WO2011068047A1 - 電線被覆材用組成物、絶縁電線およびワイヤーハーネス - Google Patents
電線被覆材用組成物、絶縁電線およびワイヤーハーネス Download PDFInfo
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- WO2011068047A1 WO2011068047A1 PCT/JP2010/070733 JP2010070733W WO2011068047A1 WO 2011068047 A1 WO2011068047 A1 WO 2011068047A1 JP 2010070733 W JP2010070733 W JP 2010070733W WO 2011068047 A1 WO2011068047 A1 WO 2011068047A1
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- polyolefin
- wire
- silane
- composition
- mass
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Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B7/00—Insulated conductors or cables characterised by their form
- H01B7/17—Protection against damage caused by external factors, e.g. sheaths or armouring
- H01B7/29—Protection against damage caused by extremes of temperature or by flame
- H01B7/292—Protection against damage caused by extremes of temperature or by flame using material resistant to heat
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D123/00—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers
- C09D123/02—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/0025—Crosslinking or vulcanising agents; including accelerators
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
Definitions
- the present invention relates to a composition for a wire covering material, an insulated wire, and a wire harness, and more particularly, a composition for a wire covering material suitable as a covering material for an insulated wire applied to a place where high heat resistance is required,
- the present invention relates to an insulated wire and a wire harness.
- Patent Document 1 1 to 3 parts by weight of a silane coupling agent and 0.025 to 0.063 parts by weight of a crosslinking agent are blended with 100 parts by weight of a polyolefin elastomer, and the mixture is heated and kneaded to prepare a silane coupling agent.
- non-halogen flame-retardant silane-crosslinked polyolefin composition formed by kneading and heat-crosslinking a catalyst master batch (component B) impregnated with 7.14 to 31.3 parts by weight of a catalyst.
- composition used for a wire coating material 100 parts by mass of at least one polymer selected from the group consisting of a thermoplastic resin, a rubber, and a thermoplastic elastomer, an organic peroxide 0.
- a resin composition for mixing with a silane crosslinkable polyolefin, comprising 01 to 0.6 parts by weight, silanol condensation catalyst 0.05 to 0.5 parts by weight, and magnesium hydroxide 100 to 300 parts by weight is disclosed. .
- the conventional wire coating composition has room for improvement in the following points.
- silane crosslinking regardless of electron beam crosslinking, as a flame retardant magnesium hydroxide, instead of magnesium hydroxide chemically synthesized from seawater, water derived from natural minerals
- magnesium oxide instead of magnesium hydroxide chemically synthesized from seawater, water derived from natural minerals
- mechanical properties such as wear resistance and tensile elongation are significantly reduced. Therefore, there is a problem that it is difficult to achieve both heat resistance and mechanical properties while using a combination of silane crosslinking and magnesium hydroxide derived from natural minerals.
- the present invention has been made in view of the above circumstances, and the problem to be solved by the present invention is to achieve both heat resistance and mechanical characteristics even when silane crosslinking and natural mineral-derived magnesium hydroxide are used.
- An object of the present invention is to provide a wire coating composition that can be used. Moreover, it is providing the insulated wire and wire harness excellent in heat resistance and mechanical characteristics.
- the composition for an electric wire coating material according to the present invention is modified with (A) a silane-grafted polyolefin obtained by grafting a silane coupling agent to a polyolefin, (B) an unmodified polyolefin, and (C) a functional group.
- the gist of the present invention is to contain modified polyolefin, (D) magnesium hydroxide derived from natural minerals, and (E) a crosslinking catalyst.
- the composition for a wire covering material includes 10 to 70 in total of (A) 30 to 90 parts by mass of a silane-grafted polyolefin, (B) an unmodified polyolefin and (C) a modified polyolefin modified with a functional group. It is preferable that 30 to 200 parts by mass of magnesium hydroxide derived from natural mineral (D) is included with respect to 100 parts by mass in total of parts by mass and (A), (B) and (C).
- the functional group is preferably one or more selected from a carboxylic acid group, an acid anhydride group, an amino group, and an epoxy group.
- the polyolefin is preferably one or more selected from ultra-low density polyethylene, linear low density polyethylene, and low density polyethylene.
- the said composition for electric wire coating materials contains the (F) zinc oxide and / or the benzimidazole type compound further.
- the gist of the insulated wire according to the present invention is to have a wire covering material obtained by crosslinking the above composition for a wire covering material with silane.
- the gist of the wire harness according to the present invention is to have the above insulated wire.
- composition for an electric wire coating material comprises (A) a silane-grafted polyolefin obtained by grafting a polyolefin with a silane coupling agent, (B) an unmodified polyolefin, (C) a modified polyolefin modified with a functional group, (D ) Magnesium hydroxide derived from natural minerals and (E) a crosslinking catalyst. Therefore, when silane crosslinking is performed, high heat resistance and excellent mechanical properties can be exhibited, and both heat resistance and mechanical properties can be achieved.
- composition for wire coating material (A) 30 to 90 parts by mass of silane-grafted polyolefin, (B) unmodified polyolefin and (C) modified polyolefin modified with a functional group in a total of 10 to 70 parts by mass.
- component range of 30 to 200 parts by mass of magnesium hydroxide derived from natural minerals with respect to 100 parts by mass of parts (A), (B) and (C) heat resistance and mechanical properties Excellent balance with characteristics.
- the functional group is one or more selected from a carboxylic acid group, an acid anhydride group, an amino group, and an epoxy group, it is derived from (C) a modified polyolefin and (D) a natural mineral. Good adhesion with magnesium hydroxide is obtained, which can contribute to improvement of mechanical properties.
- the polyolefin is one or more selected from ultra-low density polyethylene, linear low density polyethylene, and low density polyethylene, it is possible to improve tensile elongation characteristics and flexibility of electric wires. Can contribute.
- composition for wire coating materials further contains (F) zinc oxide and / or a benzimidazole type compound, it can contribute to an improvement in heat resistance.
- the insulated wire according to the present invention has a wire covering material obtained by silane crosslinking the above composition for wire covering material, it is excellent in heat resistance and mechanical properties. Moreover, since expensive electron beam irradiation crosslinking and synthetic magnesium hydroxide are not used, it can contribute to cost reduction.
- the wire harness according to the present invention has the above insulated wire, it is excellent in heat resistance and mechanical properties. Moreover, since expensive electron beam irradiation crosslinking and synthetic magnesium hydroxide are not used, it can contribute to cost reduction.
- composition for a wire coating material includes (A) a silane-grafted polyolefin, (B) an unmodified polyolefin, (C) a modified polyolefin modified with a functional group, (D) a magnesium hydroxide derived from a natural mineral, ( E) Contains a crosslinking catalyst.
- Silane-grafted polyolefin is obtained by grafting a silane coupling agent to polyolefin.
- polystyrene resin examples include ethylene copolymers such as homopolymers of olefins such as ethylene and propylene, ethylene- ⁇ olefin copolymers, ethylene-vinyl acetate copolymers, and ethylene- (meth) acrylic acid ester copolymers.
- ethylene copolymers such as polymers, propylene- ⁇ olefin copolymers, propylene-vinyl acetate copolymers, propylene- (meth) acrylate copolymers, olefin elastomers such as ethylene elastomers and propylene elastomers, etc. Can be illustrated. These may be used alone or in combination.
- polyethylene polypropylene, ethylene-vinyl acetate copolymer, ethylene-acrylic acid ester copolymer, ethylene-methacrylic acid ester copolymer, and the like are used.
- polyethylene examples include high density polyethylene (HDPE), medium density polyethylene (MDPE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE), and ultra low density polyethylene. These may be used alone or in combination. Preferably, it is a metallocene ultra-low density polyethylene from the viewpoint of improving the tensile elongation characteristics.
- HDPE high density polyethylene
- MDPE medium density polyethylene
- LDPE low density polyethylene
- LLDPE linear low density polyethylene
- ultra low density polyethylene ultra low density polyethylene
- silane coupling agent examples include vinyl alkoxysilanes such as vinyltrimethoxysilane, vinyltriethoxysilane, and vinyltributoxysilane, normal hexyltrimethoxysilane, vinylacetoxysilane, ⁇ -methacryloxypropyltrimethoxysilane, ⁇ - Examples thereof include methacryloxypropylmethyldimethoxysilane. These may be used alone or in combination of two or more.
- the upper limit of the graft amount of the silane coupling agent is preferably from the viewpoint of foreign matter generation due to excessive crosslinking in the wire coating step, It is good that it is 15 mass% or less, More preferably, it is 10 mass% or less, More preferably, it is 5 mass% or less.
- the upper limit of the graft amount is preferably 0.1% by mass or more, more preferably 1% by mass or more, and still more preferably 2.5% from the viewpoint of the degree of cross-linking (gel fraction) of the wire coating. It is good if it is at least mass%.
- a method of grafting a silane coupling agent onto polyolefin a method of adding a silane coupling agent, a free radical generator, etc. to polyolefin and mixing them with a twin screw extruder can be used.
- a method of adding a silane coupling agent may be used.
- the blending amount of the silane coupling agent is preferably in the range of 0.5 to 5 parts by mass with respect to 100 parts by mass of the polyolefin to which the silane coupling agent is grafted. More preferably, it is in the range of 2.5 to 5 parts by mass.
- the blending amount of the silane coupling agent is less than 0.5 parts by mass, the graft amount of the silane coupling agent is small, and it is difficult to obtain a sufficient degree of crosslinking during silane crosslinking.
- it exceeds 5 parts by mass the crosslinking reaction proceeds too much during kneading, and a gel-like substance is likely to be generated. If it does so, an unevenness
- the melt viscosity becomes too high, overloading the extruder, and workability tends to deteriorate.
- the free radical generator examples include dicumyl peroxide (DCP), benzoyl peroxide, dichlorobenzoyl peroxide, di-tert-butyl peroxide, butyl peracetate, tert-butyl perbenzoate, and 2,5-dimethyl-2.
- An organic peroxide such as, 5-di (tert-butylperoxy) hexane can be exemplified. More preferred is dicumyl peroxide (DCP).
- DCP dicumyl peroxide
- the preparation temperature of the silane graft batch is preferably 200 ° C. or higher in order to graft polymerize the silane coupling agent to the polyolefin.
- the blending amount of the free radical generator is preferably in the range of 0.01 to 0.3 parts by mass with respect to 100 parts by mass of the silane-modified polyolefin. More preferably, it is in the range of 0.025 to 0.1 parts by mass. If the amount is less than 0.01 parts by mass, the grafting reaction of the silane coupling agent does not proceed sufficiently and it is difficult to obtain a desired gel fraction. On the other hand, when it exceeds 0.3 parts by mass, undesired peroxide crosslinking is likely to proceed. Therefore, when the wire coating material is formed by extrusion coating on the outer periphery of the conductor, irregularities are generated on the surface of the coating material, and the appearance tends to deteriorate. In addition, the melt viscosity becomes too high, the extruder is overloaded, and workability is likely to deteriorate.
- Unmodified polyolefin is a polyolefin that has not been modified with a functional group.
- specific polyolefin the polyolefin mentioned above in (A) can be illustrated, and detailed explanation here is omitted.
- the functional group examples include a carboxylic acid group, an acid anhydride group, an amino group, an epoxy group, a silane group, and a hydroxyl group.
- a carboxylic acid group, an acid anhydride group, an amino group, an epoxy group, and the like are preferable. This is because good adhesion between (C) the modified polyolefin and (D) magnesium hydroxide derived from natural minerals can be obtained, which can contribute to the improvement of mechanical properties.
- These modified polyolefins may contain one or more functional groups.
- one or more of the same or different polyolefins modified with different functional groups and different polyolefins modified with the same functional groups may be contained.
- the amount of the functional group in the modified polyolefin modified with the functional group is preferably 0.01 to 20% by mass, more preferably 0.05 to 15% by mass, and further preferably 0.1 to 10% by mass. It is good to be within the range. This is because if the amount of the functional group is within these ranges, the balance between the effect of modification by the functional group and the peelability when applied to the wire coating material is excellent.
- Specific examples of the method for modifying the polyolefin with a functional group include a method in which a compound having a functional group is graft-polymerized to the polyolefin, or a compound having a functional group and an olefin monomer are copolymerized to obtain an olefin copolymer. Methods and the like.
- Specific examples of the compound that introduces a carboxylic acid group or an acid anhydride group as a functional group include ⁇ , ⁇ -unsaturated dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, and itaconic acid, or anhydrides thereof.
- unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, furanic acid, crotonic acid, vinyl acetic acid and pentenoic acid.
- Specific examples of compounds that introduce amino groups as functional groups include aminoethyl (meth) acrylate, propylaminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, and dibutylaminoethyl.
- Specific examples of compounds that introduce an epoxy group as a functional group include glycidyl acrylate, glycidyl methacrylate, itaconic acid monoglycidyl ester, butenetricarboxylic acid monoglycidyl ester, butenetricarboxylic acid diglycidyl ester, butenetricarboxylic acid triglycidyl.
- Glycidyl esters such as esters, ⁇ -chloroacrylic acid, maleic acid, crotonic acid, fumaric acid, glycidyl ethers such as vinyl glycidyl ether, allyl glycidyl ether, glycidyloxyethyl vinyl ether, styrene-p-glycidyl ether, p-glycidyl Examples include styrene.
- Magnesium hydroxide derived from a natural mineral uses a natural mineral-derived one as magnesium hydroxide.
- Magnesium hydroxide derived from natural minerals can be typically obtained by pulverizing a mineral mainly composed of magnesium hydroxide. Therefore, compared with synthetic magnesium hydroxide synthesized using a Mg source contained in seawater as a raw material, the surface has many surface irregularities.
- the upper limit of the particle diameter of the natural mineral-derived magnesium hydroxide is preferably 20 ⁇ m or less, more preferably 10 ⁇ m or less, and even more preferably 5 ⁇ m or less, from the viewpoint of excellent appearance when used as a wire coating material. And good.
- the lower limit of the particle diameter is preferably 0.5 ⁇ m or more from the viewpoint that secondary agglomeration hardly occurs and mechanical characteristics are hardly deteriorated.
- natural mineral-derived magnesium hydroxide has large irregularities on the particle surface. Therefore, basically the adhesion with the polymer component is poor.
- the surface of the natural mineral-derived magnesium hydroxide may be surface-treated with a surface treating agent from the viewpoint of easily obtaining good adhesion with the polymer component.
- the surface treatment agent examples include silane coupling agents, titanate coupling agents, fatty acids or fatty acid salts or fatty acid ester compounds, and olefinic waxes. These can be used alone or in combination of two or more.
- the treatment with the surface treatment agent is preferably performed in a range of 0.1 to 10% by mass with respect to 100 parts by mass of magnesium hydroxide derived from natural minerals. More preferably, it is in the range of 0.5 to 5% by mass. This is because the treatment within the above range is excellent in the balance between the improvement effect of the mechanical properties when the wire coating material is used and the suppression effect of the deterioration of the mechanical properties due to the treatment agent remaining as impurities.
- composition for electric wire coating materials which concerns on this invention contains the magnesium hydroxide derived from a natural mineral essential, you may contain synthetic
- crosslinking catalyst is a silanol condensation catalyst for silane-crosslinking a silane graft polyolefin.
- metal carboxylates such as tin, zinc, iron, lead and cobalt, titanate esters, organic bases, inorganic acids, organic acids and the like can be exemplified.
- dibutyltin dilaurate, dibutyltin dimaleate, dibutyltin mercaptide such as dibutyltin bisoctylthioglycol ester salt, dibutyltin ⁇ -mercaptopropionate polymer
- composition for wire covering material according to the present invention contains the above (A) to (E), and optionally further includes (F) zinc oxide and / or a benzimidazole compound. Also good. This is because the inclusion of these can contribute to an improvement in heat resistance.
- Zinc oxide can be partially or entirely replaced with zinc sulfide.
- a benzimidazole compound containing sulfur can be suitably used. Specific examples include 2-mercaptobenzimidazole, 2-mercaptomethylbenzimidazole, 4-mercaptomethylbenzimidazole, 5-mercaptomethylbenzimidazole, and zinc salts thereof. Particularly preferred is 2-mercaptobenzimidazole and its zinc salt.
- the benzimidazole compound may have a substituent such as an alkyl group at another position of the benzimidazole skeleton.
- the wire coating material composition according to the present invention may be added with one or more of various additives as long as the wire characteristics are not impaired.
- various additives for example, lubricants such as stearic acid, antioxidants, copper damage inhibitors, ultraviolet absorbers, processing aids (waxes, lubricants, etc.), flame retardant aids, pigments, etc. are exemplified. can do.
- the wire coating material composition is composed of (A) 30 to 90 parts by mass of silane-grafted polyolefin, preferably 40 to 80 parts by mass, more preferably 50 to 70 parts by mass, (B) unmodified polyolefin and (C) functional group. 10 to 70 parts by weight, preferably 20 to 60 parts by weight, more preferably 30 to 50 parts by weight, and a total of 100 of (A), (B) and (C) with the modified polyolefin modified with a group It is preferable that 30 to 200 parts by mass of magnesium hydroxide derived from natural mineral (D), preferably 50 to 120 parts by mass, and more preferably 60 to 100 parts by mass with respect to parts by mass. This is because it has an excellent balance of heat resistance, mechanical properties, flame retardancy, and the like.
- D natural mineral
- the (E) crosslinking catalyst is preferably in the range of 0.3 to 10 parts by mass, more preferably 0.5 to 5 parts by mass with respect to 100 parts by mass of the (A) silane-grafted polyolefin. preferable. This is because by setting the amount to 0.5 parts by mass or more, it is possible to obtain an appropriate degree of cross-linking and to easily improve the heat resistance, and it is possible to improve the appearance by setting the amount to 5 parts by mass or less.
- the (F) zinc oxide and / or benzimidazole compound is preferably 1 to 20 parts by mass, more preferably, with respect to 100 parts by mass in total of (A), (B) and (C). It is preferably in the range of 3 to 10 parts by mass.
- the amount is 1 part by mass or more, heat resistance is easily improved, and when the amount is 20 parts by mass or less, aggregation of particles is prevented, the appearance of the electric wire is improved, and mechanical properties such as wear resistance are improved. It is difficult to adversely affect
- the lubricant such as stearic acid is preferably 5 parts by mass or less, more preferably 3 parts by mass or less, with respect to 100 parts by mass of the resin component excluding the lubricant. This is because the above-mentioned lubricant has an effect of improving the appearance of the electric wire, but if added in a large amount, it adversely affects electric wire workability, wire harness workability, and the like.
- the composition for a wire coating material includes (A) a silane-grafted polyolefin, (B) an unmodified polyolefin polyolefin, (C) a modified polyolefin modified with a functional group, and (D) a water derived from a natural mineral.
- Magnesium oxide, (E) cross-linking catalyst, and other additives if necessary, using a conventional kneader such as a Banbury mixer, a pressure kneader, a kneading extruder, a twin screw extruder, or a roll. It can be obtained by heat-kneading and molding.
- the silane-grafted polyolefin can be made into a crosslinked product by silane crosslinking (water crosslinking).
- silane crosslinking water crosslinking
- the composition for a wire coating material according to the present invention is preferably a silane graft batch comprising a silane graft polyolefin or a silane graft polyolefin forming material (polyolefin, silane coupling agent, free radical generator), and polyolefin (unmodified and / or Or modified) by heating and kneading a flame retardant batch comprising a natural mineral-derived magnesium hydroxide or a crosslinking catalyst as a flame retardant, or the above silane graft batch and the above flame retardant batch excluding the crosslinking catalyst, A catalyst batch obtained by blending a polyolefin (unmodified and / or modified) with a crosslinking catalyst is heated and kneaded, or the silane graft batch, the flame retardant batch excluding the crosslinking catalyst, and a crosslinking catalyst.
- a silane graft batch comprising a silane graft polyolefin or a silane
- the silane-grafted polyolefin can be made into a crosslinked body by subsequent silane crosslinking (water crosslinking).
- the insulated wire according to the present invention has a wire covering material obtained by silane-crosslinking the above composition for wire covering material on the outer periphery of a conductor made of copper, copper alloy, aluminum, aluminum alloy or the like.
- the conductor is not particularly limited, such as the diameter of the conductor or the material of the conductor, and can be appropriately determined according to the application. Moreover, there is no restriction
- the wire covering material may be a single layer or a plurality of layers.
- the composition for an electric wire coating material after silane crosslinking preferably has a crosslinking degree of 50% or more from the viewpoint of heat resistance. More preferably, it is 60% or more.
- the degree of crosslinking can be adjusted by the graft amount of the silane coupling agent of the silane-grafted polyolefin to be used, the type and amount of the crosslinking catalyst, silane crosslinking (water crosslinking) conditions (temperature and time), and the like.
- each batch is heated and kneaded by the above-described method, and then the obtained kneaded product is extrusion-coated on the outer periphery of the conductor, and then the extrusion-coated coating material is crosslinked with silane. (Water cross-linking) may be performed.
- each batch formed into a pellet shape can be dry blended using a mixer or an extruder.
- the wire coating material may be extrusion coated on the outer periphery of the conductor using a normal extrusion molding machine or the like.
- the wire covering material formed in the extrusion coating step can be crosslinked by exposing it to water vapor or water.
- the conditions at this time are preferably performed within 48 hours within a temperature range of room temperature to 90 ° C., for example. More preferably, it is carried out within a temperature range of 60 to 80 ° C. and within a range of 12 to 24 hours.
- the wire harness which concerns on this invention has the insulated wire mentioned above.
- covered with the wire harness protective material can be illustrated.
- the number of wires included in a single wire bundle and a mixed wire bundle can be arbitrarily determined and is not particularly limited.
- the structure of other insulated wires included is not particularly limited.
- the wire covering material may have a single layer structure or a two layer structure.
- covering material of another insulated wire is not specifically limited, either.
- the wire harness protective material has a role of covering the outer periphery of the wire bundle and protecting the inner wire bundle from the external environment, etc., and an adhesive is applied to at least one surface of the tape-shaped substrate.
- Examples include those coated and those having a substrate formed in a tube shape, a sheet shape, or the like. These can be appropriately selected and used according to the application.
- the substrate constituting the wire harness protective material include, for example, various non-halogen flame retardant resin compositions, vinyl chloride resin compositions, or halogen resin compositions other than the vinyl chloride resin compositions. Can be mentioned.
- Test material and manufacturer The test materials used in the present examples and comparative examples are shown together with the manufacturer, product name and the like.
- the gel fraction was measured according to JASO-D608-92. That is, about 0.1 g of the insulator sample of the electric wire is weighed and put into a test tube, 20 ml of xylene is added, and heated in a constant temperature oil bath at 120 ° C. for 24 hours. Thereafter, the sample was taken out, dried in a dryer at 100 ° C. for 6 hours, and allowed to cool to room temperature. Then, the weight was precisely weighed, and the mass percentage with respect to the mass before the test was taken as the gel fraction. A case where the gel fraction was 50% or more was evaluated as “good”, and a case where the gel fraction was less than 50% was determined as “failed”.
- the gel fraction is generally used for crosslinked electric wires as an index representing the crosslinked state of water crosslinking.
- the tensile elongation was measured according to the tensile test of JIS C 3005. In other words, an insulated wire is cut to a length of 100 mm, a conductor is removed to form a tubular test piece made only of a wire covering material, and both ends of the test piece are attached to a chuck of a tensile tester at room temperature of 23 ⁇ 5 ° C. After that, the test piece was pulled at a pulling rate of 200 mm / min, and the load and elongation at break of the test piece were measured.
- Comparative Example 1 does not contain (A) a silane-grafted polyolefin and (C) a modified polyolefin modified with a functional group. Therefore, silane crosslinking is not performed and heat resistance is poor. Also, the tensile properties are inferior.
- Comparative Example 2 does not contain (C) a modified polyolefin modified with a functional group. Therefore, the adhesion between the resin component and (D) natural mineral-derived magnesium hydroxide is poor, and the wear resistance and tensile properties are poor. Further, due to the poor adhesion, the surface of the electric wire has a large roughness and is inferior in appearance.
- Comparative Example 3 does not contain (D) magnesium hydroxide derived from natural minerals. Therefore, there is no problem in heat resistance, abrasion resistance, tensile properties, etc., but it does not have the flame retardancy necessary for electric wires.
- Example 3 containing (F) zinc oxide and / or a benzimidazole type compound has high heat resistance compared with another Example.
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Abstract
Description
シラングラフトポリオレフィンは、ポリオレフィンにシランカップリング剤がグラフトされてなるものである。
未変性ポリオレフィンとは、官能基により変性されていないポリオレフィンのことである。具体的なポリオレフィンとしては、(A)にて上述したポリオレフィンを例示することができ、ここでの詳細な説明は省略する。
官能基により変性された変性ポリオレフィンを構成する具体的なポリオレフィンとしては、(A)にて上述したポリオレフィンを例示することができ、ここでの詳細な説明は省略する。
本発明に係る電線被覆材用組成物は、水酸化マグネシウムとして、天然鉱物由来のものを用いる。天然鉱物由来の水酸化マグネシウムは、典型的には、水酸化マグネシウムを主成分とする鉱物を粉砕処理することにより得ることができる。そのため、海水に含まれるMg源を原料として合成される合成水酸化マグネシウムに比較して、表面の凹凸が多い特徴を有している。
架橋触媒は、シラングラフトポリオレフィンをシラン架橋させるためのシラノール縮合触媒である。例えば、錫、亜鉛、鉄、鉛、コバルト等の金属カルボン酸塩や、チタン酸エステル、有機塩基、無機酸、有機酸などを例示することができる。
本実施例および比較例において使用した供試材料を製造元、商品名等とともに示す。
・シラングラフトPE(1)[三菱化学(株)製、「リンクロンXLE815N(LLDPE)」]
・シラングラフトPE(2)[三菱化学(株)製、「リンクロンXCF710N(LDPE)」]
・シラングラフトPE(3)[三菱化学(株)製、「リンクロンQS241HZ(HDPE)」]
・シラングラフトPE(4)[三菱化学(株)製、「リンクロンSH700N(VLDPE)」]
・シラングラフトEVA[三菱化学(株)製、「リンクロンXVF600N」]
・PPエラストマー[日本ポリプロ(株)製、「ニューコンNAR6」]
・PE(1)[デュポン ダウ エラストマー ジャパン(株)製、「エンゲージ 8003」(VLDPE)]
・PE(2)[日本ユニカー(株)製、「NUC8122」(LDPE)]
・PE(3)[プライムポリマー(株)製、「ウルトゼックス10100W」(LLDPE)]
・マレイン酸変性PE[日本油脂(株)製、「モディックAP512P」]
・エポキシ変性PE[住友化学(株)製、「ボンドファーストE(E-GMA)」]
・マレイン酸変性PP[三菱化学(株)製、「アドマーQB550」]
・天然鉱物由来の水酸化マグネシウム[神島化学(株)製、「マグシーズW」]
・合成水酸化マグネシウム[協和化学(株)製、「キスマ5」]
・酸化防止剤(1)[チバスペシャリティケミカルズ社製、「イルガノックス1010」]
・酸化防止剤(2)[チバスペシャリティケミカルズ社製、「イルガノックス1330」]
・銅害防止剤[(株)アデカ製、「CDA-1」]
・酸化亜鉛[ハクスイテック(株)製、「亜鉛華二種」]
・硫化亜鉛[Sachtleben Chemie Gmbh製、「SachtolithHD-S」]
・ベンズイミダゾール系化合物(川口化学工業(株)製、「アンテージMB」)
・潤滑剤(1)[日本油脂(株)製、「アルフローP10」(エルカ酸アミド)]
・潤滑剤(2)[日本油脂(株)製、「アルフローS10」(ステアリン酸アミド)]
・架橋触媒[三菱化学(株)製、「リンクロンLZ0515H」]
表1、2に示した実施例、比較例の難燃剤バッチの配合割合となるように各材料を二軸押出混練機に加え、200℃で0.1~2分間加熱混練した後、ペレット化し、各難燃剤バッチを調製した。
表1、2に示した実施例、比較例の配合割合となるように上記難燃剤バッチと、シラングラフトポリオレフィン(比較例1は無し)と、架橋触媒とを押出機のホッパーで混合して押出機の温度を約180℃~200℃に設定して、押出加工を行なった。外径2.4mmの導体上に厚さ0.7mmの絶縁体として押出被覆した(被覆外径3.8mm)。その後、60℃、95%湿度の高湿高温槽で24時間水架橋処理を施して絶縁電線を作製した。
JASO-D608-92に準拠して、ゲル分率を測定した。すなわち、電線の絶縁体試料を約0.1g秤量しこれを試験管に入れ、キシレン20mlを加えて、120℃の恒温油槽中で24時間加熱する。その後試料を取り出し、100℃の乾燥器内で6時間乾燥後、常温になるまで放冷してから、その重量を精秤し、試験前の質量に対する質量百分率をもってゲル分率とした。ゲル分率50%以上であった場合を合格「○」、ゲル分率50%未満であった場合を不合格「×」とした。なお、ゲル分率は、水架橋の架橋状態を表す指標として架橋電線に一般的に用いられている。
ISO6722に準拠し、70秒以内に消火する場合を合格「○」、70秒を越えて消火する場合を不合格「×」とした。
JIS C 3005の引張試験に準拠して、引張伸びを測定した。すなわち、絶縁電線を100mmの長さに切り出し、導体を取り除いて電線被覆材のみの管状試験片とした後、23±5℃の室温下にて、試験片の両端を引張試験機のチャックに取り付けた後、引張速度200mm/分で引っ張り、試験片の破断時の荷重および伸びを測定した。引張伸びが125%以上であった場合を合格「○」、とりわけ300%以上であった場合を良好「◎」とした。引張伸びが125%未満であった場合を不合格「×」とした。
ISO6722に準拠し、500回以上のブレード磨耗に耐えられた場合を合格「○」、耐えられなかった場合を不合格「×」とした。
ISO6722に準拠し、絶縁電線に対して150℃×3000時間もしくは10000時間の老化試験を行った後、1kv×1min.の耐電圧試験を行った。老化時間3000時間後に1kv×1min.の耐電圧試験に耐えることができた場合を「○」、老化時間10000時間後に1kv×1min.の耐電圧試験に耐えることができた場合を「◎」、老化時間3000時間後に1kv×1min.の耐電圧試験に耐えることができなかった場合を「×」とした。
針形の検出器(Mitutoyo製「サーフテストSJ301」)を用いて、絶縁電線の表面の平均粗さ(Ra)を測定し、Ra=1未満の場合を表面粗さが良好であるとして「○」、Ra=0.5未満の場合を表面粗さに優れるとして「◎」とした。なお、電線表面粗さは、参考データである。
Claims (7)
- (A)ポリオレフィンにシランカップリング剤がグラフトされたシラングラフトポリオレフィン
(B)未変性ポリオレフィン
(C)官能基により変性された変性ポリオレフィン
(D)天然鉱物由来の水酸化マグネシウム
(E)架橋触媒
を含むことを特徴とする電線被覆材用組成物。 - 前記(A)シラングラフトポリオレフィン30~90質量部、
前記(B)未変性ポリオレフィンと前記(C)官能基により変性された変性ポリオレフィンとを合計で10~70質量部、
前記(A)、(B)および(C)の合計100質量部に対し、
前記(D)天然鉱物由来の水酸化マグネシウム30~200質量部
を含むことを特徴とする請求項1に記載の電線被覆材用組成物。 - 前記官能基は、カルボン酸基、酸無水物基、アミノ基およびエポキシ基から選択される1種または2種以上であることを特徴とする請求項1または2に記載の電線被覆材用組成物。
- 前記ポリオレフィンは、超低密度ポリエチレン、直鎖状低密度ポリエチレン、および、低密度ポリエチレンから選択される1種または2種以上であることを特徴とする請求項1から3のいずれか1項に記載の電線被覆材用組成物。
- (F)酸化亜鉛、および/または、ベンズイミダゾール系化合物を含むことを特徴とする請求項1から4のいずれか1項に記載の電線被覆材用組成物。
- 請求項1から5のいずれか1項に記載の電線被覆材用組成物をシラン架橋させてなる電線被覆材を有することを特徴とする絶縁電線。
- 請求項6に記載の絶縁電線を有することを特徴とするワイヤーハーネス。
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US13/509,931 US20120241190A1 (en) | 2009-12-02 | 2010-11-19 | Composition for wire coating material, insulated wire, and wiring harness |
DE112010004666T DE112010004666T5 (de) | 2009-12-02 | 2010-11-19 | Zusammensetzung für Leitungsbeschichtungsmaterial, isolierte Leitung und Kabelstrang |
CN2010800546769A CN102648499A (zh) | 2009-12-02 | 2010-11-19 | 电线包覆材料用组合物、绝缘电线及线束 |
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US (1) | US20120241190A1 (ja) |
JP (1) | JP2011119083A (ja) |
CN (1) | CN102648499A (ja) |
DE (1) | DE112010004666T5 (ja) |
WO (1) | WO2011068047A1 (ja) |
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US20130273367A1 (en) * | 2011-01-31 | 2013-10-17 | Autonetworks Technologies, Ltd. | Composition for wire coating material, insulated wire, and wiring harness |
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CN105348625A (zh) * | 2014-04-28 | 2016-02-24 | 赵月 | 一种无卤低烟阻燃电缆的制备方法 |
JP6295886B2 (ja) * | 2014-08-22 | 2018-03-20 | 株式会社オートネットワーク技術研究所 | 電線被覆材用組成物、絶縁電線およびワイヤーハーネス |
JP6344200B2 (ja) * | 2014-11-04 | 2018-06-20 | 住友電気工業株式会社 | 難燃性樹脂組成物及び難燃性絶縁電線・ケーブル |
JP6287919B2 (ja) * | 2015-03-24 | 2018-03-07 | 株式会社オートネットワーク技術研究所 | 電線被覆材組成物、絶縁電線及びワイヤーハーネス |
JP2018154679A (ja) * | 2017-03-16 | 2018-10-04 | 株式会社オートネットワーク技術研究所 | 電線被覆材用組成物、絶縁電線およびワイヤーハーネス |
DE112019000429T5 (de) * | 2018-01-16 | 2021-05-12 | Toagosei Co., Ltd. | Batterieklebstoffzusammensetzung und Batterieklebeelement unter Verwendung derselben |
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US20120241190A1 (en) | 2012-09-27 |
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CN102648499A (zh) | 2012-08-22 |
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