JP2013082870A - Thermoplastic polymer composition, molding comprising the same, and wire - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermoplastic polymer composition that excels in the balance of mechanical strength, elongation at breakage, hardness, flexibility and heat resistance; and to provide a molding comprising the composition, an insulator using the composition, and/or a wire with a sheath.SOLUTION: The thermoplastic polymer composition includes: a polymer component comprising 50-100 mass% of a propylene polymer (A) whose pull initial elastic modulus measured based on JIS K 7113-2 is less than 500 MPa, 0-40 mass% of a propylene polymer (B) whose pull initial elastic modulus is at least 500 MPa, and 0-20 mass% of an ethylene polymer (C), wherein the total of (A), (B) and (C) is 100 mass%; and 1-150 pts.mass of a phosphorus flame-retardant composition based on 100 pts.mass of the polymer component.

Description

  The present invention relates to a thermoplastic polymer composition comprising a specific propylene-based polymer and a phosphorus-based flame retardant composition, a molded article comprising the same, and an electric wire having an insulator or sheath of the electric wire comprising the thermoplastic polymer composition.

  A propylene-based polymer is a material excellent in heat resistance, mechanical strength, and scratch resistance, and its molded product is used in a wide range of applications. A molded product obtained from a resin composition comprising general polypropylene and an inorganic filler is also excellent in heat resistance and mechanical strength, but on the other hand, it is inferior in flexibility and impact resistance. For this reason, ethylene-based copolymers have been mainly used for applications that require characteristics such as flexibility and impact resistance. However, since an ethylene-based copolymer is inferior in heat resistance, a crosslinking step is often required. For this reason, a large-scale cross-linking facility is required, leading to an increase in overall cost.

  In order to solve this, a molded body made of a propylene-based polymer and an inorganic filler (a flame retardant) is known as an electric wire or a wire harness that requires scratch resistance (Patent Document 1).

In addition, it is known that a propylene / butene copolymer, polyethylene and an inorganic filler are blended in polypropylene (Patent Document 2).
In addition, it is known that an ethylene / α-olefin random copolymer elastomer or a styrene elastomer is blended with an inorganic filler in a propylene polymer (Patent Document 3).

On the other hand, compositions in which polypropylene, maleic acid-modified polyethylene and metal hydrate are blended with an ethylene / vinyl acetate copolymer are known (Patent Documents 4 to 8).
As described above, in the thermoplastic polymer composition using the propylene polymer and the ethylene / vinyl acetate copolymer, various improvements have been made, but in the balance of mechanical strength, hardness, flexibility, and heat resistance. Further, there is a demand for a composition having excellent performance, a molded body made of the composition, an insulator made of the composition, and an electric wire having a sheath.

JP 2003-313377 A JP 2008-97918 A JP 2008-169257 A JP 2008-94977 A JP 2009-114230 A JP 2009-54388 A JP 2009-19190 A JP 2009-216836 A

  An object of the present invention is to provide a thermoplastic polymer composition having an excellent balance of mechanical strength, elongation at break, flexibility, and heat resistance. Moreover, the objective of this invention is providing the electric wire which has the molded object which consists of this composition, and the insulator or sheath which uses this composition.

  By using a specific propylene-based polymer, the present invention has good flame retardant uptake, that is, good dispersibility of the flame retardant in the thermoplastic polymer composition, and mechanical strength, elongation at break, flexibility This is based on the finding that a thermoplastic polymer composition having an excellent balance between heat resistance and heat resistance can be obtained. Furthermore, it has been found that by using such a specific thermoplastic polymer composition, a molded article having an excellent balance of mechanical strength, elongation at break, flexibility, and heat resistance can be obtained, and the present invention has been achieved. .

  That is, the present invention relates to a propylene polymer (A) having an initial tensile modulus of elasticity of less than 500 MPa measured based on JIS K7113-2: 50 to 100% by mass, and a propylene polymer having an initial tensile modulus of 500 MPa or more. Polymer (B): 0 to 40% by mass and ethylene polymer (C): 0 to 20% by mass of polymer components [(A), (B) and (C) in total 100% by mass And ) And a thermoplastic polymer composition comprising 1 to 150 parts by mass of the phosphorus-based flame retardant composition (D) with respect to 100 parts by mass of the polymer component.

According to a preferred embodiment of the present invention, the propylene polymer (A) used in the present invention is a thermoplastic polymer composition satisfying the following (a), (b) and (c).
(A) Melting point measured by differential scanning calorimetry (DSC) is less than 120 ° C. or no melting point is observed.
(B) The molecular weight distribution (Mw / Mn) measured by gel permeation chromatography (GPC) is 1-3.
(C) The melt flow rate (MFR) at 230 ° C. is 50 g / 10 min or less.

Furthermore, according to a preferred embodiment of the present invention, the propylene polymer (A) used in the present invention satisfies the following (m) and (n): propylene / ethylene / α-olefin random having 4 to 20 carbon atoms It is a thermoplastic polymer composition which is a copolymer.
(M) 40 to 85 mol% of a structural unit derived from propylene, 5 to 30 mol% of a structural unit derived from ethylene, and 5 to 30 mol% of a structural unit derived from an α-olefin having 4 to 20 carbon atoms ( Here, the sum total of the structural unit derived from propylene, the structural unit derived from ethylene, and the structural unit derived from an α-olefin having 4 to 20 carbon atoms is 100 mol%.
(N) The initial tensile modulus measured based on JIS K7113-2 is less than 100 MPa.

Furthermore, in the thermoplastic polymer composition of the present invention, the phosphorus-based flame retardant composition (D) preferably contains 15 to 25% nitrogen element.
Moreover, in the thermoplastic polymer composition of this invention, it is preferable that a phosphorus flame retardant composition (D) contains 3-8 mass% of zinc oxide.

  Furthermore, this invention relates to the molded object which consists of said thermoplastic polymer composition, and relates to the insulator or electric wire sheath of an electric wire as the molded object.

  The thermoplastic polymer composition of the present invention has excellent performance in the balance of mechanical strength, elongation at break, flexibility, and heat resistance, and can be widely used suitably for molded articles, particularly electric wires. it can.

Below, the thermoplastic polymer composition of this invention is demonstrated.
Propylene polymer (A)
The propylene-based polymer (A) used in the thermoplastic polymer composition of the present invention has an initial tensile elastic modulus measured based on JIS K7113-2 of less than 500 MPa, and in particular, a propylene-based polymer having a weight of 1 to 100 MPa. A coalescence is preferable, and a propylene polymer of 10 to 50 MPa is particularly preferable.

  Examples of the propylene polymer (A) according to the present invention include a propylene homopolymer having low stereoregularity, or a copolymer of propylene and at least one olefin having 2 to 20 carbon atoms other than propylene. A polymer can be mentioned. Here, as the α-olefin having 2 to 20 carbon atoms other than propylene, ethylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene and the like can be mentioned, and ethylene or an α-olefin having 4 to 10 carbon atoms is preferable. These α-olefins may form a random copolymer with propylene or a block copolymer.

  Specific examples of the propylene polymer (A) according to the present invention include, for example, polypropylene having a low stereoregularity (propylene homopolymer), propylene / ethylene copolymer, propylene / 1-butene copolymer. And propylene / α-olefin copolymers such as propylene / 1-ethylene / 1-butene copolymer, propylene / 1-hexene copolymer, and propylene / 1-butene / 1-hexene copolymer. it can.

The propylene polymer (A) according to the present invention preferably satisfies the following (a), (b) and (c).
(A) The melting point (Tm) measured by differential scanning calorimetry (DSC) is less than 120 ° C. or the melting point (Tm) is not observed.
(B) The molecular weight distribution (Mw / Mn) measured by gel permeation chromatography (GPC) is 1-3.
(C) The melt flow rate (MFR) at 230 ° C. is 0.1 to 50 g / 10 minutes.

  In addition, the propylene-based polymer (A) according to the present invention preferably has a propylene-derived constituent unit usually in an amount of 40 to 100 mol%, preferably 40 to 99 mol%, more preferably 40 to 92 mol%. More preferably, the constituent unit is derived from an α-olefin having 2 to 20 carbon atoms (excluding propylene) used as a comonomer, containing 50 to 90 mol%, and usually 0 to 60 mol%, preferably 1 to 60. Mol%, more preferably 8 to 60 mol%, still more preferably 10 to 50 mol% (here, the total of propylene and the α-olefin having 2 to 20 carbon atoms is 100 mol%).

  The propylene-based polymer (A) according to the present invention usually has a melt flow rate (MFR, ASTM D1238, temperature 230 ° C., under a load of 2.16 kg) of 0.1 to 50 g / 10 minutes.

  The propylene polymer (A) has a melting point (Tm) measured by differential scanning calorimetry (DSC) of less than 120 ° C., among which the melting point (Tm) is less than 110 ° C., of which the melting point ( Tm) is preferably less than 100 ° C., more preferably no melting point (Tm) is observed.

  Here, that the melting point (Tm) is not observed means that a crystal melting peak having a heat of crystal melting of 1 J / g or more is not observed in the range of −150 to 200 ° C. Create a DSC curve obtained when measuring at 23 ° C ± 2 ° C for 72 hours or longer and cooling to -40 ° C and then measuring at a heating rate of 10 ° C / min. Determined by

  The propylene-based polymer (A) according to the present invention has an intrinsic viscosity [η] measured in decalin at a temperature of 135 ° C. is usually 0.01 to 10 dl / g, preferably 0.05 to 10 dl / g. Is in range.

The propylene polymer (A) according to the present invention preferably has a triad tacticity (mm fraction) measured by ¹³ C-NMR of 85% or more, more preferably 85 to 97.5%, and still more preferably. It is in the range of 87 to 97%, particularly preferably 90 to 97%. When the triad tacticity (mm fraction) is in this range, the balance between flexibility and mechanical strength is particularly excellent, which is suitable for the present invention. The mm fraction can be measured by the method described in International Publication No. 2004-087775 pamphlet, page 21, line 7 to page 26, line 6.

  The production method of the propylene polymer (A) according to the present invention is not particularly limited, but a known catalyst capable of stereoregular polymerization of an α-olefin with an isotactic structure or a syndiotactic structure, for example, a solid titanium component And propylene in the presence of a catalyst mainly composed of an organometallic compound, or a metallocene catalyst using a metallocene compound as a component of the catalyst, or copolymerization of propylene and another α-olefin. Can be manufactured. Further, it can be produced by polymerizing propylene using a known catalyst capable of polymerizing an α-olefin with an atactic structure, or copolymerizing propylene and another α-olefin. Preferably, it is obtained by polymerizing propylene in the presence of a metallocene catalyst or copolymerizing propylene and an α-olefin having 2 to 20 carbon atoms (excluding propylene).

  Among the propylene-based polymers (A) having the above-described characteristics, as preferred embodiments, propylene / ethylene random copolymer (A0), propylene / α-olefin random copolymer having 4 to 20 carbon atoms ( A1) and at least one copolymer selected from propylene / ethylene / α-olefin random copolymer (A2) having 4 to 20 carbon atoms may be mentioned.

  More preferably, the thermoplastic polymer composition of the present invention is a propylene / ethylene / C4-20 α-olefin random copolymer (A1) or propylene / ethylene / C4-20 α-olefin random copolymer. By using the polymer (A2), for example, compatibility with the polypropylene crystal component contained in the propylene polymer (B) is exhibited, and the thermoplastic composition is excellent in mechanical strength, elongation at break, and scratch resistance. Is obtained.

  More preferably, by using propylene / ethylene / α-olefin random copolymer having 4 to 20 carbon atoms (A2), in addition to exhibiting excellent properties due to mechanical strength, elongation at break, and scratch resistance, A thermoplastic composition having excellent flexibility can be obtained.

  Propylene / ethylene random copolymer (A0), propylene / ethylene atom 4 to 20 α-olefin random copolymer (A1), and propylene / ethylene / carbon atom 4 to 20 are preferably used in the present invention. The α-olefin random copolymer (A2) preferably has a molecular weight distribution (Mw / Mn) of 1 to 3 as measured by (a) gel permeation chromatography (GPC). In the present invention, a propylene polymer (A) having high stereoregularity is preferably used from the viewpoint of heat resistance. As a preferable range, isotactic triad (mm) is 85% or more. The structure may be an isotactic structure or a syndiotactic structure. However, when the thermoplastic resin composition of the present invention contains a propylene polymer (B) described later, the propylene polymer (B). It is preferable to use a polymer having the same structure as in view of compatibility.

Propylene / ethylene random copolymer (A0)
The propylene / ethylene random copolymer (A0) preferably used in the present invention is a random copolymer obtained by random copolymerization of propylene and ethylene, and the structural unit derived from propylene is usually 50 to 95 mol%, Preferably it contains 55 to 90 mol%, more preferably 60 to 88 mol%, and the ethylene-derived structural unit used as a comonomer is usually 5 to 50 mol%, preferably 10 to 45 mol%, more preferably 12 to 40 mol%. Including mol% (wherein the total of propylene and ethylene is 100 mol%).

Propylene / α-olefin random copolymer having 4 to 20 carbon atoms (A1)
The propylene / α-olefin random copolymer (A1) having 4 to 20 carbon atoms preferably used in the present invention is a copolymer of propylene and at least one α-olefin having 4 to 20 carbon atoms. Can be mentioned. Here, examples of the α-olefin having 4 to 20 carbon atoms include 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1 -Tetradecene, 1-hexadecene, 1-octadecene, 1-eicocene and the like.

In the propylene / α-olefin random copolymer (A1) having 4 to 20 carbon atoms,
(D) The degree of crystallinity measured by X-ray diffraction is preferably 40% or less, more preferably 35% or less. (In the present invention, “below” includes non-crystalline having a crystallinity of 0%. ).

In the propylene / α-olefin random copolymer (A1) having 4 to 20 carbon atoms, the content of the structural unit derived from the α-olefin having 4 to 20 carbon atoms is preferably 5 to 50 mol%, more preferably. 10 to 35 mol%. In particular, 1-butene is preferably used as the α-olefin having 4 to 20 carbon atoms.
Such a propylene polymer can be obtained by, for example, a method described in International Publication No. 2004/87775 pamphlet.

Propylene / ethylene / α-olefin random copolymer having 4 to 20 carbon atoms (A2)
The α-olefin random copolymer (A2) of propylene / ethylene / carbon atoms 4 to 20 preferably used in the present invention is propylene, ethylene, and an α-olefin having 4 to 20 carbon atoms other than propylene. Mention may be made of at least one copolymer. Here, examples of the α-olefin having 4 to 20 carbon atoms other than propylene include the same as in the case of the α-olefin random copolymer (A1) having 4 to 20 carbon atoms.

In addition, the propylene / ethylene / C4-20 α-olefin random copolymer (A2) suitable in the present invention satisfies the following (m) and (n).
(M) 40 to 85 mol% of a structural unit derived from propylene, 5 to 30 mol% of a structural unit derived from ethylene, and 5 to 30 mol% of a structural unit derived from an α-olefin having 4 to 20 carbon atoms ( Here, the total of the structural unit derived from propylene, the structural unit derived from ethylene, and the structural unit derived from an α-olefin having 4 to 20 carbon atoms is 100 mol%). Moreover, it is preferable that the sum total of the structural unit derived from ethylene and the structural unit derived from a C4-C20 alpha olefin is 60-15 mol%.
(N) The initial tensile elastic modulus measured based on JIS K7113-2 is 1 to 100 MPa, preferably 10 to 50 MPa.

In the propylene / ethylene / α-olefin random copolymer (A2) having 4 to 20 carbon atoms, it is preferable that at least one of the following (o) and (p) is satisfied, more preferably both are satisfied. desirable.
(O) Shore A hardness is 30 to 90, preferably 35 to 60.
(P) The degree of crystallinity measured by X-ray diffraction is 20% or less, preferably 10% or less.

  The melting point (Tm) of propylene / ethylene / α-olefin random copolymer (A2) having 4 to 20 carbon atoms (A2) measured by DSC is preferably 50 ° C. or less, or the melting point (Tm) is observed. It is desirable not to be. More preferably, the melting point (Tm) is not observed.

  The propylene component and the amount of other comonomer components are more specifically described. The constituent unit derived from propylene is preferably 60 to 82 mol%, more preferably 61 to 75 mol%, and the constituent unit derived from ethylene is preferably 8 to 15. It is desirable to include a constituent unit derived from a mol%, more preferably 10 to 14 mol%, and an α-olefin having 4 to 20 carbon atoms, preferably in an amount of 10 to 25 mol%, more preferably 15 to 25 mol%. (Here, the total of the structural unit derived from propylene, the structural unit derived from ethylene, and the structural unit derived from α-olefin having 4 to 20 carbon atoms is 100 mol%). In particular, 1-butene is preferably used as the α-olefin having 4 to 20 carbon atoms.

  Such a propylene / ethylene / C4-20 α-olefin random copolymer (A2) can be obtained, for example, by a method described in JP-A No. 2007-186664.

  In the present invention, by using a propylene / ethylene / α-olefin random copolymer (A2) having 4 to 20 carbon atoms, the flexibility is further improved, the elongation at break is large, and the embrittlement temperature at a low temperature. A molded product having a low is obtained. For example, when this molded body is an electric wire, it has an advantage that the electric wire coating is not easily broken even when exposed to low temperatures.

  The propylene-based polymer (A), specifically, a propylene / ethylene random copolymer (A0), a propylene / α-olefin random copolymer (A1) having 4 to 20 carbon atoms, and propylene / ethylene.・ As for the α-olefin random copolymer (A2) having 4 to 20 carbon atoms, a polymer in which a part or all of the α-olefin random copolymer (A2) is modified with a vinyl compound having a polar group described below is used as necessary. Is also done.

Propylene polymer (B)
The propylene-based polymer (B) that may be used in the thermoplastic polymer composition of the present invention is a polymer having an initial tensile modulus measured based on JIS K7113-2 of 500 MPa or more. A propylene polymer of 1000 to 3000 MPa is preferred, and a propylene polymer of 1500 to 2500 MPa is particularly preferred.

  The propylene polymer (B) according to the present invention includes a propylene homopolymer having high stereoregularity, or a steric structure of propylene and at least one α-olefin having 2 to 20 carbon atoms other than propylene. A copolymer with high regularity can be mentioned.

  Here, as the α-olefin having 2 to 20 carbon atoms other than propylene, ethylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene and the like can be mentioned, and ethylene or an α-olefin having 4 to 10 carbon atoms is preferable. These α-olefins may form a random copolymer with propylene or a block copolymer.

The structural unit derived from these α-olefins may be contained in the entire structural unit of the propylene-based polymer (B) in a proportion of 35 mol% or less, preferably 30 mol% or less.
Specific examples of the propylene polymer (B) according to the present invention include, for example, polypropylene having a high stereoregularity (propylene homopolymer), propylene / ethylene copolymer, propylene / ethylene / 1-butene copolymer, Examples include propylene / 1-butene copolymer and propylene / ethylene / 1-hexene copolymer.

  The propylene-based polymer (B) according to the present invention has a melt flow rate (MFR) measured at a temperature of 230 ° C. and a load of 2.16 kg in accordance with ASTM D 1238, usually 0.01 to 1000 g / 10 min. Preferably, it is 0.05-100 g / 10min, More preferably, it exists in the range of 0.1-50 g / 10min.

  The propylene-based polymer (B) according to the present invention preferably has a melting point (Tm) measured by a differential scanning calorimeter (DSC) in the range of 120 to 170 ° C, and particularly preferably 125 to 165 ° C. A range is preferable.

  The propylene-based polymer (B) according to the present invention may have either an isotactic structure or a syndiotactic structure, but is isotactic structure from the viewpoint of being easily available at a low price. Those having the following are preferred.

Moreover, a some propylene polymer (B) can be used together as needed, for example, 2 or more types of components from which melting | fusing point and rigidity differ can also be used.
Moreover, as a propylene polymer (B), the propylene homopolymer which is excellent in heat resistance, the block polypropylene which is excellent in the balance of heat resistance and impact resistance (usually 3-30 mass% of n-decane elution components are publicly known) Propylene / α-olefin random copolymer having a good balance between flexibility and transparency (usually a melting peak temperature measured by a differential scanning calorimeter (DSC) of 120 ° C. or higher, preferably from 125 ° C. to Known ones in the range of 150 ° C. may be selected and used to obtain the desired physical properties, or these may be used in combination.

  Such a propylene polymer (B) includes, for example, a solid catalyst component containing magnesium, titanium, halogen and an electron donor as essential components, a Ziegler catalyst system comprising an organoaluminum compound and an electron donor, or a metallocene compound. It can be produced by polymerizing propylene or copolymerizing propylene and other olefins using a metallocene catalyst system used as a component of the catalyst.

Ethylene polymer (C)
The ethylene polymer (C) that may be used in the thermoplastic polymer composition of the present invention is an ethylene homopolymer, ethylene and an α-olefin having 3 or more carbon atoms such as propylene, 1-butene, 1 A copolymer with -pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicocene, or the like, or A copolymer of ethylene and an unsaturated ester compound, which is a polymer containing ethylene as a main component.

  These ethylene polymers (C) are preferably ethylene / α-olefin random copolymers having an melting point (Tm) of 100 ° C. or lower, more preferably 80 ° C. or lower, or ethylene / unsaturated esters. A system compound copolymer is preferred.

  Copolymers of ethylene and unsaturated ester compounds include copolymers of ethylene and vinyl esters such as vinyl acetate and vinyl propionate, or ethylene and acrylic acid, methacrylic acid, maleic acid, anhydrous Mention may be made of copolymers of unsaturated carboxylic acids such as maleic acid, fumaric acid, itaconic acid and itaconic anhydride with alkyl esters having up to about 20 carbon atoms. Specific examples of such a copolymer include ethylene, methyl acrylate, ethyl acrylate, isopropyl acrylate, acrylic acid-n-propyl, acrylic acid isobutyl, acrylic acid-n-butyl, acrylic acid-2- Illustrate a copolymer with an unsaturated carboxylic acid ester such as ethylhexyl, methyl methacrylate, ethyl methacrylate, isobutyl methacrylate, -n-butyl methacrylate, glycidyl methacrylate, dimethyl maleate, diethyl maleate, etc. Can do.

  Furthermore, in addition to these binary copolymers, multi-component copolymers obtained by copolymerizing two or more compounds selected from the above unsaturated ester compounds with ethylene may be used. Further, other polar monomers such as acrylic acid, methacrylic acid, maleic acid, itaconic acid, maleic anhydride, itaconic anhydride can be used as long as the performance of the ethylene / unsaturated ester compound copolymer is not substantially changed. A product obtained by copolymerizing a small amount of acid, carbon monoxide, or the like may be used.

  Among these, a copolymer of ethylene and a vinyl ester compound is preferable, and examples thereof include an ethylene / vinyl acetate copolymer and an ethylene / vinyl propionate copolymer. Moreover, the ratio of the unit of an unsaturated ester compound among the copolymers with these ethylene / unsaturated ester compounds is usually 5 to 70% by mass, among which 15 to 60% by mass is preferable. Furthermore, 25-50 mass% is suitable. When the ratio of the unsaturated ester compound is within these ranges, the balance between mechanical strength and flame retardancy is excellent. If the amount is less than 15% by mass, the flame retardancy tends to decrease, and if it exceeds 60% by mass, the mechanical strength tends to decrease.

  In addition, these ethylene polymers (C) have a melt flow rate (based on JIS K7210-99, 190 ° C., 2160 g load) of 0.1 to 0.1 in consideration of physical properties, processability, and the like of the obtained composition. It is preferably in the range of 50 g / 10 minutes, particularly preferably 0.5 to 10 g / 10 minutes.

  Among the ethylene polymers (C) according to the present invention, an ethylene homopolymer or an ethylene / α-olefin random copolymer may be selected from, for example, ethylene using various known Ziegler catalysts or metallocene catalysts, or ethylene and α -Ethylene homopolymer or ethylene / unsaturated ester compound copolymer can be obtained by copolymerizing olefin, for example, ethylene or ethylene and unsaturated ester compound at high temperature and high pressure. It can be obtained by radical copolymerization below.

For example, a copolymer with good randomness produced by a high-pressure radical polymerization process by a normal autoclave method can be used.
Phosphorus flame retardant composition (D)
The phosphorus-based flame retardant composition (D) according to the present invention includes phosphorus-based flame retardant agents such as red phosphorus, phosphate esters, phosphate amides, and organic phosphinates, ammonium polyphosphate (APP), and the like. These include, for example, known phosphorous-containing flame retarding agents that are used as flame retardants. Specific examples thereof include ammonium phosphate, melamine pyrophosphate, ammonium polyphosphate, and melamine polyphosphate, and polyphosphate compounds such as melamine pyrophosphate and melamine polyphosphate. Examples of the flame-imparting agent include a modified phosphate compound whose surface is modified or coated with melamine, a melamine resin, or a fluorine-based polymer; a melamine-crosslinked phosphate compound that has been crosslinked with melamine and then crosslinked. These phosphorus-containing flame retardant imparting agents can be used alone or in combination of two or more.

  Preferred examples of the compound contained in the phosphorus-based flame retardant composition according to the present invention include a phosphate compound (d1) represented by the chemical formula (1) and a phosphate compound (d2) represented by the chemical formula (3). Can be mentioned.

（式中、ｎは１〜１００の数を示し、Ｘ₁はアンモニア又は下記一般式（２）で表わされるトリアジン誘導体であり、０＜ｐ≦ｎ＋２ である。）

(In the formula, n represents a number of 1 to 100, X ₁ is ammonia or a triazine derivative represented by the following general formula (2), and 0 <p ≦ n + 2).

（式中、Ｚ₁及びＺ₂は同一でも異なっていてもよく、−ＮＲ₅Ｒ₆基〔ここでＲ₅及びＲ₆は同一又は異なって水素原子、炭素原子数１〜６の直鎖もしくは分岐のアルキル基もしくはメチロール基〕、水酸基、メルカプト基、炭素原子数１〜１０の直鎖もしくは分岐のアルキル基、炭素原子数１〜１０の直鎖もしく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。）

(In the formula, Z ₁ and Z ₂ may be the same or different, and —NR ₅ R ₆ group [wherein R ₅ and R ₆ are the same or different and represent a hydrogen atom, a straight chain of 1 to 6 carbon atoms or Branched alkyl group or methylol group], hydroxyl group, mercapto group, linear or branched alkyl group having 1 to 10 carbon atoms, linear or branched alkoxy group having 1 to 10 carbon atoms, phenyl group and vinyl group A group selected from the group consisting of:

（式中、ｒは１〜１００を示し、Ｙ₁は〔Ｒ₁Ｒ₂Ｎ（ＣＨ₂）ｍＮＲ₃Ｒ₄〕、ピペラジン又はピペラジン環を含むアミンであり、Ｒ₁、Ｒ₂、Ｒ₃及びＲ₄はそれぞれ水素原子、炭素原子数１〜５の直鎖もしくは分岐のアルキル基であり、Ｒ₁、Ｒ₂、Ｒ₃及びＲ₄は同一の基であってもよく異なってもよく、ｍは１〜１０の整数であり、０＜ｑ≦ｒ＋２である。）
このように、リン系難燃性組成物（Ｄ）は上記化学式（１）で表わされるリン酸塩化合物（ｄ１）または、化学式（３）で表わされるリン酸塩化合物（ｄ２）を用いることが好適であり、特に上記化学式（１）で表わされるリン酸塩化合物（ｄ１）及び化学式（３）で表わされるリン酸塩化合物（ｄ２）を併用することが好適である。

(Wherein, r represents 1 to 100, Y ₁ is [R ₁ R ₂ N (CH ₂ ) mNR ₃ R ₄ ], a piperazine or an amine containing a piperazine ring, R ₁ , R ₂ , R ₃ and R ₄ is a hydrogen atom, a linear or branched alkyl group having 1 to 5 carbon atoms, and R ₁ , R ₂ , R ₃ and R ₄ may be the same group or different, m Is an integer from 1 to 10, and 0 <q ≦ r + 2.
Thus, the phosphorus-based flame retardant composition (D) uses the phosphate compound (d1) represented by the chemical formula (1) or the phosphate compound (d2) represented by the chemical formula (3). In particular, it is preferable to use the phosphate compound (d1) represented by the chemical formula (1) and the phosphate compound (d2) represented by the chemical formula (3) in combination.

  That is, in the present invention, the phosphorus-based flame retardant composition (D) is a compound containing a triazine structure, particularly a melamine phosphate, or a phosphate compound having a piperazine ring, and especially a piperazine phosphate. Is preferred.

  Among them, phosphate compounds containing a triazine structure, in particular, salts of melamine and phosphoric acid, and phosphate compounds having a piperazine ring, in which piperazine and a salt of phosphoric acid are used in combination (in other words, triazine Among them, a compound having a structure of melamine, a compound having a piperazine ring, among which a piperazine and a phosphoric acid unit are preferable).

Therefore, it is preferable that the phosphorus-based flame retardant composition (D) particularly contains units of melamine, piperazine, and phosphoric acid.
Specific examples of the phosphate compound (d1) represented by the general formula (1) include ammonia or a salt of a triazine derivative with respect to phosphoric acid.

This triazine derivative is represented by the general formula (2). Examples of the linear or branched alkyl group or alkoxy 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, tertiary heptyl, n-octyl, isooctyl, tertiary octyl, 2-ethylhexyl, nonyl, decyl, etc., these alkyls And an alkoxy group derived from the group.

  Specific examples of these triazine derivatives 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.

  Examples of the phosphate compound (d1) represented by the general formula (1) preferably used in the present invention include salts of phosphoric acid and melamine or ammonium polyphosphate compounds. The salt of phosphoric acid and melamine can be obtained by the following method. For example, in the case of melamine pyrophosphate, sodium pyrophosphate and melamine are reacted by adding hydrochloric acid at an arbitrary reaction ratio, and neutralized with sodium hydroxide to obtain melamine pyrophosphate. Specific examples of the melamine phosphate compound preferably used in the present invention include, for example, melamine orthophosphate, melamine pyrophosphate, and other melamine polyphosphates.

  The ammonium polyphosphate compound is a compound containing ammonium polyphosphate alone or the main component of the ammonium polyphosphate. Commercially available products can be used as the ammonium polyphosphate. Examples of commercially available products include Exolit-422 (trade name) manufactured by Hoechst, Exolit-700 (trade name), and Fostech-P / 30 (manufactured by Monsanto). Product name), Foschek-P / 40 (product name), Sumitomo-P (product name) manufactured by Sumitomo Chemical Co., Ltd., Terrage-S10 (product name) manufactured by Chisso Co., Ltd., Terrage-S20 (product) Name).

  In addition, as a compound containing ammonium polyphosphate as a main component, the surface of the ammonium polyphosphate is coated with a material in which the ammonium polyphosphate is coated or microencapsulated with a thermosetting resin, a melamine monomer, or another nitrogen-containing organic compound. Some are coated, some are treated with a surfactant or silicon, and others are made slightly soluble by adding melamine or the like in the process of producing ammonium polyphosphate.

  As commercial products of these compounds containing ammonium polyphosphate as a main component, Exolit-462 (trade name) manufactured by Hoechst Co., Sumisafe-PM (trade name) manufactured by Sumitomo Chemical Co., Ltd., manufactured by Chisso Corporation No. Terrage-C60 (trade name), Terrage-C70 (trade name), Terrage-C80 (trade name) and the like.

The phosphate compound (d2) represented by the general formula (3) that may be used in the present invention is a salt of diamine or piperazine with respect to phosphoric acid.
Specific examples of the diamine represented by Y ₁ in the general formula (3) include N, N, N ′, N′-tetramethyldiaminomethane, ethylenediamine, N, N′-dimethylethylenediamine, and N, N′—. Diethylethylenediamine, N, N-dimethylethylenediamine, N, N-diethylethylenediamine, N, N, N ′, N′-tetramethylethylenediamine, N, N, N ′, N′-diethylethylenediamine, tetramethylenediamine, 1, 2-propanediamine, 1,3-propanediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane Piperazine, trans-2,5-dimethylpiperazine, 1, - bis (2-aminoethyl) piperazine, 1,4-bis (3-aminopropyl) piperazine, and the like, it is possible to use all commercially available.

  Examples of the phosphate compound (d2) represented by the general formula (3) preferably used in the present invention include salts of phosphoric acid and piperazine. The salt of phosphoric acid and piperazine can be obtained by the following method. For example, in the case of a pyroperidic acid piperazine salt, it is easily obtained as a poorly water-soluble precipitate by reacting piperazine and pyrophosphoric acid in water or an aqueous methanol solution. Specific examples of preferable piperazine phosphate compounds used in the present invention include orthophosphate piperazine salts, pyrophosphate piperazine salts, and other polyphosphate piperazine salts. However, in the case of piperazine polyphosphate, phosphoric acid may be a salt obtained from polyphosphoric acid and piperazine made of a mixture of orthophosphoric acid, pyrophosphoric acid, tripolyphosphoric acid and other polyphosphoric acids, and the composition of the raw polyphosphoric acid is particularly limited Not.

  The phosphorus-based flame retardant composition (D) according to the present invention is preferably a composition containing the phosphate compound (d1) and the phosphate compound (d2), and particularly as a blending ratio (mass basis). Is preferably phosphate compound (d1) / phosphate compound (d2) = 20/80 to 60/40, and phosphate compound (d1) / phosphate compound (d2) = 30/70 to 50/50 is more preferable.

  Further, the phosphate compound (d1) represented by the general formula (1) and the phosphate compound (d2) represented by the general formula (3) used in the present invention are measured by a laser diffraction method. Each having an average particle size of 100 μm or less, more preferably 10 μm or less is suitable. If the average particle size of the phosphate compound is larger than 100 μm, the dispersibility with respect to the resin is deteriorated, and not only high flame retardancy cannot be obtained, but also the mechanical strength of the obtained molded article is lowered. May bring.

  In the phosphorus-based flame retardant composition according to the present invention, at least one selected from the above-mentioned phosphorus-containing flame retardant imparting agents is used. Further, other flame retardant imparting agents may be used in combination with these phosphorus-containing flame retardant imparting agents.

Such flame retardants that may be used in combination include antimony compounds such as antimony trioxide, antimony pentoxide, sodium antimonate, zinc sulfate, zinc stannate, zinc hydroxystannate, zinc borate, etc. Zinc compounds, iron compounds such as hydroxyzinc ferrous oxide and ferric oxide, tin compounds such as metastannic acid, stannous oxide and stannic oxide, metal salts of tungstic acid, composite oxides of tungsten and metalloid Examples thereof include a tungsten compound such as an acid, a zirconium-based compound, and hydrotalcite, and may be surface-treated with a fatty acid or a silane coupling agent. Of these, zinc compounds, particularly at least one zinc salt selected from zinc stannate, zinc hydroxystannate and zinc borate are preferred.
Thereby, a flame retardance can be improved further. By blending these compounds, the speed of shell formation during combustion increases, and the shell formation becomes stronger. These zinc borate, zinc hydroxystannate, and zinc stannate preferably have an average particle size of 5 micrometers (μm) or less, and more preferably 3 microns (μm) or less. Examples of these zinc borates include Alkanex FRC-500 (2ZnO / 3B ₂ 0 ₃ · 3.5H ₂ 0), FRC-600 (trade name, manufactured by Mizusawa Chemical Co., Ltd.), and zinc stannate (ZnSnO ₃ ) and zinc hydroxystannate (ZnSn (OH) ₆ ) include Alkanex ZS (trade name) and Alkanex ZHS (trade name, manufactured by Mizusawa Chemical Co., Ltd.).

Examples of the silicone flame retardant imparting agent include silicone resins and silicone oils. Examples of the silicone resin include resins having a three-dimensional network structure formed by combining structural units of SiO ₂ , RSiO _3/2 , R ₂ SiO, and R ₃ SiO _1/2 . Here, R represents an alkyl group such as a methyl group, an ethyl group or a propyl group, an aromatic group such as a phenyl group or a benzyl group, or a substituent containing a vinyl group in the above substituent. These include, for example, silicone oils such as dimethyl silicone oil and methylphenyl silicone oil, modified silicone oils such as epoxy modification, alkyl modification, amino modification, carboxy modification, alcohol modification, ether modification, dimethylpolysiloxane rubber, methylvinylpolysiloxane. Silicone rubber such as rubber, silicone resin such as methylsilicone resin and ethylsilicone resin, fine particle silicone powder (Si powder), and the like.

These silicone powders ((Si powder) and the like also have a function as a molding aid and a function as a lubricant.
The phosphorus-based flame retardant composition (D) according to the present invention preferably contains 15 to 25% by mass of nitrogen element.

Furthermore, it is desirable that the phosphorus-based flame retardant composition (D) according to the present invention contains 3 to 8% by mass of zinc oxide.
Thermoplastic polymer composition In the thermoplastic polymer composition of the present invention, the propylene polymer (A) is 50 to 100% by mass, preferably 50 to 90% by mass, and the propylene polymer (B) is 0. -40 mass%, preferably 10-30 mass%, and the ethylene polymer (C) is 0-40 mass%, preferably 0-25 mass% [of (A), (B) and (C) The total amount is 100% by mass. The thermoplastic polymer composition containing 1 to 150 parts by mass, preferably 1 to 100 parts by mass of the phosphorus-based flame retardant composition (D) with respect to 100 parts by mass of the polymer component.

  When the thermoplastic polymer composition of the present invention contains the propylene polymer (B), the ratio of elastic modulus between the propylene polymer (A) and the propylene polymer (B) [propylene polymer weight]. The blend (A) / propylene polymer (B)] is preferably in the range of 10 to 3000, more preferably in the range of 30 to 250.

In the polymer component, when the propylene polymer (A) is less than 50% by mass, the flexibility, elongation at break, and flame retardancy of the obtained molded article may be lowered.
By setting the amount of the phosphorus-based flame retardant composition (D) within the above range, it is possible to balance the flame retardancy, mechanical properties, and flexibility of the obtained molded article.

  In the thermoplastic polymer composition of the present invention, other synthetic resins, other rubbers, antioxidants, heat stabilizers, ultraviolet absorbers, weathering stability, and the like, as long as the object of the present invention is not impaired. An additive such as an agent, an antistatic agent, a slip agent, an antiblocking agent, a crystal nucleating agent, a pigment, a dye, a lubricant, a hydrochloric acid absorbent, and a copper damage inhibitor may be included.

  The addition amount of such other synthetic resins, other rubbers, additives and the like is not particularly limited as long as the object of the present invention is not impaired. For example, in the whole thermoplastic polymer composition, (A) , (B), (C), and (D) are preferably contained such that the total of each component is 60 to 100% by mass, preferably 80 to 100% by mass. The remainder is the above-mentioned other synthetic resin, other rubber, additive, etc., and as such components, polyolefin waxes such as polyethylene wax and polypropylene wax, low density polyethylene, medium density polyethylene, low density polyethylene, ethylene And LLDPE, ethylene-based elastomers, styrene-based elastomers, and the like, which are copolymers of α-olefins having 4 to 10 carbon atoms.

  The thermoplastic polymer composition of the present invention can be produced by a conventionally known method. For example, the above components are mixed simultaneously or sequentially into, for example, a Henschel mixer, a V-type blender, a tumbler mixer, a ribbon blender, etc., and then mixed into a multi-screw such as a single screw extruder or a twin screw extruder. It can be obtained by melt-kneading with an extruder, kneader, Banbury mixer or the like.

  Among these, when an apparatus excellent in kneading performance such as a multi-screw extruder, a kneader, and a Banbury mixer is used, a high-quality thermoplastic polymer composition in which each component is more uniformly dispersed can be obtained. Moreover, the said other additive, for example, antioxidant, etc. can also be added as needed in these arbitrary steps.

  The order of blending the components is not particularly limited, but the propylene polymer (A), the propylene polymer (B) as necessary, and the ethylene polymer (C) as needed are melted. After kneading, it is desirable to melt-knead with other components such as the flame retardant composition (D), or, further, melt and knead a part of these polymer components and the flame retardant composition (D) as a master. It is desirable to use these after melt-kneading after making into a batch. Thereby, the composition excellent in the balance of mechanical strength, hardness, flexibility, and heat resistance can be obtained.

Molded body The molded body of the present invention comprises the thermoplastic polymer composition as described above. The molded article of the present invention can be melt-molded into various shapes by the conventionally known melt-molding method using the above thermoplastic polymer composition. Examples of conventionally known melt molding methods include extrusion molding, rotational molding, calendar molding, injection molding, compression molding, transfer molding, powder molding, blow molding, and vacuum molding. In one aspect of the propylene-based resin composition of the present invention, the filler is contained in a high proportion, and the balance of mechanical strength, flexibility, and heat resistance is excellent.

Furthermore, the thermoplastic polymer composition of the present invention can be widely used for molded products having flame retardancy, such as electric wires and building materials.
The molded body may be a complex with a molded body made of other materials, for example, a laminated body.

  In addition, since the above-mentioned molded article has excellent balance of performance that is excellent in flexibility and scratch resistance while maintaining mechanical strength, for example, an insulator of an electric wire including an optical fiber coating, Can be used suitably for wire sheathing applications such as wire sheathing, and can improve the scratch resistance of molded products such as electric wires with a cylindrical shape. It is suitable for use as an electric wire sheath and electric wire covering for household appliances.

  Moreover, the coating layers such as the electric wire insulator and the electric wire sheath are formed around the electric wire by a conventionally known method, for example, a method such as extrusion molding.

EXAMPLES Hereinafter, although this invention is demonstrated further more concretely based on an Example and a comparative example, this invention is not limited to these Examples.
(1) Component of composition (1-1) Propylene polymer (A)
(1-1-1) Propylene / ethylene / 1-butene copolymer (A2-1)
Based on the method described in JP 2007-186664 A, a polymerization catalyst diphenylmethylene (3-tert-butyl-5-ethylcyclopentadienyl) (2,7-di-tert-butylfluorenyl) zirconium dichloride is used. And propylene / ethylene / 1-butene copolymer (A2) by polymerizing ethylene, propylene and 1-butene as raw materials in a hexane solution using a continuous polymerization facility in the presence of cocatalyst methylaluminoxane (manufactured by Tosoh Finechem) -1) was obtained. Table 1 shows the physical property values of the obtained copolymer.

(1-2) Propylene polymer (B)
A propylene homopolymer (B-1) having physical properties shown in Table 2 was used.
(1-3) Ethylene polymer (C)
(1-3-1) Ethylene / 1-butene copolymer (C-1)
As the ethylene / 1-butene copolymer, a copolymer having the following physical properties (trade name: Toughmer A-4085S, manufactured by Mitsui Chemicals, Inc.) was used.

Fluidity (MFR) (190 ° C.): 3.6 g / 10 min Density: 885 kg / m ³
Melting point (Tm): 69 ° C
-Surface hardness (Shore A): 86
(1-3-2) Ethylene / vinyl acetate copolymer (C-2)
As the ethylene / vinyl acetate copolymer, a copolymer having the following physical properties (trade name: EVAFLEX EV270, manufactured by Mitsui DuPont Polychemical Co., Ltd.) was used.

-Fluidity (MFR) (190 ° C): 1.0 g / 10 min-Vinyl acetate content: 28 wt%
・ Density: 970kg / m ³
Tm (2nd): 69 ° C
-Surface hardness (Shore A): 82
(1-4) Phosphorus flame retardant composition (D)
Phosphorus flame retardant compositions (D-1) (manufactured by Adeka Corp., Adeka Stub FP-2200) and (D-2) (manufactured by Adeka Corp., Adeka Stub FP-2400) are used as phosphoric acid flame retardant compositions. It was. These phosphoric acid flame retardant compositions (D-1) have an average particle size of 10 μm or less as measured by a laser diffraction formula. In addition, the phosphorus-based flame retardant composition (D-1) (manufactured by Adeka Corporation, Adeka Stab FP-2200) includes a phosphate compound (d-1) represented by the above chemical formula (1) and a chemical formula ( It contains the phosphate compound (d-2) represented by 3) and contains units of melamine, piperazine and phosphoric acid.

(1-5) Magnesium hydroxide (Mg (OH) ₂ )
Magnesium hydroxide surface-treated with silane (manufactured by Albert, Magnifine H5IV) was used.

(1-6) Zinc borate (2ZnO / 3B ₂ 0 ₃ · 3.5H ₂ 0)
Zinc borate (Mizusawa Chemical Co., Ltd., Alkanex FRC-500) was used.
(1-7) Fatty acid amide Ethylene biserucic acid amide (manufactured by NOF Corporation, Alflow AD221) was used.

The physical properties of the polymers and compositions used in Examples and Comparative Examples were measured by the following methods.
[Melting point Tm]
Tm (1st): DSC obtained when measured at 23 ° C. ± 2 ° C. for 72 hours or longer and then cooled to −40 ° C. and then measured at a heating rate of 10 ° C./min. A curve was created. The melting point obtained at this time was Tm (1st), and the melting enthalpy was ΔH (1st).

  Tm (2nd): held at 200 ° C. for 10 minutes in the DSC measuring apparatus, then cooled to −20 ° C. at a cooling rate of 10 ° C./min, held at −20 ° C. for 1 minute, and then again at a heating rate of 10 ° C./min. The DSC curve obtained when measured by (1) was prepared. With respect to the melting point (Tm) in the present invention, the melting point obtained at this time was Tm (2nd), and the melting enthalpy was ΔH (2nd).

[Comonomer content (composition)]
^It was determined by analysis of ¹³ C-NMR spectrum.
[Stereoregularity]
Mm was determined by analysis of ¹³ C-NMR spectrum.

[Regularity (inversion)]
^The amount of 2,1-bond was determined by analysis of ¹³ C-NMR spectrum.
[Molecular weight distribution Mw / Mn]
GPC (gel permeation chromatography) was used as an orthodichlorobenzene solvent (mobile phase) and measured at a column temperature of 140 ° C. (polystyrene conversion, Mw: weight average molecular weight, Mn: number average molecular weight). Specifically, the molecular weight distribution (Mw / Mn) was measured as follows using a gel permeation chromatograph Alliance GPC-2000 manufactured by Waters. The separation columns are two TSKgel GNH6-HT and two TSKgel GNH6-HTL, the column size is 7.5 mm in diameter and 300 mm in length, the column temperature is 140 ° C., and the mobile phase The sample was transferred at 1.0 ml / min using o-dichlorobenzene (Wako Pure Chemical Industries) and BHT (Takeda Pharmaceutical) 0.025 wt% as an antioxidant, and the sample concentration was 15 mg / 10 ml. The amount was 500 μl, and a differential refractometer was used as a detector. Standard polystyrene used was manufactured by Tosoh Corporation for molecular weights of Mw <1000 and Mw> 4 × 10 ⁶ , and used by Pressure Chemical Co. for 1000 ≦ Mw ≦ 4 × 10 ⁶ .

[Fluidity (MFR)]
Based on ASTM D 1238, it was measured at 190 ° C. or 230 ° C. and 2.16 kgf.

[density]
It measured at 23 degreeC using the density gradient tube based on ASTMD1505.
[Surface hardness Shore A]
Pressurize for 2 minutes using a hydraulic hot press molding machine (manufactured by Kansai Roll Co., Ltd.) set at 190 ° C, pressurize for 2 minutes, immediately cool for 4 minutes in a cooling tank set at 20 ° C, and press the sheet with a thickness of 2 mm Was made. A 100 μm PET film (manufactured by Toray Industries Inc., Lumirror) was used as a release film during press molding. This was stored for 72 hours in an environment of 23 ° C. ± 2 ° C., and then the physical properties were measured. In accordance with ASTM D-2240, the scale was read immediately after contact with the pressing needle using an A-type measuring instrument.

[Tensile properties]
Using the press sheet prepared by the above method, the yield strength, the strength at break, the elongation at break (between chucks), and the initial elastic modulus were measured according to JIS K 7113-2 (measurement temperature 23 ° C., tensile (Speed = 200 mm / min, maximum strain = 800%). Moreover, the thing which was not fracture | ruptured by distortion = 800% made the stress at this time the breaking point stress.

(2) Production method of composition After dry blending each of the above components in the proportions shown in Table 3, it was melt-kneaded by a twin screw extruder (JSW, screw diameter 32 mm, L / D = 42) ( Resin temperature: 220-230 ° C.) and pelletized.

(3) Test Sample Preparation Method (3-1) Injection Molding Using an injection molding machine (manufactured by Meiki Co., Ltd.) in which the resin composition obtained by the method of (2) is set at a cylinder temperature of 200 ° C and a mold temperature of 40 ° C Specimen or square plate was molded.

(3-2) Press molding Using a hydraulic hot press molding machine (manufactured by Kansai Roll Co., Ltd.) in which the resin composition obtained by the method of (2) is set to 190 ° C, pressurize for 2 minutes and then pressurize for 2 minutes. Immediately, it was cooled for 4 minutes in a cooling tank set at 20 ° C. to produce a 2 mm thick press sheet. A 100 μm PET film (manufactured by Toray Industries Inc., Lumirror) was used as a release film during press molding. This was stored in an environment at 23 ° C. for 72 hours, and then the physical properties were measured.

(3-3) Electric Wire Molding The resin composition obtained by the method of (2) was molded into an electric wire by using an electric wire coater (manufactured by Mitsuba Manufacturing Co., Ltd.) (covering thickness 1.4 mm). At that time, the core wire used was a flexible copper strand (1.2 mm diameter, 30 pitches of 0.18 mm, 13 pitch (right), manufactured by Musashikinsen).

(4) Evaluation method and results (4-1) Evaluation of flexibility [Shore D (surface hardness)]
Using the press sheet obtained by the method described in (3-2), in accordance with ASTM D 2240, the scale after 5 seconds was read after contact with the pressing needle with a D-type measuring instrument.

(4-2) Evaluation of mechanical properties [Tensile properties]
Using the ASTM-IV specimen prepared by the method described in (3-1), the strength at break, elongation at break (between chucks), and initial elastic modulus were measured according to ASTM D 638 (measurement temperature: 23 ° C., (Tensile speed = 200 mm / min, maximum strain = 800%). Moreover, the thing which was not fracture | ruptured by distortion = 800% made the stress at this time the breaking point stress.

[Bending characteristics]
Using the test piece prepared by the method described in (3-1), the bending elastic modulus and bending strength were measured at a temperature of 23 ° C. and a bending speed of 5 mm / min according to ASTM D790.

(4-3) Evaluation of heat resistance [Heating deformation rate]
Using the press sheet obtained by the method described in (3-2), the deformation rate was measured at a heating temperature of 120 ° C. and a load of 10 N in accordance with 4.23 of JIS C 3005.

(4-4) Evaluation of low temperature characteristics [Low temperature embrittlement temperature]
Using a square plate prepared by the method described in (3-1), the embrittlement temperature was measured in accordance with JIS K 7216.

(4-5) Evaluation of flame retardancy [Vertical flame retardant test (VW-1)]
Using the electric wire created by the method described in (3-3), a vertical flame retardant test was performed in accordance with UL1581-1080 (test gas: methane, methane gas flow rate: 0.97 L / min, methane pressure: 1 .23 kPa, burner flame length: 125 mm, burner flame length: 40 mm, test chamber temperature: 29 ° C., humidity: 55%).

(4-6) Evaluation of insulation [Volume resistivity]
Using the press sheet obtained by the method described in (3-2), the resistance value is measured at a measurement temperature of 23 ° C., a humidity of 50%, an applied voltage of 500 V, and an applied time of 1 minute in accordance with JIS K 6922-2. did.

Examples 1-12, Comparative Examples 1-7
A composition having the composition shown in Table 3 was kneaded using a lab plast mill (manufactured by Toyo Seiki Co., Ltd.).

  Table 1 and Table 2 show the physical properties of each component.

プレス成形機によって、これを厚さ２ｍｍのシートに成形した（加熱：温度１９０℃、７分間、冷却：温度１５℃、４分間、冷却速度約：４０℃／分）。このシートについて実施した破断点応力、破断点伸び、曲げ強さ、曲げ弾性率、加熱変形率、低温脆化温度、垂直難燃試験、体積抵抗率の評価結果を表３に示す。

This was formed into a sheet having a thickness of 2 mm by a press molding machine (heating: temperature 190 ° C., 7 minutes, cooling: temperature 15 ° C., 4 minutes, cooling rate: about 40 ° C./minute). Table 3 shows the evaluation results of the stress at break, elongation at break, flexural strength, flexural modulus, heat deformation rate, low temperature embrittlement temperature, vertical flame retardant test, and volume resistivity performed on this sheet.

  The thermoplastic polymer composition of the present invention has an excellent balance of mechanical strength, flexibility, and heat resistance. Furthermore, the thermoplastic polymer composition of the present invention can be widely used for molded products having flame retardancy, such as electric wires and building materials.

  When the thermoplastic polymer composition according to the present invention is used for the insulating layer of the electric wire sheath and the electric wire coating, the molded body according to the present invention is the electric wire sheath and / or the covering layer, and the electric wire sheath and the covering layer. Is formed around the electric wire by a conventionally known method such as an extrusion method.

According to the present invention, it is possible to provide a thermoplastic polymer composition having a high degree of flame retardancy and being flexible, and a molded body thereof.
Since the thermoplastic polymer composition according to the present invention has the effects as described above, it is suitable for various molded products such as wire coating, tape, film, flame retardant sheet, pipe, blow molded product, flame retardant wallpaper and the like. It is particularly suitable for an electric wire sheath including an optical fiber coating and the like, as well as its insulating layer and electric wire coating. In particular, the flexibility and heat resistance are suitable for the use of electric wire sheaths and electric wire coverings for consumer and household devices such as power cords.

Claims (8)

  Propylene polymer (A) having an initial tensile modulus of elasticity of less than 500 MPa measured based on JIS K 7113-2: 50 to 100% by mass, Propylene polymer (B) having an initial tensile modulus of 500 MPa or more : 0 to 40% by mass, and ethylene-based polymer (C): Polymer component consisting of 0 to 20% by mass [(A), (B) and (C) in total is 100% by mass. ), And a thermoplastic polymer composition comprising 1 to 150 parts by mass of the phosphorus-based flame retardant composition (D) with respect to 100 parts by mass of the polymer component. The thermoplastic polymer composition according to claim 1, wherein the propylene polymer (A) satisfies the following (a), (b) and (c).
(A) Melting point measured by differential scanning calorimetry (DSC) is less than 120 ° C. or no melting point is observed.
(B) The molecular weight distribution (Mw / Mn) measured by gel permeation chromatography (GPC) is 1-3.
(C) The melt flow rate (MFR) at 230 ° C. is 0.1 to 50 g / 10 minutes. 3. The thermoplastic heavy polymer according to claim 1, wherein the propylene polymer (A) is a propylene / ethylene / α-olefin random copolymer having 4 to 20 carbon atoms satisfying the following (m) and (n): Combined composition.
(M) 40 to 85 mol% of a structural unit derived from propylene, 5 to 30 mol% of a structural unit derived from ethylene, and 5 to 30 mol% of a structural unit derived from an α-olefin having 4 to 20 carbon atoms ( Here, the sum total of the structural unit derived from propylene, the structural unit derived from ethylene, and the structural unit derived from an α-olefin having 4 to 20 carbon atoms is 100 mol%.
(N) The initial tensile modulus measured based on JIS K 7113-2 is 1 to 100 MPa.   The phosphorus-based flame retardant composition (D) contains a compound having a triazine structure, a compound having a piperazine ring, and a unit of phosphoric acid. Thermoplastic polymer composition.   The thermoplastic polymer resin composition according to any one of claims 1 to 4, wherein the phosphorus-based flame retardant composition (D) contains 15 to 25% by mass of a nitrogen element.   The thermoplastic polymer resin composition according to any one of claims 1 to 5, wherein the phosphorus-based flame retardant composition (D) contains 3 to 8% by mass of zinc oxide.   The molded object which consists of a thermoplastic polymer composition of any one of Claims 1-6.   The molded body according to claim 6, wherein the molded body is an electric wire insulator or an electric wire sheath.