JP5092912B2 - Non-halogen flame retardant thermoplastic elastomer resin composition, method for producing the same, and electric wire / cable using the same - Google Patents

Description

  The present invention relates to a non-halogen flame retardant thermoplastic elastomer resin composition that uses a dynamic crosslinking technique to form a dispersed phase in an olefinic resin matrix, and in particular, by using silane crosslinked EEA as the dispersed phase, The present invention relates to a non-halogen flame-retardant thermoplastic elastomer resin composition that can be extruded at high speed even when highly filled with a flame retardant and exhibits good elongation, a method for producing the same, and an electric wire / cable using the same.

  The awareness of environmental issues is increasing worldwide, and thermoplastic elastomer resins that do not generate harmful gases during combustion and that can be recycled are becoming widespread.

  Various thermoplastic elastomers have been developed so far. For example, as shown in Patent Document 1, by using a dynamic crosslinking technique, a fluid component olefin resin is used as a matrix, and the matrix is contained in the matrix. There is a technique for dispersing olefin rubber.

  Generally, non-halogen highly flame-retardant thermoplastic resins used for insulating materials for electric wires and cables need to be highly filled with metal hydroxides such as aluminum hydroxide and magnesium hydroxide.

JP-A-11-228750

  However, the flame retardant thermoplastic elastomer resin highly filled with metal hydroxide has poor melt flowability, and therefore high torque is applied during extrusion processing, making high-speed extrusion difficult. Not only that, the elongation decreases significantly. In applications where heat resistance is required, such as for electric wires for equipment, the heat deformation resistance, cut-through resistance, and the like are improved by crosslinking with an electron beam.

  Accordingly, an object of the present invention is to solve the above-mentioned problems and use silane-crosslinked EEA as a dispersed phase when forming a dispersed phase in an olefin resin matrix using a dynamic crosslinking technique. Non-halogen flame retardant thermoplastic elastomer resin composition having high mechanical strength and heat resistance without cross-linking, being capable of high-speed extrusion even when highly filled with a flame retardant, and exhibiting good elongation, and a method for producing the same We provide electric wires and cables using this.

In order to achieve the above object, the invention of claim 1 is based on (A) an ethylene-ethyl acrylate copolymer (hereinafter referred to as EEA) having an ethyl acrylate content of 15 mass% or more and an MFR value of 0.8 g / 10 min or more. 30 to 80 parts by weight, (B) 20 to 70 parts by weight of a thermoplastic polyolefin resin, (C) 50 to 300 parts by weight of a non-halogen flame retardant with respect to a total of 100 parts by weight of (A) and (B) , And a silanol condensation catalyst , wherein the EEA is silane-crosslinked, and the phase of the component (A) is dispersed in the phase of the component (B). It is a thing.

The invention according to claim 2 is the non-halogen flame retardant thermoplastic elastomer resin composition according to claim 1, wherein the component (C) is a metal hydroxide.

Invention of Claim 3 is (A) 30-80 weight part of ethylene-ethyl acrylate copolymer ( EEA ) whose ethyl acrylate content is 15 mass% or more and MFR value is 0.8 g / 10min or more, (B) 20 to 70 parts by weight of a plastic polyolefin resin and (C) a non-halogen flame retardant thermoplastic elastomer resin containing 50 to 300 parts by weight of a non-halogen flame retardant based on a total of 100 parts by weight of (A) and (B) In producing the composition, EEA is obtained by graft copolymerizing a silane compound with EEA and then graft copolymerizing the silane compound, (B) a thermoplastic polyolefin resin, (C) a non-halogen flame retardant and a silanol condensation catalyst. the kneaded, the component (a), the uncrosslinked EEA, a silane compound is a silane crosslinked by copolymerizing the A) component of the phase is a manufacturing method of the (B) non-halogen flame retardant thermoplastic elastomer resin composition characterized in that it dispersed phase in the component.

The invention according to claim 4 is an electric wire characterized by using the non-halogen flame retardant thermoplastic elastomer resin composition according to claim 1 or 2 as an insulator.

The invention according to claim 5 is a cable characterized by using the non-halogen flame-retardant thermoplastic elastomer resin composition according to claim 1 or 2 as a sheath.

  According to the present invention, it is possible to provide a non-halogen flame retardant thermoplastic elastomer resin composition capable of high-speed extrusion in a highly filled flame retardant system and capable of obtaining good elongation.

  A preferred embodiment of the present invention will be described below in detail with reference to the accompanying drawings.

  First, an electric wire / cable to which the halogen-free flame retardant thermoplastic elastomer resin composition of the present invention is applied will be described with reference to FIGS.

  FIG. 1 shows an electric wire 10 in which a copper conductor 1 is coated with an insulator 2 made of a halogen-free flame retardant thermoplastic elastomer resin composition.

  FIG. 2 shows a cable 20 in which three wires 10 shown in FIG. 1 are twisted and the outer periphery thereof is covered with a sheath 3 made of a non-halogen flame-retardant thermoplastic elastomer resin composition.

  3 shows a core 6 formed by twisting a plurality of wires 10 (four in the figure) shown in FIG. The cable 30 which coat | covered the sheath 7 which consists of a flammable thermoplastic elastomer resin composition is shown.

  The insulator 2 and the sheaths 3 and 7 made of the non-halogen flame retardant thermoplastic elastomer resin composition shown in FIGS. 1 to 3 are coated by extrusion molding.

  This non-halogen flame retardant thermoplastic elastomer resin composition of the present invention comprises (A) an ethylene-ethyl acrylate copolymer (EEA) having an EA content of 15 mass% or more and an MFR value of 0.8 g / 10 min or more. 80 parts by weight, (B) 20 to 70 parts by weight of thermoplastic polyolefin resin, (C) a non-halogen flame retardant containing 50 to 300 parts by weight with respect to a total of 100 parts by weight of (A) and (B), EEA Are silane cross-linked.

  The component (A) is a resin composition obtained by copolymerizing a silane compound for silane crosslinking.

  The component (A) EEA is crosslinked and dispersed by dynamic crosslinking in the component (B) of the thermoplastic polyolefin resin.

  As the EEA of the component (A), when the EA content is less than 15 mass%, excellent flame retardancy cannot be obtained. When the MFR value is less than 0.8 g / 10 min, the melt flowability is poor, and the appearance when extrusion molding or the like is deteriorated. When the component (A) is less than 30 parts by weight, sufficient crosslinking cannot be obtained and the heat resistance is poor. Moreover, when more than 80 weight part, melt flowability is bad and the external appearance at the time of extrusion molding etc. deteriorates.

  Furthermore, when the component (C) is less than 50 parts by weight relative to the total of 100 parts by weight of (A) and (B), excellent flame retardancy cannot be obtained, while if it exceeds 300 parts by weight, the machine The mechanical strength is significantly reduced.

  In this way, the present invention uses non-halogen capable of high-speed extrusion with good flowability even when highly filled with a flame retardant, by using EEA as a material for forming a dispersed phase in an olefin matrix using dynamic crosslinking technology. A flame retardant thermoplastic elastomer resin composition can be obtained.

  That is, firstly, in the present invention, a flame retardant such as a metal hydroxide is mainly distributed in a dispersed phase (crosslinked EEA) formed by dynamic crosslinking, and other than the dispersed phase (island phase). In addition to preventing deterioration of mechanical properties due to metal hydroxide in the sea phase (thermoplastic polyolefin-based resin) of the seawater, it is possible to disperse foreign substances (flame retardants such as metal hydroxide) in the resin that cause a decrease in fluidity. By confining to (island phase), fluidity in the sea phase can be secured and good extrudability can be obtained.

  Secondly, in EEA, since the amount of silane grafted is small compared to other ethylene copolymers, crosslinking is suppressed to some extent, and sufficient crosslinking effect is obtained to obtain heat resistance. Meanwhile, it is possible to prevent the extrudability from being lowered due to the crosslinked product.

  For the first and second reasons described above, in the present invention, a non-halogen flame-retardant thermoplastic elastomer resin composition that can be extruded at high speed and at high speed can be obtained.

  In the present invention, the reason for selecting silane cross-linking is that there is a problem of off-flavor associated with the generation of sulfur-based gas in the cross-linking with sulfur and a problem that it is difficult to freely set the hue of the molded product for coloring. In the case of cross-linking with peroxide, the polyolefin resin, which is a fluid component, is simultaneously cross-linked, so it is necessary to select a resin that is difficult to cross-link as the polyolefin-based resin, and there is a problem that only polypropylene that is substantially hard can be selected. Because there is.

  The silane compound is required to have both a group capable of reacting with a polymer and an alkoxy group that forms a crosslink by silanol condensation. Specifically, vinyltrimethoxysilane, vinyltriethoxylane, vinyltris (β -Methoxyethoxy) silane and other vinylsilane compounds, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-β- (aminoethyl) γ-aminopropyltrimethoxysilane, β- (aminoethyl) γ- Aminosilane compounds such as aminopropylmethyldimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, β- (3,4 epoxy cyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycid Xylpropylmethyldiethoxysilane Epoxy silane compounds such as γ-methacryloxypropyltrimethoxysilane, and other polysilane silane compounds such as bis (3-methacryloxysilyl) propyl) disulfide and bis (3- (triethoxysilyl) propyl) tetrasulfide And mercaptosilane compounds such as 3-mercaptopropyltrimethoxysilane and 3-mercaptopropyltriethoxysilane.

  In order to copolymerize the silane compound, a method of melt kneading a predetermined amount of the silane compound and a free radical generator in the base EEA can be used.

  As the free radical generator, organic peroxides such as dicumyl peroxide can be mainly used. The addition amount of the silane compound is not particularly limited, but is preferably 0.5 to 10.0 parts by weight with respect to 100 parts by weight of EEA in order to obtain good physical properties. When the amount is less than 0.5 part by weight, a sufficient crosslinking effect cannot be obtained, and the strength and heat resistance of the composition are inferior. If it exceeds 10.0 parts by weight, the workability is remarkably lowered.

  The optimum amount of the organic peroxide that is a free radical generator is 0.001 to 3.0 parts by weight with respect to 100 parts by weight of EEA. When the amount is less than 0.001 part by weight, the silane compound is not sufficiently copolymerized and a sufficient crosslinking effect cannot be obtained. When the amount exceeds 3.0 parts by weight, EEA scorch tends to occur.

  As the metal oxide as the component (C), magnesium hydroxide is most excellent in flame retardancy, but aluminum hydroxide, calcium hydroxide, or the like may be used. In addition, these metal hydroxides may be used which are surface-treated with a silane coupling agent, a titanate coupling agent, a fatty acid such as stearic acid or calcium stearate, or a fatty acid metal salt.

  (B) Known thermoplastic polyolefin resins can be used, particularly polypropylene, high density polyethylene, straight-chain low density polyethylene, ultra low density polyethylene, ethylene-butene-1 copolymer, ethylene-hexene-1. It contains at least one selected from a copolymer, an ethylene-octene-1 copolymer, an ethylene-vinyl acetate copolymer, and an ethylene-ethyl acrylate copolymer, and is used alone or in combination of two or more. Is desirable.

Further, when kneading the silane-crosslinked component (A), the component (B) and the component (C) for dynamic crosslinking, it is preferable to add a kneaded silanol condensation catalyst such as dibutyltin laurate in advance to EVA.

The material is a process of graft copolymerizing a silane compound with EEA, and a compounding agent of EEA grafted with silane compound, thermoplastic polyolefin resin, metal hydroxide, silanol condensation catalyst ( dibutyltin laurylate ). , EEA was prepared by the step of cross-linking silane.

  In the step of graft-copolymerizing the silane compound with EEA, a material in which raw materials EEA, vinyltrimethoxysilane, and dicumyl peroxide are impregnated and mixed in the ratio of component (A) shown in Tables 1 and 2 is prepared. Extrusion was conducted with a 40 mm extruder (L / D = 24) at 200 ° C. so that the residence time was about 5 minutes, and a graft reaction was carried out.

  Next, each component of the formulation shown in each example of Table 1 was kneaded by batch feeding into a 40 mm twin screw extruder (L / D = 60), and EEA in which a silane compound was graft copolymerized during kneading. A kneaded product was prepared by dynamically cross-linking.

  The temperature was 180 ° C. and the screw rotation speed was 100 rpm. This was pelletized and used as a material for cable production.

  The cable was produced by using a 40 mm extruder (L / D = 24) preheated to 180 ° C. and extrusion covering the cable core with a thickness of 0.41 mm.

  Mechanical strength, heat resistance, and flame retardancy were evaluated according to JISC3005. A tensile strength of 10 MPa or more and an elongation at break of 150% or more were regarded as acceptable. The heat resistance was evaluated by a heat deformation test (conditions of 75 ° C. and a load of 10 N), and a reduction rate of 10% or less with respect to the coating thickness (0.41 mm in the example) was accepted.

  For the flame retardancy evaluation, a 60-degree inclined combustion test was performed, the fire spread time after removing the flame was measured, and the fire extinguisher within 60 seconds was regarded as acceptable.

  Moreover, in order to confirm the presence or absence of silane crosslinking, the material was extracted in hot xylene at 110 ° C. for 24 hours. If there was a residual insoluble polymer, it was determined that crosslinking was introduced. Extrusion processability was confirmed by visual inspection of the appearance at the time of extrusion molding, and judged to be “good” if smooth and “bad” if uneven.

Example 1
A-703 (manufactured by Mitsui DuPont Chemical Co., MFR = 5 g / 10 min, EA = 25%) as EEA, S210 (manufactured by Chisso) as vinyltrimethoxysilane, DCP (manufactured by NOF Corporation, half-life temperature: 179) 1 minute) at a ratio of 60 / 1.2 / 0.006 parts by weight with the above kneading method, and then the component (A) is mixed with the component (B), the component (C), and the catalyst. It knead | mixed with the mixing | blending shown in Table 1, and evaluated.

  As a result, good results were obtained in all evaluations.

Example 2
A-703 (EEA), S210, and DCP were grafted by the above kneading method at a ratio of 80 / 1.6 / 0.008 parts by weight, and then kneaded and evaluated according to the formulation shown in Table 1.

  As a result, good results were obtained in all evaluations.

Example 3
A1150 (manufactured by Nippon Polyethylene, MFR = 0.8 g / 10 min, EA = 15%) was used as EEA, and S210 and DCP were subjected to a graft reaction by the above kneading method at a ratio of 80 / 1.6 / 0.008 parts by weight. These were kneaded with the formulation shown in Table 1 and evaluated.

  As a result, good results were obtained in all evaluations.

Example 4
A-703 (EEA), S210, and DCP were graft-reacted by the above kneading method at a ratio of 30 / 0.6 / 0.003 parts by weight, and then kneaded with the formulation shown in Table 1 and evaluated.

  As a result, good results were obtained in all evaluations.

Example 5
A-703 (EEA), S210, and DCP were grafted by the above kneading method at a ratio of 80 / 1.6 / 0.008 parts by weight, and then kneaded and evaluated according to the formulation shown in Table 1.

  As a result, good results were obtained in all evaluations.

Example 6
A-703 (EEA), S210, and DCP were grafted by the above kneading method at a ratio of 80 / 1.6 / 0.008 parts by weight, and then kneaded and evaluated according to the formulation shown in Table 1.

  As a result, good results were obtained in all evaluations.

Example 7
A-703 (EEA), S210, and DCP were grafted by the above kneading method at a ratio of 80 / 0.4 / 0.008 parts by weight, and then kneaded and evaluated according to the formulation shown in Table 1.

  As a result, good results were obtained in all evaluations.

Example 8
A-703 (EEA), S210, and DCP were grafted by the above kneading method at a ratio of 80/8 / 2.4 parts by weight, and then kneaded with the formulation shown in Table 1 and evaluated.

  As a result, good results were obtained in all evaluations.

Comparative Example 1
MFR = 5 g / 10 min, EA = 25% of EEA (A-703), vinyltrimethoxysilane (S210), dicumyl peroxide (DCP) at a ratio of 90 / 1.8 / 0.009 parts by weight After the graft reaction by the kneading method, the mixture shown in Table 2 was kneaded and evaluated.

  In Comparative Example 1, since the component (В) was small (10 parts by weight) compared to Example 2, the tensile strength, elongation, presence / absence of crosslinking, heat resistance, and flame retardancy were good. The surface of the extruded product was rough and judged to be defective.

Comparative Example 2
MFR = 5 g / 10 min, EA = 25% EEA (A-703), vinyltrimethoxysilane, dicumyl peroxide were grafted by the above kneading method at a ratio of 20 / 0.4 / 0.002 parts by weight. These were kneaded with the formulation shown in Table 2 and evaluated.

  In Comparative Example 2, since there were more (В) components (80 parts by weight) than Example 4, the tensile strength, elongation, flame retardancy, and extrusion processability were good, but there was no crosslinking. As a result, no residual polymer was confirmed. Therefore, the heat resistance heat deformation test was also judged to be defective because the reduction rate was less than 10%.

Comparative Example 3
MFR = 5 g / 10 min, EA = 9% EEA, vinyltrimethoxysilane, dicumyl peroxide were grafted by the above kneading method at a ratio of 80 / 1.6 / 0.008 parts by weight, and shown in Table 2. The kneading was conducted and evaluated.

  In Comparative Example 3, the EA content of EEA was low (9%). As a result, the tensile strength, elongation, and extrudability were good, but 60 seconds or more passed in the flame retardancy evaluation. Even if it did not extinguish spontaneously, it was judged as unacceptable.

Comparative Example 4
MFR = 0.5 g / 10 min, EA = 15% EEA, vinyltrimethoxysilane and dicumyl peroxide were grafted by the above kneading method at a ratio of 80 / 1.6 / 0.008 parts by weight, and Table 2 Kneading was carried out with the formulation shown in Fig. 1 and evaluated.

  In Comparative Example 4, since the MFR was 0.5 g / 10 min, the tensile strength, the presence / absence of crosslinking, heat resistance, and flame retardance were good, but the torque during extrusion processing was 1 to It was higher than 8, and the appearance was also judged as poor because the melt flow was conspicuous.

Comparative Example 5
MFR = 5 g / 10 min, EA = 25% EEA, vinyltrimethoxysilane, dicumyl peroxide were grafted by the above kneading method at a ratio of 80 / 1.6 / 0.008 parts by weight, and shown in Table 2. The kneading was conducted and evaluated.

  In Comparative Example 5, the amount of magnesium hydroxide filled was larger than that in Example 5 (450 parts by weight), so the elongation was less than 150% and the surface of the extruded product was rough. Judged.

Comparative Example 6
MFR = 5 g / 10 min, EA = 25% EEA, vinyltrimethoxysilane, dicumyl peroxide were grafted by the above kneading method at a ratio of 80 / 1.6 / 0.008 parts by weight, and shown in Table 2. The kneading was conducted and evaluated.

  In this comparative example 6, since the filling amount of magnesium hydroxide is smaller (40 parts by weight) than in example 4, in the flame retardancy evaluation, even if 60 seconds or more have passed, the fire does not spontaneously extinguish and it is determined as rejected. did.

Comparative Example 7
MFR = 30 g / 10 min, VA = 42% EVA, vinyltrimethoxysilane, dicumyl peroxide were grafted by the above kneading method at a ratio of 80 / 1.6 / 0.008 parts by weight, and shown in Table 2. The kneading was conducted and evaluated.

  In Comparative Example 7, since EVA was used, the torque during extrusion was higher than in Examples 2 and 3, and the melt flow was conspicuous in appearance, so that the extrusion processability was judged to be poor.

Comparative Example 8
MFR = 0.37 g / 10 min of HDPE, vinyltrimethoxysilane, and dicumyl peroxide were grafted at a ratio of 80 / 1.6 / 0.008 parts by weight by the above kneading method, and the formulation shown in Table 2 was used. Kneaded and evaluated.

  In Comparative Example 8, since HDPE was used, no crosslinked residual polymer could be confirmed. Moreover, as a flame retardant evaluation, even if 60 seconds or more passed, it did not extinguish spontaneously. Furthermore, the surface of the extruded product was rough and judged to be defective.

  From the above, using a dynamic cross-linking technique, when the flame retardant is highly charged without using EEA as the dispersed phase in the olefin-based resin matrix, the extrusion torque becomes high, high-speed extrusion becomes difficult, and elongation increases. It drops significantly. Therefore, in order to improve the extrudability and elongation, the dispersed phase needs to be EEA.

  Further, the EEA of the component (A) and the component (В) are preferably in the range of 80/20 to 20/80, and the flame retardant of the component (C) is 100 parts by weight in total of (A) and (B). On the other hand, it was found that addition of 50 to 300 parts by weight has flame retardancy and good extrudability.

It is a detailed sectional view of an electric wire to which the present invention is applied. It is a detailed sectional view of a cable to which the present invention is applied. It is a detailed sectional view of a cable to which the present invention is applied.

Explanation of symbols

1 Copper conductor 2 Insulator 3, 7 Sheath 10 Electric wire 20, 30 Cable

Claims (5)

(A) 30-80 parts by weight of an ethylene-ethyl acrylate copolymer (hereinafter referred to as EEA) having an ethyl acrylate content of 15 mass% or more and an MFR value of 0.8 g / 10 min or more, and (B) a thermoplastic polyolefin resin. 20 to 70 parts by weight, (C) a non-halogen flame retardant containing 50 to 300 parts by weight and a silanol condensation catalyst with respect to a total of 100 parts by weight of (A) and (B) , and the EEA is silane-crosslinked The non-halogen flame retardant thermoplastic elastomer resin composition , wherein the phase of the component (A) is dispersed in the phase of the component (B) .   The non-halogen flame retardant thermoplastic elastomer resin composition according to claim 1, wherein the component (C) is a metal hydroxide. (A) 30-80 parts by weight of ethylene-ethyl acrylate copolymer (EEA) having an ethyl acrylate content of 15 mass% or more and an MFR value of 0.8 g / 10 min or more, and (B) 20-70 thermoplastic polyolefin resin. In producing a non-halogen flame retardant thermoplastic elastomer resin composition containing 50 parts by weight of (C) a non-halogen flame retardant with respect to a total of 100 parts by weight of (A) and (B), After graft copolymerizing a silane compound with EEA, kneading EEA graft-copolymerized with the silane compound, (B) a thermoplastic polyolefin resin, (C) a non-halogen flame retardant and a silanol condensation catalyst, ) Component is silane-crosslinked by copolymerizing a non-crosslinked EEA with a silane compound, and the phase of the component (A) is (B) The manufacturing method of the halogen-free flame-retardant thermoplastic elastomer resin composition characterized by disperse | distributing in the phase of a component . An electric wire comprising the non-halogen flame retardant thermoplastic elastomer resin composition according to claim 1 or 2 as an insulator. A cable comprising the non-halogen flame-retardant thermoplastic elastomer resin composition according to claim 1 or 2 as a sheath.

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