extrudability of the flame retardant polyolefin resin composition tends to decrease. If the MFR is less than the above lower limit, the fluidity is insufficient, and the moldability of the flame retardant polyolefin resin composition tends to be reduced.

  Since the flame-retardant polyolefin resin composition of the present invention has good flame retardancy, it can be used as a suitable molded article in applications where flame retardancy at the V-0 level of UL-94V is desired. In particular, even in the case of a molded product having a small thickness, it exhibits good flame retardancy, so a test piece having a thickness of 1.0 mm can have flame retardancy of V-0 level. Even a test piece having a thickness of 0.7 mm, particularly a thickness of 0.5 mm, can have flame retardancy of V-0 level.

  Thus, as a factor that the flame retardancy of the flame retardant polyolefin resin composition of the present invention is good, the combustibility is suppressed when the resin composition or a molded product obtained from the resin composition comes into contact with a fire source. At the same time, the drip phenomenon during combustion is significantly suppressed. When the flame retardant polyolefin resin composition of the present invention comes into contact with a fire source, the foaming of the resin occurs at an early stage, but the foamed resin is appropriately carbonized to block heat conduction to the inside. It is considered that good combustibility can be exhibited even in the case of a thin molded product. This effect uses the component (A) and the component (B) as essential components as a resin component, the component (C) and the component (D) as essential components as a flame retardant, and further uses the component (E) as a filler. This is considered to be a synergistic effect.

<Method for Producing Flame Retardant Polyolefin Resin Composition>
The flame-retardant polyolefin resin composition of the present invention can be obtained by mixing the above-described components at a predetermined ratio. The mixing method is not particularly limited as long as the raw material components are uniformly dispersed. That is, a resin composition in which each component is uniformly distributed can be obtained by mixing the above-described raw material components simultaneously or in any order.
For more uniform mixing / dispersion, it is preferable to melt and mix a predetermined amount of the above raw material components. For example, the raw material components of the flame retardant polyolefin resin composition of the present invention are mixed in an arbitrary order. Or may be mixed while sequentially melting all the raw material components, etc., or each raw material may be appropriately blended (dry blended) at the time of molding when producing the desired molded product and melt mixed. .

  The mixing method and mixing conditions are not particularly limited as long as each raw material component is uniformly mixed, but from the viewpoint of productivity, the raw materials are mixed using, for example, a tumbler blender, V blender, ribbon blender, Henschel mixer, etc. A melt kneading method using a continuous kneader such as a single screw extruder or a twin screw extruder and a batch kneader such as a mill roll, a Banbury mixer, or a pressure kneader is preferable. The production conditions for producing the resin composition by these methods are not limited, and can be appropriately set under known conditions. The temperature at the time of melt mixing may be a temperature at which at least one of the respective raw material components is in a molten state, but usually a temperature at which all the components used are melted is selected, and is generally performed at 150 to 250 ° C.

<Molded products and applications>
There is no limitation in the molded product obtained from the flame-retardant polyolefin resin composition of the present invention, and it can be various extrusion molded products, injection molded products, and the like. Therefore, the method for molding the flame retardant polyolefin fat composition of the present invention is not particularly limited to extrusion molding, compression molding, injection molding and the like. The molding temperature is not limited as long as it is higher than the melting temperature of the resin composition, but is preferably 150 ° C to 220 ° C. If the molding temperature is higher than the lower limit, the melted resin composition has high fluidity, and a molded product having a desired shape can be easily obtained. Further, if the molding temperature is lower than the upper limit, molding defects due to alteration of the flame retardant hardly occur. In particular, extrusion molding is desirable from the viewpoint of fluidity in the molten state of the resin composition.

  The use of the molded product obtained by using the flame retardant polyolefin resin composition of the present invention is not particularly limited, but it has excellent flame resistance, mechanical properties, heat resistance, and has an excellent appearance. The body and sheath can be suitably used for electric wires and cables. Furthermore, it can be suitably used for various insulating films, insulating pipes, power supply boxes, and the like in addition to tubes that bundle a plurality of resin-coated electric wires.

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples unless it exceeds the gist.
In the examples and comparative examples of the present invention, the following raw materials were used.

<Component (A)>
A-1: Ethylene / vinyl acetate copolymer (trade name: Everflex EV40LX, manufactured by Mitsui DuPont Polychemical Co., Ltd., vinyl acetate content 41 wt%, MFR (190 ° C., 21.2 N) 2.0 g / 10 Min).
A-2: Ethylene / vinyl acetate copolymer (trade name: Everflex EV180, manufactured by Mitsui DuPont Polychemical Co., Ltd., vinyl acetate content 33% by weight, MFR (190 ° C., 21.2 N) 0.2 g / 10 Min).
A-3: Ethylene / ethyl acrylate copolymer (trade name: UNICAR NUC-6510, manufactured by Nippon Unicar Co., Ltd., ethyl acrylate content 23% by weight, MFR (190 ° C., 21.2N) 0.5 g / 10 Min).

<Component (B)>
B-1: Propylene / ethylene copolymer containing propylene as a main component (trade name: Novatec EG8, manufactured by Nippon Polypro Co., Ltd., density 0.90 g / cm ³ , MFR (230 ° C., 21.2 N) 0.8 g / 10 minutes, flexural modulus 1150 MPa).
B-2: Propylene / ethylene copolymer mainly composed of propylene (trade name: Novatec EC7, manufactured by Nippon Polypro Co., Ltd., density 0.90 g / cm ³ , MFR (230 ° C., 21.2 N) 1.5 g / 10 minutes, flexural modulus 1200 MPa).
B-3: Ethylene / 1-butene copolymer (trade name: Engage ENR7256, manufactured by Dow Chemical Japan, density 0.885 g / cm ³ , MFR (190 ° C., 21.2 N) 2.0 g / 10 minutes, Flexural modulus 27 MPa).
B-4: High density polyethylene (trade name: Novatec HY540, manufactured by Nippon Polypro Co., Ltd., density 0.96 g / cm ³ , MFR (190 ° C., 21.2 N) 1.0 g / 10 min, flexural modulus 1450 MPa).

<Components (C) and (D)>
CD-1: Phosphate flame retardant (trade name: ADK STAB FP2200, manufactured by ADEKA Corporation, pH 3.0 to 4.0 (measured at 25 ° C., 10% by weight suspension in water), density 1.78 g / Cm ³ ). A mixture of (poly) phosphate compounds corresponding to the general formula (1) and the general formula (2). (Japanese Patent Laid-Open No. 2009-185214 describes that the product is a flame retardant containing component (C) and component (D)).

<Ingredient (E)>
E-1: Talc (Fuji Talc Kogyo Co., Ltd., trade name: PKP-53S).
E-2: Talc (Fuji Talc Kogyo Co., Ltd., trade name: TP-A20).
<Other resins>
F-1: Hydrogenated styrene / isoprene / butadiene block copolymer (trade name: Hiblar 7311, manufactured by Kuraray Co., Ltd., density 0.89 g / cm ³ ).
<Antioxidant>
G-1: A hindered phenol antioxidant (manufactured by BASF Japan, trade name: IRGANOX 1010).

<Example 1>
All the raw materials were dry blended with the raw material composition shown in Table 1, and melt-kneaded for 10 minutes at 160 ° C. and 60 rpm in a lab plast mill manufactured by Toyo Seiki Seisakusho, thereby producing a flame retardant polyolefin resin composition. Produced.
The obtained flame-retardant polyolefin resin composition was molded into a sheet having a thickness of 0.5 mm using an electric press at 180 ° C.
It shows in Table 1 about the result of having performed the combustion test based on UL-94V by the method mentioned later using the shape | molded sheet | seat.

<Examples 2 and 3, Comparative Examples 1 and 2>
A flame retardant polyolefin resin composition was prepared in the same manner as in Example 1 except that the raw material composition was as shown in Table-1. The obtained flame retardant polyolefin resin composition was molded into a sheet in the same manner as in Example 1 to obtain a sheet having a thickness of 0.5 mm. It shows in Table 1 about the result of having performed the combustion test based on UL-94V by the method mentioned later using the shape | molded sheet | seat.

<Examples 4-8, Comparative Examples 3-5>
A flame retardant polyolefin resin composition was prepared in the same manner as in Example 1 except that the raw material composition was as shown in Table-2. A sheet was obtained in the same manner as in Example 1 except that the obtained flame-retardant polyolefin resin composition had a thickness of 0.7 mm. It shows in Table-2 about the result of having performed the combustion test based on UL-94V by the method mentioned later using the shape | molded sheet | seat.

<Examples 9 to 12, Comparative Examples 6 and 7>
A flame retardant polyolefin resin composition was prepared in the same manner as in Example 1 except that the raw material composition was as shown in Table-3. A sheet was obtained in the same manner as in Example 1 except that the obtained flame-retardant polyolefin resin composition had a thickness of 1.0 mm. Table 3 shows the results of performing a combustion test based on UL-94V using a molded sheet by a method described later.

<UL-94V combustion test>
A test piece (length: 127 mm, width: 12.7 mm, thickness is either 0.5 mm, 0.7 mm, or 1.0 mm) obtained by an electric press is kept vertical, and a burner is fired at the lower end. After 10 seconds of indirect flame, the flame was removed, and the time for the fire that ignited the test piece to extinguish was measured. Next, at the same time that the fire was extinguished, the second flame contact was performed for 10 seconds, and the time when the ignited fire extinguished was measured in the same manner as the first time. Furthermore, it was evaluated whether or not the cotton installed under the test piece was ignited by the falling fire type.
From the results of the first and second burning times and the presence or absence of cotton ignition, the flammability was evaluated according to the UL-94V standard. Combustion performance was good in the order of V-0, V-1, and V-2, and "X" was inferior to V-2.

  From the results of Table-1 to Table-3, the flame-retardant polyolefin resin composition of the present invention has UL94V combustion regardless of whether the thickness of the test piece is 0.5 mm, 0.7 mm, or 1.0 mm. In the test, it was confirmed to have flame retardancy of V-0 level. On the other hand, when the component (E) is not contained or when the component (E) is excessively contained with respect to the total amount of the component (C) and the component (D), flame retardancy of V-0 is achieved. I did not.

That is, the gist of the present invention is the following [1] to [10] .
[1] Containing the following components (A) to (E), with respect to the total amount of the components (A) and (B)
The component (A) is contained in a proportion of 5 to 95% by weight, the component (B) is contained in a proportion of 95 to 5% by weight, and the content of the component (E) with respect to the total amount of the component (C) and the component (D) 1 to 70% by weight of a flame retardant polyolefin resin composition.
Component (A): Ethylene-vinyl acetate copolymer and / or ethylene- (meth) acrylate copolymer Component (B): Polyolefin resin Component (C): Represented by the following general formula (1) ) Phosphate compound Component (D): (Poly) phosphate compound represented by the following general formula (3) Component (E): Talc

[2] The flame retardant polyolefin resin composition according to [1], wherein the vinyl acetate content in the total amount of the component (A) and the component (B) is 1 to 45% by weight .
[3] The flame-retardant polyolefin resin composition according to [1] or [2], wherein the (meth) acrylic acid ester content in the total amount of the component (A) and the component (B) is 1 to 45% by weight.
[4] The flame-retardant polyolefin resin composition according to any one of [1] to [3], wherein the total content of the component (C) and the component (D) is 15 to 60% by weight in the resin composition.
[5] The flame retardant polyolefin resin composition according to any one of [1] to [4], wherein the content of the component (A) is 3 to 75% by weight in the resin composition.
[6] The flame retardant polyolefin resin composition according to any one of [1] to [5], wherein the content of the component (B) is 3 to 75% by weight in the resin composition.
[7] The flame retardant polyolefin resin composition according to any one of [1] to [6], wherein the content of the component (E) is 0.5 to 40% by weight in the resin composition.
[8] In any one of [1] to [7], the ethylene-vinyl acetate copolymer and / or the ethylene- (meth) acrylate copolymer has a vinyl acetate content of 10 wt% or more and 55 wt%. Flame retardancy that is an ethylene-vinyl acetate copolymer and / or an ethylene- (meth) acrylate copolymer having a (meth) acrylate content of 10 wt% to 50 wt% Polyolefin resin composition.
[9] The flame-retardant polyolefin resin according to any one of [1] to [8], wherein the flame-retardant performance is V-0 when a UL-94V combustion test is performed as a test piece having a thickness of 0.5 mm. Composition.
[10] A molded article obtained by molding the flame retardant polyolefin resin composition according to any one of [1] to [9].

Claims (7)

Flame retardancy characterized in that it contains the following components (A) to (E), and the content ratio of the component (E) to the total amount of the components (C) and (D) is 1 to 70% by weight. Polyolefin resin composition.
Component (A): Ethylene-vinyl acetate copolymer and / or ethylene- (meth) acrylate copolymer Component (B): Polyolefin resin Component (C): Represented by the following general formula (1) ) Phosphate compound Component (D): (Poly) phosphate compound represented by the following general formula (3) Component (E): Talc

However, n in the formula (1) is a number from ^{1 to} 100, X ¹ is ammonia or a triazine derivative represented by the following general formula (2), and p is a number satisfying the relational expression 0 <p ≦ n + 2. .

However, Z ¹ and Z ² in the formula (2) may be the same or different, and are each independently a —NR ⁵ R ⁶ group (where R ⁵ and R ⁶ are each independently a hydrogen atom, a carbon atom, A linear or branched alkyl group or methylol group having 1 to 6 carbon atoms), a hydroxyl group, a mercapto group, a linear or branched alkyl group having 1 to 10 carbon atoms, a linear or branched alkoxy group having 1 to 10 carbon atoms. And a group selected from the group consisting of a group, a phenyl group and a vinyl group.

However, in the formula (3), r is a number of 1 to 100, Y ¹ is [R ¹ R ² N (CH ₂ ) _m NR ³ R ⁴ ], a piperazine or a diamine containing a piperazine ring, R ¹ , R ² , R ³ and R ⁴ are each independently a hydrogen atom or a linear or branched alkyl group having 1 to 5 carbon atoms, m is an integer of 1 to 10, and q satisfies the relational expression 0 <q ≦ r + 2. Is a number.   The flame retardant according to claim 1, comprising 5 to 95% by weight of component (A) and 95 to 5% by weight of component (B) relative to the total amount of component (A) and component (B). Polyolefin resin composition.   The flame-retardant polyolefin resin composition according to claim 1 or 2, wherein the vinyl acetate content in the total amount of the component (A) and the component (B) is 1 to 45% by weight.   The flame-retardant polyolefin resin composition according to claim 1 or 2, wherein the content of (meth) acrylate in the total amount of component (A) and component (B) is 1 to 45% by weight.   The flame retardant polyolefin resin composition according to any one of claims 1 to 4, wherein the total content of the component (C) and the component (D) is 15 to 60% by weight in the resin composition.   The molded object formed by shape | molding the flame-retardant polyolefin resin composition of any one of Claims 1-5.   The electric wire formed by coat | covering the flame-retardant polyolefin resin composition of any one of Claims 1-5.