JP3829646B2 - Non-halogen flame retardant insulated wire with excellent wire strip properties - Google Patents

Description

【００４３】
表１から判るように脂肪酸アマイドが配合されていない従来のノンハロゲン難燃絶縁電線である比較例１及び比較例２のノンハロゲン難燃絶縁電線は、難燃性試験であるＵＬ ｓｕｂｊｅｃｔ ７５８に準拠した垂直燃焼試験（ＶＷ−１）に合格すると共に引張強度や伸びも良好であるが、その半面ワイヤストリップ性を示す密着力が４３Ｎと大きく、それによってワイヤストリップ性が劣る。
【００４４】
脂肪酸アマイドの配合量を本発明の規定以上に配合した比較例３のノンハロゲン難燃絶縁電線は、混練作業が円滑にできなく、その結果特性試験が不可能であった。
【００４５】
また、オルガノポリシロキサンを本発明の規定以上に配合した比較例４のノンハロゲン難燃絶縁電線も、混練作業が円滑にできなく、その結果特性試験が不可能であった。
【００４６】
水酸化アルミニウムを本発明の規定以下しか配合しなかった比較例５のノンハロゲン難燃絶縁電線は難燃性試験であるＵＬ ｓｕｂｊｅｃｔ ７５８に準拠した垂直燃焼試験（ＶＷ−１）に不合格となった。
【００４７】
水酸化アルミニウムを本発明の規定以上に配合した比較例６のノンハロゲン難燃絶縁電線は難燃性試験であるＵＬ ｓｕｂｊｅｃｔ ７５８に準拠した垂直燃焼試験（ＶＷ−１）に合格するが、機械的特性である引張強度と伸びとが最も低い値であった。
【００４８】
これらに対して実施例１〜６のノンハロゲン難燃絶縁電線は、難燃性試験であるＵＬ ｓｕｂｊｅｃｔ ７５８に準拠した垂直燃焼試験（ＶＷ−１）に合格すると共に引張強度や伸びも良好で、しかもワイヤストリップ性を示す密着力が１１Ｎ以下と小さく、それによって優れたワイヤストリップ性を発揮した。
【００４９】
【発明の効果】
本発明のノンハロゲン難燃絶縁電線は難燃性試験であるＵＬ ｓｕｂｊｅｃｔ７５８に準拠した垂直燃焼試験（ＶＷ−１）に合格すると共に引張強度や伸びも良好で、しかも優れたワイヤストリップ性を発揮するものであり、工業上有用である。
【図面の簡単な説明】
【図１】ノンハロゲン難燃絶縁電線のワイヤストリップ性試験方法を示した斜視説明図である。
【符号の説明】
１ ノンハロゲン難燃絶縁電線
２ 銅線撚線導体
３ 金属治具板[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a non-halogen flame retardant insulated electric wire excellent in wire strip properties.
[0002]
[Prior art]
In general, an insulated wire used as a lead wire for home appliances and OA equipment is formed by extruding and covering an electrically insulating material on a conducting wire.
[0003]
Conventionally, vinyl chloride resin blends have been most often used as the electrical insulation coating material for the lead wires of these home appliances and OA equipment. The reason for this is considered to be that the vinyl chloride resin blend is inexpensive and has excellent flame retardancy, and also has excellent flexibility, colorability, electrical characteristics, and the like.
[0004]
However, since the vinyl chloride resin blend contains a large amount of chlorine in the vinyl chloride resin molecular skeleton, which is the base polymer, it is a toxic and corrosive gas or smoke such as hydrogen chloride gas or chlorine gas when burned or subjected to high heat. There is a difficulty of generating a large amount. In addition, since this vinyl chloride resin mixture contains a large amount of chlorine in the molecular skeleton of the vinyl chloride resin which is the base polymer, it becomes one of the causes of dioxins when disposed of in landfills.
[0005]
In addition, heavy metal compounds such as lead, plasticizers, etc. are blended in the vinyl chloride resin blend, so the vinyl chloride resin blend insulated wire formed by extruding the vinyl chloride resin blend onto the conductor is disposed of in landfills. There is a concern that soil, groundwater, etc. may be contaminated with heavy metal compounds, plasticizers and the like.
[0006]
Against this background, in recent years, there has been a demand for an environment-friendly insulated wire that does not generate harmful gas during combustion and does not contain harmful heavy metals.
[0007]
[Problems to be solved by the invention]
Conventionally, a base polymer that does not contain halogen elements is used as the base polymer for the environment-friendly insulated wire that does not generate harmful gases during combustion and does not contain harmful heavy metals. In addition, a filler containing no halogen element or toxic heavy metal is added.
[0008]
Here, ethylene polymers such as ethylene / vinyl acetate copolymer and ethylene / ethyl acrylate polymer have been used as the base polymer containing no halogen element.
[0009]
On the other hand, metal hydroxides and the like have been used as fillers that do not contain halogen elements or harmful heavy metals.
[0010]
However, these ethylene / vinyl acetate copolymers and ethylene / ethyl acrylate polymers have polar groups in their molecular skeletons, and therefore have great polarity. For this reason, the non-halogen flame retardant insulating material obtained by blending these polar polymers with a metal hydroxide also has a large polarity. For this reason, it is known that the non-halogen flame retardant insulating material is formed by extruding and coating the non-halogen flame retardant insulating material on the conductive wire, and the adhesion between the non-halogen flame retardant insulating material and the conductive wire is strengthened by the polarity of the polar polymer coated with the extrusion coating. Yes.
[0011]
The strong adhesion between the non-halogen flame retardant insulating material and the conductive wire is advantageous for the electrical characteristics, mechanical characteristics, chemical characteristics, etc. of the non-halogen flame retardant insulated wire. This is inconvenient when the non-halogen flame retardant insulating layer at the end of the electric wire is peeled off from the conductor. In other words, in a non-halogen insulated wire formed by extruding and coating a non-halogen flame retardant insulating material formed by blending a metal hydroxide with an ethylene / vinyl acetate copolymer or ethylene / ethyl acrylate polymer, the end workability, that is, the wire There is a drawback that the strip property is remarkably inferior.
[0012]
The present invention has been made in view of this point, and the object of the present invention is to eliminate the drawbacks of the prior art described above, and to comply with the flame retardant standard UL subject 758 vertical combustion test (VW-1). An object of the present invention is to provide a non-halogen flame-retardant insulated electric wire having excellent flame stripping properties that pass and excellent in wire strip properties that exhibit excellent mechanical properties and wire strip properties.
[0013]
[Means for Solving the Problems]
The gist of the present invention is that 0.1 to 10 parts by mass of a fatty acid amide, 100 parts by mass of an unmodified polyolefin , organopolysiloxane, a copolymer of an organopolysiloxane and a polyolefin, or a blend of both. wire comprising 0.1 to 20 parts by weight of polymer of silicone, characterized in that the non-halogen flame燃絶edges composition the metal hydroxide formed by blending 10 to 300 parts by mass formed by extrusion coating on a conductor from Non-halogen flame retardant insulated wire with excellent strip properties.
[0014]
DETAILED DESCRIPTION OF THE INVENTION
Next, an embodiment of the non-halogen flame retardant insulated electric wire excellent in wire strip property of the present invention will be described.
[0015]
In the present invention, as the polyolefin, ultra-low density polyethylene, linear low density polyethylene, low density polyethylene, medium density polyethylene, high density polyethylene, polypropylene, ethylene / propylene copolymer, ethylene / propylene / dienter polymer, ethylene / methyl acrylate copolymer And ethylene / ethyl acrylate copolymer, ethylene / vinyl acetate copolymer, ethylene / butene copolymer, ethylene / methyl methacrylate copolymer, and ethylene / octene copolymer. These can be used alone or in combination of two or more. In addition, when imparting high flame retardancy such as the VW-1 level of the vertical combustion test based on UL subject 758, which is a flame retardancy test, ethylene / acetic acid has a large endothermic amount due to deacetic acid reaction during thermal decomposition Binirukoporima, it is desirable to use ethylene-acrylic acid Echiruko poly Ma like.
[0016]
As the fatty acid amide in the present invention, lauric acid amide, palmitic acid amide, stearic acid amide, oxystearic acid amide, behenic acid amide, erucyl amide, oleic acid amide, methylol amide, mono-amide of higher fatty acid, methylene bis-stearic acid amide, Methylene bis-oleic acid amide, ethylene bis-stearic acid amide, ethylene bis-lauric acid amide, higher fatty acid bis-amide, stearic oleic acid amide, N-stearic acid / erucamide, N-oleic acid / palmidoamide, composite amide And special fatty acid amides.
[0017]
Further, the blending amount of fatty acid amide per 100 parts by weight polyolefin unmodified in the present invention was defined as 0.1 to 10 parts by mass, no effect of improving the wire strip with a 0.1 parts by mass or less of the formulation, Conversely, when the blending amount is 10 parts by mass or more, the slipperiness becomes too large and the kneading property deteriorates.
[0018]
In the present invention, the silicone is preferably an organopolysiloxane, a copolymer of an organopolysiloxane and a polyolefin, or a blend of both.
[0019]
In the present invention, the organopolysiloxane preferably has a polymerization degree of 3000 or more. This is because when the degree of polymerization is 3000 or less, the viscosity is small, and as a result, slipping occurs in the kneader when kneading with polyolefin, thereby making the kneading operation difficult.
[0020]
Here, the copolymer of organopolysiloxane and polyolefin is a graft of silicone having reactive groups such as vinyl group, methacryl group, carbinol group, mercapto group, phenol group, amino group at one end or both ends of polyolefin. It is what. The silicone content in the copolymer of organopolysiloxane and polyolefin is not particularly specified, but is desirably 20 to 60% by weight.
[0021]
In the present invention, the blending amount of silicone with respect to 100 parts by weight of unmodified polyolefin is defined as 0.1 to 20 parts by weight. When the blending is 0.1 parts by weight or less, there is no effect of improving the wire strip property. This is because if the blending amount is at least part by mass , the slipperiness becomes too great and the kneading property deteriorates.
[0022]
In the present invention, the metal hydroxide is an environment-friendly metal such as aluminum, magnesium, calcium or the like. Specific metal hydroxides include aluminum hydroxide, magnesium hydroxide, calcium hydroxide, Ni solid solution magnesium hydroxide, hydrotalcite and the like. These may be used as they are, or these surfaces may be used after being subjected to a surface treatment using a fatty acid, a fatty acid metal salt, a titanate, a silane coupling agent or the like. These may be used alone or in combination of two or more.
[0023]
The reason the mixing amount of the metal hydroxide with respect to 100 parts by weight polyolefin unmodified in the present invention was defined as 10-300 parts by mass, no effect of improving flame retardancy in the following 10 parts by mass, conversely, 300 parts by mass or more This is because the mechanical characteristics are greatly deteriorated.
[0024]
In the present invention, the non-halogen flame retardant insulating material obtained by blending these materials may be used as it is, or may be crosslinked by irradiation with an electron beam or ultraviolet light. You may chemically cross-link what added the peroxide.
[0025]
Furthermore, the halogen-free flame retardant insulating material obtained by blending these materials in the present invention may contain other compounding agents as necessary, for example, a crosslinking agent, a crosslinking aid, a flame retardant, an antioxidant, a lubricant, a stabilizer, You may mix | blend a filler, a coloring agent, etc.
[0026]
【Example】
Next, an example of the non-halogen flame retardant insulated wire excellent in wire strip property of the present invention will be described together with a comparative example.
[0027]
Initially, the manufacturing method of the halogen-free flame-retardant insulated wire of an Example and a comparative example is demonstrated.
(1) Preparation of Non-Halogen Flame Retardant Insulating Material Composition First, each material of the non-halogen flame retardant insulating material composition was weighed and sampled according to the composition table of Examples and Comparative Examples.
[0028]
Next, each weighed and collected material was put into an 8-inch open roll and kneaded at 100 to 130 ° C.
[0029]
In this kneading operation, the quality of the non-halogen flame retardant insulating material compositions of Examples and Comparative Examples was examined.
(2) Manufacture of non-halogen flame retardant insulated wires Next, the kneaded materials of the examples and comparative examples obtained above were put into 40 mm extruders with L / D = 24, respectively, and copper having a conductor size of 22 AWG at 180 ° C. A wire stranded conductor (7 copper wires having a conductor diameter of φ 0.26 mm) was extruded and coated.
[0030]
Next, the non-crosslinked non-halogen flame retardant insulated electric wire obtained here was irradiated with an electron beam of 10 Mrad by passing through an electron beam irradiating apparatus and crosslinked to obtain non-halogen flame retardant insulated electric wires of Examples and Comparative Examples.
(3) Characteristic test of non-halogen flame retardant insulated wire Next, the non-halogen flame retardant insulated wires of Examples and Comparative Examples obtained here were subjected to the following characteristic test.
[0031]
a. A vertical combustion test (VW-1) was performed in accordance with flame retardancy test UL subject 758.
[0032]
As a result, a sample that self-extinguished within 1 minute passed, and a sample that did not self-extinguish within 1 minute was rejected.
[0033]
b. Tensile property test First, a copper wire stranded wire conductor was pulled out from the non-halogen flame retardant insulated wires of Examples and Comparative Examples.
[0034]
Next, the non-halogen flame retardant insulation coating layer obtained by drawing out the copper wire stranded conductor was subjected to a tensile test at a tensile speed of 200 mm / min in accordance with JIS-C3005.
[0035]
The results showed tensile strength and elongation.
[0036]
c. Wire strip property test First, non-halogen flame-retardant insulated wires of Examples and Comparative Examples having a length of 100 mm were prepared.
[0037]
Next, a non-halogen flame retardant insulation coating layer from the tip to 50 mm was peeled off to prepare a wire strip test piece.
[0038]
Next, the wire strip property test piece thus prepared is set in the wire strip property test apparatus shown in FIG. 1, and then a tensile test is performed at a tensile speed of 200 mm / min in accordance with JIS-C3005 to insulate the conductor. The adhesion (unit: N) with the coating layer was measured.
[0039]
In FIG. 1, 1 is a non-halogen flame retardant insulated wire, 2 is a copper wire stranded wire conductor, and 3 is a metal jig plate.
(Test results)
Table 1 shows the results of these tests.
[0040]
The notes in Table 1 are as follows.
[0041]
(Note 1): Vinyl acetate content: 28%, MI; 1.0
(Note 2) .... Vinyl acetate content: 40%, MI; 0.3
(Note 3) ..... amount of ethyl acrylate; 15%, MI; 0.75
(Note 4) ......... Mercaptobenzimidazole (Note 5) ......... Heidilite H42STV from Showa Denko KK
(Note 6) ... Kisuma 5A from Kyowa Chemical Industry Co., Ltd.
(Note 7) ...... Fine MAG SNT from TMG
(Note 8) …… KE76 of Shin-Etsu Chemical Co., Ltd.
(Note 9) ... Dow Corning Asia's SP-300
(Note 10) …… Nobaret 120UFA from Rin Chemical Industry Co., Ltd.
[0042]
[Table 1]

[0043]
As can be seen from Table 1, the non-halogen flame retardant insulated wires of Comparative Example 1 and Comparative Example 2 which are conventional non-halogen flame retardant insulated wires not containing fatty acid amide are vertical in accordance with UL subject 758, which is a flame retardant test. While passing the combustion test (VW-1) and having good tensile strength and elongation, the adhesive strength showing the half-surface wire strip property is as large as 43 N, thereby inferior the wire strip property.
[0044]
The non-halogen flame retardant insulated wire of Comparative Example 3 in which the blending amount of the fatty acid amide was more than specified in the present invention could not be kneaded smoothly, and as a result, the characteristic test was impossible.
[0045]
Further, the non-halogen flame retardant insulated wire of Comparative Example 4 in which organopolysiloxane was blended more than specified in the present invention could not be kneaded smoothly, and as a result, the characteristic test was impossible.
[0046]
The non-halogen flame retardant insulated wire of Comparative Example 5 in which aluminum hydroxide was blended only below the specification of the present invention failed the vertical combustion test (VW-1) based on UL subject 758, which is a flame retardant test. .
[0047]
The non-halogen flame retardant insulated wire of Comparative Example 6 in which aluminum hydroxide is blended in excess of the specification of the present invention passes the vertical combustion test (VW-1) based on UL subject 758, which is a flame retardant test, but has mechanical properties. The tensile strength and elongation were the lowest values.
[0048]
On the other hand, the non-halogen flame retardant insulated wires of Examples 1 to 6 passed the vertical combustion test (VW-1) based on UL subject 758, which is a flame retardant test, and had good tensile strength and elongation. The adhesive strength showing the wire strip property was as small as 11 N or less, thereby exhibiting excellent wire strip property.
[0049]
【The invention's effect】
The non-halogen flame retardant insulated wire of the present invention passes the vertical flame test (VW-1) based on UL subject 758, which is a flame retardant test, and has excellent tensile strength and elongation, and also exhibits excellent wire strip properties. It is industrially useful.
[Brief description of the drawings]
FIG. 1 is an explanatory perspective view showing a wire strip property test method for a halogen-free flame-retardant insulated wire.
[Explanation of symbols]
1 Non-halogen flame retardant insulated wire 2 Copper wire stranded conductor 3 Metal jig plate

Claims (2)

0.1 to 10 parts by mass of fatty acid amide with respect to 100 parts by mass of unmodified polyolefin, and 0 to 0 of a silicone- based polymer comprising either an organopolysiloxane, a copolymer of organopolysiloxane and polyolefin, or a blend of both 1. A non-halogen flame retardant having excellent wire strip properties, which is formed by extruding and coating a non-halogen flame retardant insulating composition comprising 1 to 20 parts by mass and 10 to 300 parts by mass of a metal hydroxide on a conductor. Insulated wire.   2. The non-halogen flame-retardant insulated wire according to claim 1, wherein the organopolysiloxane is an organopolysiloxane having a degree of polymerization of 3000 or more.

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