WO2004011548A1

WO2004011548A1 - Thermoplastic resin composition and molded object comprising the composition

Info

Publication number: WO2004011548A1
Application number: PCT/JP2003/009069
Authority: WO
Inventors: Hiroshi Uehara; Masayoshi Yamaguchi; Hideshi Kawachi
Original assignee: Mitsui Chemicals, Inc.
Priority date: 2002-07-25
Filing date: 2003-07-17
Publication date: 2004-02-05
Also published as: JPWO2004011548A1

Abstract

A resin composition which has excellent flame retardancy and satisfactory flexibility. The thermoplastic resin composition is characterized in that in a flame retardance test of an insulating electric wire sample, the largest inclination angle (A) among the sample inclination angles in the flame retardance test at which the fire of the sample is spontaneously extinguished satisfies the following relationship (1): A ≥ 2.3 × σ - 2.8 (1) wherein σ is the torsional rigidity of the thermoplastic resin composition and A is not smaller than 0 degree and not larger than 90 degrees. The thermoplastic resin composition is characterized by comprising: 20 to 64.9 wt.% ethylene/α-olefin copolymer obtained from ethylene and a C3-10 α-olefin, 35 to 70 wt.% metal hydroxide, and 0.1 to 10 wt.% fluorine compound.

Description

Description Thermoplastic resin composition and molded article made from the composition

The present invention relates to a thermoplastic resin composition and a molded product thereof, and more particularly, to a thermoplastic resin composition and a molded product thereof particularly suitable as a material for an insulator and a sheath of an electric wire.

Conventionally, polychlorinated vinyl (PVC) has often been used as the sheath material and partially insulating material of electric wires, and its flexibility, flame retardancy, and insulation properties have been evaluated. In general, PVC contains a large amount of plasticizer, which makes it easier to cure if the plasticizer is removed by heating, etc., and generates chlorine-based gas during combustion. It has become required.

Under these circumstances, for example, various flame-retardant resin compositions based on ethylene polymers such as polyethylene have been proposed.

USP 6, 232, and 377 include specific ethylene copolymers selected from ethylene Z-butyl ester copolymer, ethylene / α, β-unsaturated carboxylic acid copolymer, and low-density polyethylene. And a flame-retardant resin composition containing a metal hydroxide, a triazine compound and a specific flame-retardant compound. However, when these ethylene polymers are added with an increased amount of an inorganic compound such as a metal hydroxide in order to enhance the flame retardant effect, the flexibility and the flexibility are reduced. The problem is that you get stiff. Disclosure of the invention

An object of the present invention is to provide a resin thread and a molded article thereof, which is excellent in flame retardancy and has good flexibility and flexibility, particularly an insulator and / or sheath of an electric wire. is there. The ethylene resin composition according to the present invention,

(A) an ethylene-Hiichio Refuin copolymer consisting of one Orefin of ethylene and carbon number 3-1 0 20 to 64.9 weight ^_0/0

(B) 35-70% by weight of metal hydroxide;

(C) a fluorine compound from 0.1 to 1 0 weight ^_0/0

It is characterized by power.

Furthermore, the ethylene resin composition according to the present invention

(A) Ethylene comprising the following ethylene polymers (A-1) and (A-2) in a weight ratio of (A_l) / (A-2) = 20/8 0-1 100/0 -Based copolymer composition 20-64.9% by weight

(A-1): an ethylene 'a-olefin copolymer comprising ethylene and α-olefin having 3 to 10 carbon atoms

(A-2): Ethylene copolymer other than (A-1)

(B) 35-70% by weight of metal hydroxide;

(C) Fluorine compound 0.1 to 10% by weight

It is characterized by power.

Further, the ethylene α-olefin copolymer (Α) or (A-1)

(i) The density (ASTM D1505, 23 ° C) is in the range of 0.855 to 0.910 gZcm3

(Ii) 190. C, the melt flow rate (MFR2) at 2.16 kg load (ASTM D1238, load 2.16 kg, 190 ° C) is in the range of 0.1 to 100 g / 10 min, and (iii) evaluated by GPC method. Index of molecular weight distribution: Mw / Mn is in the range of 1.5 to 3.5,

Furthermore, the ethylene'hydroolefin copolymer (A) or (A-1) force (i) density (ASTM D1505, 23 ° C) is 0.857 to 0.890 g / cm3. In the range,

(ii) The melt flow rate (MFR2) (ASTM D1238, load 2.16 kg, 190 ° C) at 190 ° C and 2.16 kg load is in the range of 0.;! to 20 g / 10 minutes,

(iii) Index of molecular weight distribution evaluated by GPC method: Mw / Mn of 1.5 to 3.5 In the range,

(iv) l Ratio of melt flow rate (MFR10) at 90 ° C and 10 kg load to melt flow rate (MFR2) at 190 ° C and 2.16 kg load: MFR10 / MFR2 indicates the following relationship. Fill,

MFR10 / MFR2 ≥ 5.7

Mw / Mn + 4.7 ≤ MFR10 / MFR2,

(v) the intensity ratio (Τα / Τaa) of To; to To; in the 13C-NMR spectrum is 0.5 or less;

(vi) The 13C-NMR spectrum is characterized in that the B value obtained from the following formula is 0.9 to 1.5.

B {it = [POE] Z (2 · [PE] [PO])

(Where [PE] is the mole fraction of the structural unit derived from ethylene in the copolymer, and [PO] is the mole fraction of the structural unit derived from α-olefin in the copolymer. And [ΡΟΕ] is the ratio of the number of ethylene-free-olefin chains to all dyad chains in the copolymer.)

FIG. 1 is a schematic view of a flame retardant test apparatus according to the present invention. In FIG. 1, 1 indicates an insulated wire, and 2 indicates a burner. FIG. 2 shows the relationship between the torsional rigidity of the thermoplastic resin composition shown in Table 1 and the flame retardancy test angle. BEST MODE FOR CARRYING OUT THE INVENTION

Hereinafter, the ethylene copolymer composition and the molded article thereof according to the present invention will be specifically described.

First, the ethylene polymer according to this effort! /, I will explain.

(A) Ethylene copolymer

The ethylene copolymer (A) of the present invention is usually an ethylene 'α-olefin copolymer. The ethylene-olefin copolymer is the following ethylene-α-olefin copolymer (A-1). The ethylene 'α-olefin copolymer is the following ethylene' _α It may be a composition of -olefin copolymer (A-1) and an ethylene polymer (A-2) other than (A-1). When the ethylene 'α-olefin copolymer is a composition of the following ethylene-thioolefin copolymer (Α-1) and an ethylene polymer (Α-2) other than (A-1), its composition The ratio is (Α-1) / (Α-2) = 20Ζ80 to 100 00 by weight, preferably 50 50 to: L00Ζ0, more preferably 80/20 to 100/0 by weight. Consisting of

Ethylene 'α-olefin copolymer (A-1)

The ethylene'-hore-olefin copolymer (A-1) of the present invention is an ethylene / α-olefin copolymer comprising ethylene and α-olefin having 3 to 10 carbon atoms. As α-olefins having 3 to 10 carbon atoms, specifically, propylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene, 3-methynole 1-pentene, 3-ethyl -1-pentene, 4-methynole-1-pentene, 4-methyl-1-hexene, 4,4-dimethinole-1-pentene, 4-ethyl-1-hexene 1-otaten, 3-ethyl-1- Hexene, 1-otaten, 1-decene, and the like. Of these, 1 octene, 1 hexene, and 1 otaten are preferably used.

Ethylene 'Fei - Orefin copolymer content of each structural unit (A- 1) in the content of 50 to 98 mol of a structural unit derived from Echire emissions ^_0/0, preferably 75-9 5 molar% and a, a carbon number of 3-1 0 - content of constituent units derived from at least one compound selected from Orefin is 2-50 mole ^_0/0, is preferably 5-2 5 mol ^_0/0 . Further, the ethylene 'α-olefin copolymer (Α-1) preferably has the following characteristics.

(i) The density (ASTM D1505, 23 ° C) is in the range of 0.855 to 0.910 g / cm3, preferably 0.857 to 0.890 gcm3.

(ii) 1 90. C, 2. Melt flow rate (MFR2) at load of 16 kg (ASTM D1238, load 2.16 kg, 190 ° C) 0.1 ~: L 0 g / 10 min, preferably 0.1 ~

It is in the range of 20 g / 10 minutes.

(iii) Index of molecular weight distribution evaluated by the GPC method: Mw / Mn is in the range of 1.5 to 3.5, preferably 1.5 to 3.0, particularly preferably 1.8 to 2.5. .

(iv) l90. C, melt flow rate (MFR10) and 190 at 10 kg load. C, Ratio to melt flow rate (MFR2) at 2, 16 kg load: MFR10 / MFR2 satisfies the following relationship.

MFR10 / MFR2 ≥ 5.7

Mw / Mn + 4.7 ≤ MFR10 / MFR2

Here, when MFR10, MFR2, and MwZMn do not satisfy the above relationship, the moldability and / or the material strength are reduced.

(V) The intensity ratio of Ta jS to Ta a in the 13C-NMR spectrum (ΤαCαα) is 0.5 or less, preferably 0.4 or less.

Here, Τα and Τα in the 13C-NMR spectrum are the peak intensities of C 中 2 in the structural unit derived from α-olefins having 3 or more carbon atoms, and as shown below, Means two types of CH2 with different positions.

R R R R

C-CH -CH, C- -C-CH 2 C

H H Η Η

Ύ α β 1

Such a Τα / 3 / Ταα intensity ratio can be obtained as follows. The 13C-NMR spectrum of the ethylene'α-olefin copolymer is measured using, for example, a JEOL-GX270 NMR measurement device manufactured by Nippon Denshi. The measurement was performed at 6 7.8 MHz, 25 ° C, d6-benzene using a mixed solution of hexachlorobutadiene / d6-benzene = 2/1 (volume ratio) adjusted to a sample concentration of 5% by weight. (128ppm) Standard The measured 13C-NMR spectrum was analyzed according to Lindemann Adams's proposal (Analysis Chemistry43, pl245 (1971)) and JCRandall (Review Macromolecular Chemistry Physics, C29, 201 (1989)) to determine the Ta β / Ύα α intensity ratio. Ask. (vi) The 13 C-NMR spectrum and the B value determined from the following formula are in the range of 0.9 to 1.5, preferably 1.0 to 1.2.

8 values = [POE] / (2 · [PE] [PO])

(Wherein [PE] is the mole fraction of the structural unit derived from ethylene in the copolymer, and [PO] is the mole fraction of the structural unit derived from -olefin in the copolymer. And [POE] is the ratio of the number of ethylen'-oleophine chains to all dyad chains in the copolymer.)

This B value is an index representing the distribution state of ethylene and α-olefin having 3 to 10 carbon atoms in the ethylene ′ α-olefin copolymer, JCRandall (Macromolecules, 15, 353 (1982)), J It can be determined based on the report by Ray (Macromolecules, 10, 773 (1977)).

The larger the B value, the shorter the block chain of the ethylene or α-olefin copolymer, the more uniform the distribution of ethylene and α-olefin, and the narrower the composition distribution of the copolymer rubber. . As the Β value becomes smaller than 10, the composition distribution of the ethylene / α-olefin copolymer becomes broader and blockier, and there is a bad point such that the handleability deteriorates.

Process for Producing Ethylene 'a-olefin Copolymer (Α) or (A-1) Such an ethylene' α-olefin copolymer is obtained by mixing ethylene and a C 3 -C 10 in the presence of a meta-acene catalyst. And _α -olefin.

Such a metallocene catalyst comprises a metallocene compound (a) and a compound (c) which reacts with an organoaluminumoxy compound (b) and / or a metallocene compound (a) to form an ion pair. And (a), (b) and Z or (c) together with an organic aluminum compound (d)-.

In the presence of the above catalyst, ethylene and α-olefin having 4 to 6 carbon atoms are usually copolymerized in a liquid phase. In this case, a hydrocarbon solvent is generally used, but olefin may be used as the solvent.

This copolymerization can be carried out by any of a batch system, a semi-continuous system and a continuous system. The catalyst components are used in the following concentrations. When a metallocene catalyst comprising a metallocene compound (a) and an organoaluminoxy compound (b) or an ionizing compound (c) is used, the concentration of the metallocene compound (a) in the polymerization system Is usually 0.00005 to 0.1 mmol (polymerization volume), preferably 0.0001 to 0.05 mmol Z liter. The organoaluminoxy compound (b) has a molar ratio (A 1 / transition metal) of an aluminum atom to a transition metal in a metallocene compound in a polymerization system of 1 to 10,000, preferably 10 to 5000. Supplied in quantity.

In the case of the ionized ionic compound (c), the molar ratio of the ionized ionic compound (c) to the meta-mouth compound (a) in the polymerization system (ionized ionic compound (c) / metallocene compound) In (a)), it is supplied in an amount of 0.5 to 20, preferably 1 to 10.

When an organoaluminum compound is used, it is used in an amount of usually about 0 to 5 mmol Z liter (polymerization volume), preferably about 0 to 2 mmol / liter.

The copolymerization reaction is usually carried out at a reaction temperature of 120 to 150 ° C, preferably 0 to 120 ° C, more preferably 0 to 100 ° C, and a pressure exceeding 0 to 7.8 MPa (80 kg ^ cm2, Gauge pressure) or less, preferably more than 0 and 4.9 MPa (50 kg £ ½n2, gauge pressure) or less.

Ethylene and α-olefin are supplied to the polymerization system in such an amount that an ethylene / α-olefin copolymer having the above specific composition (Α-1) is obtained. In the copolymerization, a molecular weight regulator such as hydrogen may be used.

When ethylene and o-olefin are copolymerized as described above, a polymerization liquid containing the ethylene-hydroxy-olefin copolymer (A-1) is usually obtained. This polymerization solution is treated by a conventional method to obtain an ethylene 'α-olefin copolymer (Α-1).

Ethylene polymer (Α-2)

Examples of the ethylene polymer (Α-2) used in the present invention include a linear low-density polyethylene, a high-pressure method low-density polyethylene, an ethylene'butyric acid copolymer, an ethylene..ethyl acrylate copolymer , Ethylene methyl methacrylate copolymer, Ethylene 'Athalic acid copolymer, Ethylene' Methacrylic acid copolymer and its iono And ethylene'methacrylate copolymers.

The thermoplastic composition of the present invention covers the seven-stranded conductor (outer diameter 1.35 mm) of a soft copper wire having a wire diameter of 0.45 mm to a thickness of 0.8 mm around the thermoplastic resin composition, and has a finished diameter of 3.0 mm. When performing a flame retardancy test using a wire sample, of the flame retardancy test angles of the samples that extinguish naturally within 60 seconds after ignition, the maximum inclination angle A of the sample is expressed by the following equation (1). To be satisfied.

A≥ 2.3 X σ-2.8 (1)

(In the formula (1), σ is the torsional rigidity at 23 ° C of a 2 mm thick sheet made of the thermoplastic resin composition, and A is 0 ° or more and 90 ° or less.) The thermoplastic resin composition preferably satisfies the following formula (2).

A≥ 2.0 X σ + 1 2.5 (2)

(Α and σ have the same meaning as in equation (1).)

The flame-retardant resin composition is suitable as a material for various molded articles, particularly, a covering material for electric wires and a sheath.

The ethylene polymer (重合) used in the present invention may be silane-grafted. The silane-grafted ethylene polymer (II) is prepared using a bullsilane compound and a peroxide in combination to promote silane grafting. In the present invention, the silane-grafted ethylene polymer (Α) includes an silane-grafted ethylene polymer (Α), a metal hydroxide (Β), a fluorine compound (C), The silane-grafted ethylene-based polymer (A) is obtained by melt-mixing the product and peroxide by various conventionally known methods into the obtained thermoplastic resin composition according to the present invention. ) including.

Specific examples of the above-mentioned vinylsilane compounds include _γ -methacryloxypropyltrimethoxysilane, burtrimethoxysilane, vinyltriethoxysilane, biertributoxysilane, burtris (J3-methoxetoxysilane), biertriacetoxysilane, and the like. Examples include silane and methyltrimethoxysilane. Among them, τ / -methacryloxypropyltrimethoxysilane, vinyltrimethoxysilane, and vinylinoletriethoxysilane are preferred.

The vinylsilane compound is (A) + (B) + (C) in total 100% by weight, Usually from 0.5 to 2.5 wt ^_0/0, preferably used in a ratio of 0.5 to 2 wt%. When the bullsilane compound is used in the above ratio, the silane grafting speed is high and an appropriate degree of silane grafting can be obtained. As a result, a molded product excellent in balance between tensile elongation and tensile strength at break, for example, a wire coating layer Can be formed.

In the present invention, as described above, the peroxide is used together with the bursilane compound in order to promote the silane grafting reaction of the ethylene polymer (A).

Organic peroxides such as benzoyl peroxide, dichlorobenzoyl peroxide, dicumyl peroxide, di-t-butylperoxide, 2,5-dimethyl- 2,5-di (peroxide benzoate) hexine-3,1,4-bis (t-butylperoxyisopropyl) .benzene, lauroyl beloxide, t-butyl peracetate, 2,5 -Dimethyl-2,5-di- (t-butylperoxide) hexine-3,2,5-dimethyl-2,5-di (t-butylperoxide) hexane, t-butyl Benzoate, t-petit / reno.norefeninorea acetate, t-butynolenoleisobutyrate, t-butylper-sec-otatoate, t-butylperpivalate, cumylphenolpivalate, t-butylperjeptyla Acetate; azobisisobutyronite Le, and the like dimethyl chill § zone I isobutyrate.

Of these, dicumylperoxide, di-t-butylperoxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-3,2,5-dimethyl-2,5 -Di (t-butylperoxy) hexane and 1,4-bis (t-butylperoxyisopropyl) benzene peroxide make up a total of 100% by weight of (A) + (B) + (C). in contrast, normal 0 0 5 to 0.1 5 wt ^_0/0, preferably used is 0. 0 1 to 0.1 at a ratio of weight ^_0/0. When the peroxidic acid is used at the above ratio, the reaction of grafting the silane compound to the ethylene polymer (A) can be appropriately promoted.

Metal hydroxide (B)

Examples of the metal hydroxide used in the present invention include aluminum hydroxide, magnesium hydroxide, hydroxide hydroxide, barium hydroxide, manganese hydroxide, zinc hydroxide, and hydrotalcite alone or in combination thereof. Mixtures are preferred, with magnesium hydroxide alone and mixtures containing magnesium hydroxide being particularly preferred. Fluorine compound (c)

Examples of the fluorine compound used in the present invention include fluorine elastomers, fluororubbers, fluororesins, fibrillar polytetrafluoroethylene, and master patches based on thermoplastic resins of these fluorinated compounds. Polytetrafluoroethylene and its masterbatch are particularly preferred. When the diameter of the fibril-shaped buibril is 1 zm or less, preferably 0.5 μπι or less, the dispersion is excellent. Such fibrils have a fibrous network structure formed by bubbling polytetrafluoroethylen or the like by the shear force. The fluorine compound such as polytetrafluoroethylene is preferably modified with acrylic. One master batch is a composition of a fluorine compound such as polytetrafluoroethylene and an ethylene polymer, and the composition contains 10 to 90% by weight of a fluorine compound such as polytetrafluoroethylene. / ₀ , preferably 20 to 50% by weight.

Flame retardant aid

In the resin composition of the present invention, in addition to the above, a flame retardant auxiliary of a silicone compound may be used. The silicone compound used as a flame retardant aid is a compound having Si—o bonded to an organic group. Examples of such a silicone compound include silicone oils such as dimethinole silicone oil and methylphenol silicone oil, and epoxy resins. Modified, alkyl-, amino-, carboxy-, alcohol-, and ether-modified silicone oils, dimethyl polysiloxane rubber, methyl rubber polysiloxane rubber, etc., silicone rubber, methyl silicone resin, ethyl silicone resin, etc. Silicone resin and the like can be mentioned.

These silicone compounds contain a bond S i-O and generate compounds having a bond S i-C upon combustion.These structures serve as a barrier for heat transfer. A synergistic effect of imparting flame retardancy is obtained by thermal condensation, the amount of the metal hydroxide flame retardant is reduced, the mechanical properties of the composition can be maintained, and the generation of CO during combustion of the composition can be reduced. Can be reduced.

When a silicone compound is added, the ethylene compound is composed of ethylene and α-olefin having 3 to 10 carbon atoms.

1-: 0 parts by weight of L is added to 100 parts by weight of the olefin copolymer. If the amount is less than 2 parts by weight, the synergistic effect of imparting flame retardancy obtained with the metal hydroxide is not sufficient, and if it exceeds 10 parts by weight, the thermal stability of the composition becomes insufficient. Preferably, 2 to 8 parts by weight, particularly preferably 3 to 5 parts by weight, is added to 100 parts by weight of the polyolefin resin.

When a silicone compound that is solid at room temperature, such as silicone rubber or silicone resin, is used, it is preferable to use finely divided silicone powder in consideration of dispersibility in the resin composition. As such a silicone powder, an ordinary commercially available silicone powder can be used.

The silicone powder may be added to the composition as it is, but a known coupling agent, for example, a silane coupling agent such as butyltriethoxysilane, a-mercaptopropyltriethoxysilane, or isopropyltrisilane. Preliminary surface treatment of silicone powder using titanium coupling agent such as isostear dititanate, higher fatty acid coupling agent such as stearic acid, maleic acid, oleic acid, etc. By being incorporated therein, the adhesion between the silicone powder and the thermoplastic resin can be improved, and the mechanical properties of the obtained thermoplastic composition can be improved.

Other additives

In addition to the above, the thermoplastic resin composition according to the present invention may further include, if necessary, an antioxidant, an ultraviolet absorber, a weather stabilizer, a heat stabilizer, an antistatic agent, a flame retardant, a pigment, a dye, and a lubricant. An additive such as an agent can be blended.

The content ratio of each component in the polymer composition of the present invention is such that the content of the ethylene polymer (A) is from 20 to 64.9% by weight, preferably from 25 to 60% by weight, and more preferably from 25 to 60% by weight. 30 to 55% by weight, the metal hydroxide (B) force is 35 to 70% by weight, preferably 40 to 70% by weight, and the fluorine compound (C) is 0.1 to 0.1% by weight. 1 0 wt%, is good Mashiku a proportion of 0.1 to 6 wt ^_0/0. (When (A) + (B) + (C) = 100% by weight)

The thermoplastic resin composition according to the present invention is obtained by melt-mixing the above-mentioned components (A), (B) and (C) and, if necessary, additives, by various conventionally known methods. Be prepared. For example, the above components are charged simultaneously or sequentially, for example, into a Henschel mixer, a V-type blender, a tumbler mixer, a ribbon blender, etc. and mixed, and then a single-screw extruder, a multi-screw extruder, a kneader, It is obtained by melt-kneading with a bumper mixer.

Among these, when equipment having excellent kneading performance such as a multi-screw extruder, a kneader, and a Banbury mixer is used, a high-quality polymer composition in which each component is more uniformly dispersed can be obtained.

In addition, at any of these stages, the above additives, for example, an anti-oxidation agent, can be added as necessary.

Molded body

The molded article according to the present invention is obtained by using the polymer composition according to the present invention obtained as described above, using a conventionally known melt molding method, for example, extrusion molding, rotational molding, calendar molding, injection molding, compression molding. It can be formed into various shapes by methods such as molding, transfer molding, powder molding, blow molding, and vacuum molding.

When the polymer composition according to the present invention is used for an electric wire sheath and an electric wire covering, the molded article according to the present invention is an electric wire sheath and a z or coating layer, and the electric sheath and the coating layer are: It is formed around the electric wire by a conventionally known method, for example, an extrusion method. 【Example】

Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples. The physical properties of the ethylene 'α-olefin copolymer (Α1-1) were evaluated as follows.

[density]

The strand after MFR measurement at 190 ° C and a load of 2.16 kg was heat-treated at 120 ° C for 1 hour, gradually cooled to room temperature over 1 hour, and measured by density gradient tube method. Was.

[α-olefin content, Τ α / Τ α α, Β value]

13C—determined by NMR spectrum. [Intrinsic viscosity [77]]

1 Measured in decalin at 35 ° C.

[Mw / Mn]

Using GPC (gel permeation chromatography) with o-dichlorobenzene solvent 140. Measured at C.

[MFR10 / MFR2]

Based on ASTM D-1238, MFR10 under a load of 1 Okg at 190 ° C and MFR2 under a load of 2.16: kg were measured, and the ratio was calculated. When this ratio is large, it indicates that the polymer has excellent fluidity during melting, that is, the workability is high.

Preparation and evaluation of a sample of the insulated wire were performed by the following method. Creation of insulated wires

The polymer composition of the present invention was extruded using a melt extruder (Toyo Seiki Ne-ring, product name Labo Plast Mill) equipped with a wire coating die, die temperature: 220 ° C, screw rotation: 30 rpm, and extrusion. Amount: 1.6 to 1.8 kg / h, an insulated wire with a finished diameter of 3.0 mm covered with a 0.8 mm thick polymer composition around a 7-strand conductor (outer diameter: 1.35 mm) of soft copper wire with a strand diameter of 0.45 mm Obtain a sample. The flame resistance of the insulation coating of the obtained insulated wire sample is evaluated by the following method. That is, as shown in FIG. 1, a 17-inch long insulated wire 1 as a sample is placed in one chamber (not shown) of the test apparatus. The angle between the bottom surface and the insulated wire 1 is Θ (flame retardancy test angle).

Next, the burner 2 placed in front of the insulated wire 1 is ignited, and the flame is brought into contact with the flame at an angle of Ί 0 ° at a position 3 inches above the lower end of the insulated wire 1 and the ignition is confirmed. After continuing the indirect flame for 2 seconds, gently remove the flame and check for self-extinguishing.

Perform the above test three times, and the self-extinguishing fire at each test shall be regarded as passing the Θ inclination test. Passing A larger value of 0 indicates higher flame retardancy. Then, A (the equivalent to the left side of Equations (1) and (2)) that has the largest inclination angle among the 0s that pass is defined as I do.

A is 0 degree or more and 90 degrees or less.

Next, the right side of equation (1) will be described.

σ is the torsional stiffness of a 2 mm thick sheet made of the thermoplastic resin composition at 23 ° C.

Torsional rigidity

A sheet of the same thermoplastic resin composition as used in the flame retardancy test was used at a temperature of 23 according to JIS K6745 using a Crashberg type flexibility tester manufactured by Toyo Seiki Co., Ltd. The torsional stiffness of C was measured.

[Preparation of ethylene / 1-butene copolymer]

[Production example]

[Preparation of catalyst solution]

Triphenylcarbamate (tetrakispentafluorophenel)

18.4 mg of toluene was added and dissolved in 5 ml of toluene to prepare a toluene solution having a concentration of 0.004πιΜΖm 1. [Dimethyl (t-butylamide) (tetramethyl-7] 5-cyclopentagenenyl) silane] Take 1.8 mg of titanium dichloride, add 5 ml of toluene and dissolve, and adjust the concentration to 0.001 mM / m A toluene solution of 1 was prepared. At the beginning of the polymerization, 0.38 ml of a toluene solution of triphenylcarbenyl (tetrakispentaphenylenophenyl) porate, [dimethyl (t-butylamide) (tetramethyl-η5-cyclopentagenenyl) silane] 0.38 ml of a toluene solution of titanium dichloride is taken, and 4.24 ml of toluene for dilution is further added, so that tri-carbaldehyde (tetrakispentafluorophenyl) borate is reduced to 0.002 mM, L in terms of B, [ Dimethyl (t-butylamide) (tetramethyl-775-cyclopentapentaenyl) silane] titanium solution was prepared in an amount of 0.0005 mM / L in terms of Ti in a toluene solution of 5 ml.

[Preparation of ethylene / 1-butene copolymer A-1]

75 Oml of heptane was inserted at 23 ° C into a SUS autoclave with a stirring wing of 1.5 liters which had been sufficiently purged with nitrogen. The stirring blade was turned into this autoclave, and 10 g of 1-butene and 120 ml of hydrogen were introduced while cooling with ice. Next The lave was heated to 100 ° C. and further pressurized with ethylene to a total pressure of 6 KG. When the internal pressure of the autoclave reached 6 KG, 1,0 ml of a 1.0 mM / m 1 hexane solution of triisobutyralmium (TIBA) was injected with nitrogen. Subsequently, 5 ml of the catalyst solution prepared as described above was injected into an autoclave with nitrogen to initiate polymerization. Thereafter, the temperature of the autoclave was adjusted to 100 ° C. for 5 minutes, and ethylene was directly supplied so that the pressure became 6 kg. Five minutes after the start of the polymerization, 5 ml of methanol was inserted into the autoclave with a pump to stop the polymerization, and the autoclave was depressurized to atmospheric pressure. Three liters of methanol was poured into the reaction solution with stirring. The obtained polymer containing a solvent was dried at 130 ° C. for 13 hours at 600 torr to obtain 10 g of an ethylene / butene copolymer A-1. Table 1 shows the properties of the obtained ethylene / 1-butene copolymer.

(Examples:! ~ 3, Comparative Examples 1-1-1 ~ 3-2)

Examples 1 to 3 used the ethylene / 1-butene copolymer A-1 produced by the above-mentioned production method as the thermoplastic resin, and Comparative Examples 1-1, 2-1 and 3-1 used ethylene as the thermoplastic resin. Comparative Example 1-2, 2-Ethyl acrylate copolymer (Mitsui 'Dupont Polychemical Co., Ltd .; hM, trade name: EVA LEX-EEA' A-710, hereinafter abbreviated as E EA) 2, 3-2 are ethylene monoacetate butyl copolymer (Mitsui DuPont Polychemical Co., Ltd.) EVAFLEX · EV 360, abbreviated as EVA. ), Magnesium hydroxide as a metal hydroxide, metaprene A-300C as a fluorine compound, manufactured by Mitsubishi Rayon Co., Ltd., and a silicone resin: Z-6018 (manufactured by Dow Corning Toray) as listed in Table 1. %, And the mixture was melt-kneaded and granulated at a resin temperature of 190 ° C. using a bread pallet mixer to obtain pellets of a thermoplastic resin composition. Using this thermoplastic resin composition, A and σ were calculated by the method described above, and it was determined whether or not the expressions (1) and (2) were satisfied. Table 2 shows the results. Further, the relationship between the torsional rigidity (σ) of the thermoplastic resin composition shown in Table 2 and Α (the maximum angle at which the flame retardant test passed) was plotted in FIG. Table 2

O indicates that the equation is satisfied, and X indicates that it is not.

Industrial applicability

When the polymer composition according to the present invention is used for an electric wire sheath and an electric wire coating, the molded article according to the present invention is an electric wire sheath and / or a coating layer, and the electric wire sheath and the coating layer are conventionally known. For example, it is formed around the electric wire by an extrusion method.

According to the present invention, it is possible to provide a thermoplastic resin composition having a high degree of flame retardancy and being flexible, and a molded article thereof.

Since the thermoplastic resin composition according to the present invention has the above-described effects, it is suitable for use in various molded articles, for example, wire coating, tape, film, flame-retardant sheet, pipe, blow-molded article, flame-retardant wallpaper, and the like. It is particularly suitable for use in wire sheathing and wire coating.

Claims

The scope of the claims

1. A thermoplastic resin composition comprising the following (A) to (C).

(A) and ethylene · alpha-O olefin copolymer 20 composed of a number 3 to 0 of the alpha-Orefuin carbon 64.9 wt ^_0/0

(Iii) 35-70% by weight of metal hydroxide;

(C) Fluorine compound 0.1 to 10% by weight

2. A thermoplastic resin composition comprising the following (i) to (c) forces.

(Α) Ethylene comprising the following ethylene polymers (Α-1) and (Α-2) in a weight ratio of (Α-1) / (Α-2) = 20/8 0 ~ 100/0 system copolymer composition from 20 to 64.9 weight ⁰ main ₀

(A-1): Ethylene. Olefin copolymer consisting of ethylene and α-olefin having 3 to 10 carbon atoms

(Α-2): Ethylene copolymer other than (Α-1)

(Iii) 35-70% by weight of metal hydroxide;

(C) Fluorine compound 0.1 to 10% by weight

3. The ethylene α-olefin copolymer (Α) or (Α-1) ヽ

(i) the density (ASTM D1505, 23 ° C) is in the range of 0.855 to 0.910 g / cm3,

(ii) Melt flow rate (MFR2) at 1.90 ° C and 2.16 kg load (ASTM D1238, load 2.16 kg, 190 ° C) is in the range of 0.1 to 100 gZl O,

(iii) The thermoplastic resin composition according to any one of claims 1 to 2, wherein Mw / Mn is in the range of 1.5 to 3.5, as measured by the GPC method.

4. The ethylene-olefin copolymer (A) or (A-1) force

(i) The density (ASTM D1505, 23 ° C) is in the range of 0.857 to 0,890 g / cm3,

(ii) Melt flow rate (MF R2) at 190 ° C and 2.16 kg load (ASTMD1238, load 2.16 kg, 190 ° C) Force S 0

(iii) Index of molecular weight distribution evaluated by GPC method: Mw / Mn is in the range of 1.5 to 3.5,

(iv) l90. C, ratio of melt flow rate (MFR10) at 10 kg load to melt flow rate (MFR2) at 190 ° C and 2.16 kg load: MFR10 / M

F R2 satisfies the following relationship,

MFR10 / MFR2 ≥ 5.7

Mw / Mn + 4.7 ≤ MFR10 / MFR2

(V) the intensity ratio of Τα to T aa in the 13C-NMR spectrum (Ταβ / Τac) is 0.5 or less;

(vi) The 13C-NMR spectrum of the thermoplastic resin composition according to claim 3, wherein the B value obtained from the following formula is 0.9 to: 1,5.

B it = [POE] / (2 · [PE] [PO])

(Where [PE] is the mole fraction of the structural unit derived from ethylene in the copolymer, and [PO] is the mole fraction of the structural unit derived from α-olefin in the copolymer. ([ΡΟΕ] is the ratio of the number of ethylene-α-olefin chains to the total dyad chains in the copolymer.)

5. A molded article comprising the thermoplastic resin composition according to any one of claims 1 to 4.

6. A molded article according to claim 5, wherein the molded article is an insulator and / or a sheath of an electric wire.