Resin composition, insulated electric wire and method of manufacturing insulated electric wire
10964449 ยท 2021-03-30
Assignee
Inventors
Cpc classification
International classification
Abstract
An insulated electric wire includes a conductor and an insulating layer coated in periphery of the conductor. The insulating layer is made of a resin composition containing a base polymer and a flame retardant. The flame retardant is made of silane-treated aluminum hydroxide, aluminum hydroxide treated with a treatment agent other than a silane coupling agent and/or untreated aluminum hydroxide. The base polymer contains a polymer having a polar group. The resin composition contains the flame retardant, a content of which is more than 40 parts by mass and equal to or less than 80 parts by mass per 100 parts by mass of the base polymer. The resin composition contains the silane-treated aluminum hydroxide, a content of which is equal to or more than 10 parts by mass and equal to or less than 70 parts by mass per 100 parts by mass of the flame retardant.
Claims
1. A resin composition comprising: a base polymer; and a flame retardant, wherein the flame retardant is made of aluminum hydroxide, a surface of which is treated with a silane coupling agent, and aluminum hydroxide, a surface of which is treated with a fatty acid, the base polymer contains a polymer having a polar group, the resin composition contains the flame retardant, a content of which is more than 40 parts by mass and equal to or less than 80 parts by mass per 100 parts by mass of the base polymer, and the resin composition contains the aluminum hydroxide, a surface of which is treated with the silane coupling agent and a content of which is equal to or more than 10 parts by mass and equal to or less than 70 parts by mass per 100 parts by mass of the flame retardant.
2. The resin composition according to claim 1, wherein the polymer having the polar group is ethylene-vinyl acetate copolymer.
3. The resin composition according to claim 1, wherein the resin composition further contains a black, yellow, white, red or green colorant.
4. An insulated electric wire comprising: an insulating layer made of the resin composition according to claim 1.
5. A cable comprising: a sheath layer made of the resin composition according to claim 1.
6. The insulated electric wire according to claim 4, wherein an oxygen index is equal to or larger than 20, and a tensile strength in 100% tension is equal to or smaller than 6.0 MPa.
7. The insulated electric wire according to claim 4, wherein the insulated electric wire is used for an in-board wiring of a distribution board or a control board or for a motor lead wire.
8. A method of manufacturing an insulated electric wire comprising the steps of: (a) forming a resin composition by kneading a base polymer and a flame retardant; (b) manufacturing an uncross-linked insulated electric wire by extruding the resin composition so as to coat periphery of a conductor to form an insulating layer; and (c) manufacturing a cross-linked insulated electric wire by cross-linking the base polymer in the resin composition, wherein the flame retardant is made of aluminum hydroxide, a surface of which is treated with a silane coupling agent, and aluminum hydroxide, a surface of which is treated with a fatty acid, the base polymer contains a polymer having a polar group, the resin composition contains the flame retardant, a content of which is more than 40 parts by mass and equal to or less than 80 parts by mass per 100 parts by mass of the base polymer, and the resin composition contains the aluminum hydroxide, a surface of which is treated with the silane coupling agent and a content of which is equal to or more than 10 parts by mass and equal to or less than 70 parts by mass per 100 parts by mass of the flame retardant.
9. The method of manufacturing the insulated electric wire according to claim 8, wherein, after the step (b) and before the step (c), the method includes a step of (d) reeling up the uncross-linked insulated electric wire.
10. The method of manufacturing the insulated electric wire according to claim 8, wherein the cross-linked insulated electric wire has an oxygen index that is equal to or larger than 20, and has a tensile strength in 100% tension that is equal to or smaller than 6.0 MPa.
Description
BRIEF DESCRIPTIONS OF THE DRAWINGS
(1)
(2)
DESCRIPTIONS OF THE PREFERRED EMBODIMENTS
(3) (Embodiment)
(4) <Configuration of Resin Composition>
(5) A resin composition (non-halogen resin composition, flame-retardant resin composition) according to an embodiment of the present invention contains (A) a base polymer and (B) a flame retardant. The (A) base polymer contains (A1) a polymer having a polar group. As the (A1) polymer having the polar group, ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer and ethylene-acrylate copolymer are exemplified, and the ethylene-vinyl acetate copolymer is preferably used.
(6) To (A1) the polymer having the polar group, individual use of the ethylene-vinyl acetate copolymer may be applied. However, as described later in working examples, it is preferable to blend two or more types of the ethylene-vinyl acetate copolymer. In this case, when a vinyl acetate content (VA amount) of the ethylene-vinyl acetate copolymer is large, a glass transformation temperature becomes high, and a low-temperature property becomes low. On the other hand, when the vinyl acetate content of the ethylene-vinyl acetate copolymer is small, polarity becomes low, and a fuel resistance property becomes low. Therefore, when the polymer contains two or more types of the ethylene-vinyl acetate copolymer that are different from one another in a vinyl-acetate content ratio, a resin composition having excellent balance between the low-temperature property and the fuel resistance property can be manufactured. In the working examples described later, note that ethylene-vinyl acetate copolymer having a vinyl acetate content (VA amount) of 15 mass % (weight %) and ethylene-vinyl acetate copolymer having a vinyl acetate content (VA amount) of 28 mass % (weight %) are used.
(7) The (A) base polymer contains (A2) other polymer in addition to (A1) the polymer having the polar group. As (A2) the other polymer, a mixture of at least one or more types of ethylene-based copolymer selected from a group consisting of polyethylene, polypropylene, ethylene-(-olefin) copolymer, a ternary copolymer that has been further added with a monomer such as ethylene-propylene-diene copolymer or modified substances (such as a silane-compound copolymerized or graft-polymerized substance, or a maleic-acid modified substance) of these materials, etc., is exemplified.
(8) In the working examples described later, as (A2) the other polymer, the ethylene-(-olefin) copolymer is used. As the ethylene-(-olefin) copolymer, ethylene-propylene copolymer, ethylene-butene copolymer, ethylene-pentene copolymer, ethylene-hexene copolymer, ethylene-heptene copolymer, ethylene-octene copolymer and others are exemplified, and the ethylene-butene copolymer is preferably used as the other polymer.
(9) The (B) flame retardant of the present embodiment is made of (B1) aluminum hydroxide, a surface of which is treated with a silane coupling agent, (B2) aluminum hydroxide, a surface of which is treated with a treatment agent other than the silane coupling agent and/or (B3) aluminum hydroxide, a surface of which is untreated.
(10) A silane coupling agent is an organic silicon compound having an unsaturated bond group and a hydrolytic silane group. As the silane coupling agent, for example, -methacryloyloxy propyl trimethoxy silane, n-hexadecyl trimethoxy silane, -glycidoxy propyl trimethoxy silane, vinyl triacetoxy silane, -ureido propyl triethoxy silane, -dibutyl aminopropyl trimethoxy silane, -diallyl aminopropyl trimethoxy silane and others are exemplified. The aluminum hydroxide, a surface of which is treated with the silane coupling agent, according to the present embodiment can be manufactured by, for example, spray or immersion of aluminum hydroxide to solution of the silane coupling agent, and then, dry of them.
(11) As other treatment agent than the silane coupling agent, fatty acid such as stearic acid, fatty-acid metal salt such as calcium stearate, titanate-based coupling agent and others are exemplified. A plurality of types of these treatment agents may be used in combination.
(12) The resin composition of the present embodiment may contain not only (A) the base polymer and (B) the flame retardant but also (C) cross linking aid, (D) antioxidant, (E) copper inhibitor, (F) lubricant, (G) colorant or others if needed. As (C) the cross linking aid, for example, trimethylol propane trimethacrylate (TMPT), triallyl isocyanurate, triallyl cyanurate, N, N-meta phenylene bis maleimide, ethylene glycol dimethacrylate, zinc acrylate, zinc methacrylate and others are exemplified. As (D) the antioxidant, for example, phenol-based antioxidant, sulfur-based antioxidant, phenol/thioester-based antioxidant, amine-based antioxidant, phosphite ester-based antioxidant and others are exemplified. As (E) the copper inhibitor, for example, hydrazides such as N1, N12-bis(2-hydroxybenzoyl) dodecane dihydrazide, N, N-bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionyl] hydrazine and isophthalic acid bis(2-phenoxy propionyl hydrazine), 2-hydroxy-N-1H-1,2,4-triazol-3-ylbenzamide, alcohol carboxylic acid ester and others, that are heavy metal deactivators, are exemplified. As (F) the lubricant, for example, fatty acid amide system, zinc stearate, silicone, hydrocarbon system, ester system, alcohol system, metal soap system and others are exemplified. As (G) the colorant, for example, carbon black, inorganic pigment, organic pigment, dye and others are exemplified.
(13) As described later in the working examples, the resin composition of the present embodiment contains (B) the flame retardant, a content of which is more than 40 parts by mass and equal to or less than 80 parts by mass per 100 parts by mass of (A) the base polymer. When the addition amount of (B) the flame retardant is equal to or less than 40 parts by mass per 100 parts by mass of (A) the base polymer, the sufficient flame retardancy cannot be obtained. On the other hand, when the addition amount of (B) the flame retardant is more than 80 parts by mass per 100 parts by mass of (A) the base polymer, the flexibility becomes low.
(14) As described later in the working examples, the resin composition of the present embodiment contains (B1) the aluminum hydroxide, a surface of which is treated with a silane coupling agent and a content of which is equal to or more than 10 parts by mass and equal to or less than 70 parts by mass per 100 pars by mass of (B) the flame retardant. When a content of (B1) the aluminum hydroxide, a surface of which is treated with a silane coupling agent, is less than 10 parts by mass per 100 pars by mass of (B) the flame retardant, the whitening resistance in the uncross-linked state becomes low. On the other hand, when the content of (B1) the aluminum hydroxide, a surface of which is treated with a silane coupling agent, is more than 70 parts by mass per 100 pars by mass of (B) the flame retardant, the flexibility becomes low. As the resin composition according to an embodiment of the present invention, a non-halogen resin composition not containing a halogen element is preferable.
(15) <Configuration of Insulated Electric Wire>
(16)
(17) As the conductor 1, a generally-used metallic wire such as a copper wire, a copper alloy wire, an aluminum wire, a gold wire and a silver wire can be used. Alternatively, as the conductor 1, a metallic wire, periphery of which is metallic-plated with tin, nickel or others, may be used. Further, as the conductor 1, a stranded conductor formed by intertwining metallic wires may be also used.
(18) As shown in
(19) A cable of the present embodiment includes a sheath layer in an outer periphery of the insulating layer. In this case, in a viewpoint of prevention of the cable from being scratched and whitened during manufacturing steps, at least the sheath layer that is an outermost layer (a top layer) is preferable to be made of the resin composition of the present embodiment. In this case, a blend composition of the insulating layer is not particularly limited. However, the insulating layer is preferable to be made of the resin composition of the present embodiment.
(20) The insulated electric wire 10 of the present embodiment is applicable to various intended uses and various sizes, and can be used for each electric wire for use in a railroad vehicle, a car, an in-board wiring, an in-device wiring, and electricity. Particularly, the insulated electric wire 10 of the present embodiment is effective to be used as an in-board wiring of a distribution board/control board or a motor lead wire, and besides, effective to an intended use that needs a wiring operability in a narrow space (narrow-space wiring capability) and effective as an electric wire having high possibility of direct touching of a person.
(21) <Method of Manufacturing Insulated Electric Wire>
(22) First, an apparatus that manufactures the insulate electric wire of the present embodiment will be described.
(23) An extrusion coating apparatus 21 according to the present embodiment is, for example, a single screw extruder (L/D=20) having a screw diameter of 65 mm. The extrusion coating apparatus 21 includes a hopper 22 that loads a pellet of the resin composition, a cylinder 28 that heats the resin composition, a screw 23 that extrudes the resin composition in the cylinder 28, and a breaker plate 24 that regulates flow of the resin composition to increase a back pressure for improving a kneading state. Further, the extrusion coating apparatus 21 includes a head 25 that coats the resin composition in periphery of the conductor 1, a neck 26 that connects the cylinder 28 and the head 25, and a die 27 that defines a diameter of the electric wire. The screw 23 has a full flight shape. The cylinder 28 is divided into five cylinders, and is referred to below as cylinders 1 to 5 (not illustrated, see
(24) An electron-beam irradiation apparatus according to the present embodiment includes an electron-beam irradiation unit and a pulley for use in guiding the insulated electric wire (illustration of the electron-beam irradiation apparatus is omitted).
(25) Next, a method of manufacturing the insulated electric wire 10 of the present embodiment will be described. First, for example, (A) the base polymer and (B) the flame retardant are kneaded by a kneader, and, for example, a pellet-shaped resin composition (compound) is formed (at a kneading step).
(26) Subsequently, by the extrusion coating apparatus 21 shown in
(27) Subsequently, the uncross-linked insulated electric wire 5 is reeled out of the drum 29 by the electron-beam irradiation apparatus, and is guided and loaded into the electron-beam irradiation unit by the pulley. Then, in the electron-beam irradiation unit, the uncross-linked insulated electric wire 5 is irradiated with electron beams (at a cross-linking step). In this manner, (A) the base polymer in the resin composition making up the insulating layer 2 of the uncross-linked insulated electric wire 5 is cross-linked, so that a cross-linked insulated electric wire 10 can be manufactured. Note that the cross-linked insulated electric wire 10 is, for example, guided by the pulley and reeled up onto the drum. By the above-described steps, the insulated electric wire 10 of the present embodiment can be manufactured.
(28) Regarding the insulated electric wire 10 of the present embodiment, note that the case of the cross linking using the electron-beam irradiation method has been described as one example. However, the invention is not limited to this example. For example, a chemical cross linking method may be applied, the method manufacturing the cross-linked insulated electric wire 10 by manufacturing the uncross-linked insulated electric wire 5 with a cross linker being previously added to the resin composition, and then, performing a thermal treatment for the cross linking. That is, the resin composition of the present embodiment can be preferably used as a material of the insulating layer of the insulated electric wire (the sheath layer in the case of the cable) that is manufactured by manufacturing steps including a step of generating an external force such as bending force or friction force applied to the uncross-linked insulated electric wire 5, such as the step of reeling up the uncross-linked insulated electric wire 5 onto the drum before the cross linking.
(29) The kneading apparatus for use in manufacturing the resin composition of the present embodiment is not limited to the kneader, and a publicly-known kneading apparatus such as a batch-type kneader such as a Banbury mixer or a continuous-type kneader such as a twin-screw extruder can be adopted.
(30) <Feature and Effect of Present Embodiment>
(31) The resin composition according to an embodiment of the present invention contains (A) the base polymer and (B) the flame retardant. The (A) base polymer contains (A1) the polymer having the polar group. The (B) flame retardant of the present embodiment is made of (B1) the aluminum hydroxide, a surface of which is treated with a silane coupling agent, (B2) the aluminum hydroxide, a surface of which is treated with a treatment agent other than the silane coupling agent and/or (B3) the aluminum hydroxide, a surface of which is untreated. The resin composition according to the present embodiment contains the (B) flame retardant, a content of which is more than 40 parts by mass and equal to or less than 80 parts by mass per 100 parts by mass of the (A) the base polymer. The resin composition according to the present embodiment contains (B1) the aluminum hydroxide, a surface of which is treated with a silane coupling agent and a content of which is equal to or more than 10 parts by mass and equal to or less than 70 parts by mass per 100 parts by mass of (B) the flame retardant.
(32) As shown in
(33) The method of manufacturing the insulated electric wire according to the present embodiment includes (a) the step of forming the resin composition by kneading the base polymer and the flame retardant, (b) the step of manufacturing the uncross-linked insulated electric wire by extruding the resin composition so as to coat the periphery of the conductor to form the insulating layer, and (c) the step of manufacturing the cross-linked insulated electric wire by cross-linking the base polymer in the resin composition. The resin composition formed in the step (a) is the above-described resin composition of the present embodiment.
(34) By applying the configurations and the steps as described above, the present invention can provide the resin composition and the insulated electric wire each of which has the excellent whitening resistance, flame retardancy and flexibility in the uncross-linked state. A reason for this will be specifically described below.
(35) As described above, when the post cross linking mode is applied so that it is unnecessary to arrange the separator between the conductor and the insulating layer, it is necessary to reel up the uncross-linked insulated electric wire onto the drum or others, and the electric wire is scratched or whitened at this time. As a result, a problem that is degradation of the outer appearance of the insulated electric wire arises. In this case, it is considered that the whitening phenomenon are caused by peeling off on an interface between the resin (base polymer) to be the base material and the filler (such as the flame retardant) that disperses in the resin caused when the external force such as the bending or the friction force is applied to the material. Therefore, for the suppression of the whitening phenomenon, it is considered that adhesiveness between the resin and the filler is important.
(36) Regarding this point, the resin composition according to an embodiment of the present invention contains (A1) the polymer having the polar group as (A) the base polymer, and (B1) the aluminum hydroxide, a surface of which is treated with a silane coupling agent as (B) the flame retardant. The (B1) aluminum hydroxide, a surface of which is treated with a silane coupling agent, has an affinity for (A1) the polymer having the polar group, and therefore, the adhesiveness between (A) the base polymer and (B) the flame retardant can be enhanced. As a result, since the insulated electric wire of the present embodiment has the insulating layer made of this resin composition, the electric wire can be prevented from being scratched or whitened even when the surface of the uncross-linked insulated electric wire 5 chafes against the drum 29 shown in
(37) As described above, in the individual use of (B1) the aluminum hydroxide, a surface of which is treated with a silane coupling agent, the flexibility of the insulating layer of the insulated electric wire is reduced because of the too high affinity for (A1) the polymer having the polar group. Therefore, according to the present embodiment, (B) the flame retardant is configured so as to include not only (B1) the aluminum hydroxide, a surface of which is treated with a silane coupling agent, but also (B2) the aluminum hydroxide, a surface of which is treated with a treatment agent other than the silane coupling agent, and/or (B3) the aluminum hydroxide, a surface of which is untreated. In this manner, the resin composition of the present embodiment can enhance the adhesiveness between (A) the base polymer and (B) the flame retardant while ensuring the flame retardancy and the flexibility of the insulating layer of the insulated electric wire.
(38) In the above-described manner, the resin composition and the insulated electric wire of the present embodiment can provide the whitening resistance in the uncross-linked state, and, at the same time, can ensure the flame retardancy and the flexibility of the insulating layer of the insulated electric wire that are required for use in, for example, an in-board wiring of a distribution board/control board, a motor lead wire or others.
WORKING EXAMPLES
(39) The present invention will be described in more details below on the basis of the working examples. However, the present invention is not limited to be applied to these working examples.
(40) Each of insulated electric wires of working examples 1 to 12 and comparative examples 1 to 7 described below was configured as the insulated electric wire having the same configuration as that of the insulated electric wire 10 shown in
Raw Materials of Working Examples 1 to 12 and Comparative Examples 1 to 7
(41) The raw materials for use in the working examples 1 to 12 and the comparative examples 1 to 7 are shown in the later-described tables 2 to 4, and are only summarized below.
(42) (A) Base Polymer:
(43) (A1) Polymer having Polar Group: ethylene-vinyl acetate copolymer
(44) (A2) Other Polymer: ethylene-butene copolymer, ethylene-octene copolymer
(45) (B) Flame Retardant:
(46) (B1) Aluminum Hydroxide, a surface of which is treated with a silane coupling agent (abbreviated as silane treated in the table 2 and 3)
(47) (B2) Aluminum Hydroxide, a surface of which is treated with a fatty acid (abbreviated as fatty-acid-treated in the table 2 and 3)
(48) (B3) Aluminum Hydroxide, a surface of which is untreated (abbreviated as untreated in the table 2 and 3)
(49) (C) Cross-Linking Aid: trimethylolpropane trimethacrylate
(50) (D) Antioxidant:
(51) (D1) Phenol-based Antioxidant
(52) (D2) Sulfur-based Antioxidant
(53) (E) Copper Inhibitor: heavy metal deactivator
(54) (F) Lubricant: amide-based lubricant
(55) (G) Colorant:
(56) (G1) Carbon Black
(57) (G2) (Yellow) Color Masterbatch
(58) (G3) (Green) Color Masterbatch
Manufacturing Methods of Working Examples 1 to 12 and Comparative Examples 1 to 7
(59) Each sample of the working examples 1 to 12 and the comparative examples 1 to 7 was manufactured by the following method. In the table 1, note that the kneading condition of the single-screw extruder in each of the working examples 1 to 12 and the comparative examples 1 to 7 is summarized.
(60) TABLE-US-00001 TABLE 1 Classification Item Setting Extruder Size 65-mm single screw L/D 20 Temperature Cylinder 1 (Hopper side) 120 ( C.) Cylinder 2 125 Cylinder 3 130 Cylinder 4 135 Cylinder 5 140 Neck 160 Cross head 160 Die 160 Screw Rotational speed (rpm) 30 Shape Full flight type Reeling out Reeling-out speed (m/min) 50
(61) A compound was manufactured by kneading the raw materials of each of the working examples 1 to 12 and the comparative examples 1 to 7 shown in the later-described tables 2 and 3 in a kneader having an internal capacity of 25 L and was shaped into a pellet. The resin composition was extruded so as to coat the periphery of the conductor (tin-plated copper stranded wire) under the condition shown in the table 1 by using a single-screw extruder (corresponding to the extrusion coating apparatus 21 shown in
(62) Next, in the electron-beam irradiation apparatus, the uncross-linked insulated electric wire was reeled out of the drum, and was irradiated with the electron beams (having an acceleration voltage of 2 MV and an electron-beam irradiance level of 10 Mrad), so that the cross-linked insulated electric wire (corresponding to the insulated electric wire 10 shown in
Evaluating Method for Working Examples 1 to 12 and Comparative Examples 1 to 7
(63) An evaluating method for the working examples 1 to 12 and the comparative examples 1 to 7 will be described below. Evaluated items (1) to (3) described below were comprehensively determined so that a sample that passed all the evaluated items was evaluated as (passed) while a sample that failed even one item was evaluated as X (failed), and the samples were shown in the later-described tables 2 and 3.
(64) (1) Whitening by Friction
(65) The whitening by friction at the time of the manufacture of the electric wire was evaluated by visual observation of the surface of the uncross-linked insulated electric wire reeled up on the drum (corresponding to the uncross-linked insulated electric wire 5 reeled up on the drum 29 shown in
(66) (2) Oxygen Index (Flame Retardancy)
(67) The above-described compound was shaped into a sheet piece having a thickness of 3 mm by using a thermal pressing machine at 160 C. This sheet piece was irradiated with the electron beams having the same condition (an acceleration voltage of 2 MV and an electron-beam irradiation level of 10 Mrad) as that of the electric-wire cross linking step by using the electron-beam irradiation apparatus, so that a cross-linked sheet piece was manufactured. Then, an oxygen index of this cross-linked sheet piece was measured by a method using an OXYGEN INDEXER (produced by Toyo Seiki Co., Ltd.) and defined in JIS K7201-2 (2007). A sample having an oxygen index that is equal to or larger than 20 was evaluated as a sample having sufficient flame retardancy to be (passed) while a sample having an oxygen index that is smaller than 20 was evaluated as a sample having insufficient flame retardancy to be as X (failed).
(68) (3) Tensile Strength in 100% Tension (Flexibility)
(69) A conductor was pulled out of the cross-linked electric wire, and was cut to have a length of 150 mm, and a tubular test piece having gauge lines with a 50-mm gap therebetween at a center was prepared. A tensile load was measured when 100% tension between the gauge lines of this tubular test piece was performed under a condition of a tensile speed of 200 mm/min., by using a Schopper tensile strength tester, and a tensile strength was calculated from the following expression 1. A sample having a tensile strength in 100% tension that is equal to or smaller than 6.0 MPa was evaluated as a sample having sufficient flexibility to be (passed) while a sample having a tensile strength in 100% tension that is larger than 6.0 MPa was evaluated as a sample having insufficient flexibility to be X (failed).
=F/A (: tensile strength [MPa], F: tensile load [N], A: test-piece cross-sectional area [mm.sup.2])(Expression 1)
Evaluating Results of Working Examples 1 to 12 and Comparative Examples 1 to 7
(70) Evaluating results based on the above-described evaluating method are summarized in the tables 2 and 3.
(71) TABLE-US-00002 TABLE 2 Working Working Working Working Blend example 1 example 2 example 3 example 4 (A) Base (A1) Polymer (A1) Ethylene-vinyl 40 40 40 40 polymer having polar acetate copolymer group (VA amount 15 wt. %) *1 (A1) Ethylene-vinyl 20 20 20 20 acetate copolymer (VA amount 28 wt. %) *2 (A2) Other (A2) Ethylene-butane 40 40 40 40 polymer copolymer *3 (A2) Ethylene-octane copolymer *4 (B) Flame (B) Aluminum (B1) Silane treated 8 24 40 56 retardant hydroxide (B2) Fatty-acid 72 56 40 24 treated (B3) Untreated Other (C) Cross trimethylolpropane 2 2 2 2 components lining aid trimethacrylate (D) Antioxidant (D1) Phenol-based 0.6 0.6 0.6 0.6 antioxidant (D2) Sulfur-based 1.2 1.2 1.2 1.2 antioxidant (E) Copper Heavy metal 0.5 0.5 0.5 0.5 inhibitor deactivator (F) Lubricant Amide-based lubricant 1 1 1 1 (G) Colorant (G1) Carbon black *5 5 5 5 5 (G1) (Yellow) color masterbatch *6 (G3) (Green) color masterbatch *7 Blend Ratio of (B) Frame retardant per 100 parts by mass of (A) 80 80 80 80 ratio Base polymer Ratio of (B1) Silane-treated aluminum hydroxide per 100 10 10 10 10 parts by mass of (B) Flame retardant Evaluation Property (1) Whitening by Friction on Uncross-linked Electric Wire Surface after Reeling Up on Drum (slightly) (not (not (not observed) observed) observed) observed) (2) Oxygen index (Evaluation on sheet) (24.0) (23.9) (23.7) (23.9) (3) Tensile strength in 100% Tension (MPa) (4.3) (4.8) (5.5) (5.9) Determination Working Working Working Working Blend example 5 example 6 example 7 example 8 (A) Base (A1) Polymer (A1) Ethylene-vinyl 40 40 40 40 polymer having polar acetate copolymer group (VA amount 15 wt. %) *1 (A1) Ethylene-vinyl 20 20 20 20 acetate copolymer (VA amount 28 wt. %) *2 (A2) Other (A2) Ethylene-butane 40 40 40 40 polymer copolymer *3 (A2) Ethylene-octane copolymer *4 (B) Flame (B) Aluminum (B1) Silane treated 6 8 8 8 retardant hydroxide (B2) Fatty-acid 54 72 72 treated (B3) Untreated 72 Other (C) Cross trimethylolpropane 2 2 2 2 components lining aid trimethacrylate (D) Antioxidant (D1) Phenol-based 0.6 0.6 0.6 0.6 antioxidant (D2) Sulfur-based 1.2 1.2 1.2 1.2 antioxidant (E) Copper Heavy metal 0.5 0.5 0.5 0.5 inhibitor deactivator (F) Lubricant Amide-based lubricant 1 1 1 1 (G) Colorant (G1) Carbon black *5 5 5 (G1) (Yellow) color 5 masterbatch *6 (G3) (Green) color 5 masterbatch *7 Blend Ratio of (B) Frame retardant per 100 parts by mass of (A) 80 80 80 80 ratio Base polymer Ratio of (B1) Silane-treated aluminum hydroxide per 100 10 10 10 10 parts by mass of (B) Flame retardant Evaluation Property (1) Whitening by Friction on Uncross-linked Electric Wire Surface after Reeling Up on Drum (not (slightly (not (not observed) observed) observed) observed) (2) Oxygen index (Evaluation on sheet) (21.8) (24.1) (23.7) (23.8) (3) Tensile strength in 100% Tension (MPa) (3.8) (4.6) (4.1) (4.0) Determination *1 MFR (g/10 min@190 C., 2.16 kgf): 0.8, Melting point: 89 C. *2 MFR (g/10 min@190 C., 2.16 kgf): 6.0, Melting point: 72 C. *3 MFR (g/10 min@190 C., 2.16 kgf): 3.6, Melting point: 66 C. *4 MFR (g/10 min@190 C., 2.16 kgf): 0.5, Melting point: 49 C. *5 Thermal carbon, Average Particle Diameter: 80 nm *6 Masterbatch blended with Condensed Azo-base Pigment *7 Masterbatch blended with Phthalocyanine-Blue- and Monoazo-Yellow-base Pigment Mixture
(72) TABLE-US-00003 TABLE 3 Comparative Comparative Comparative Comparative Blend example 1 example 2 example 3 example 4 (A) Base (A1) Polymer (A1) Ethylene-vinyl 40 40 40 40 polymer having polar acetate copolmer group (VA amount 15 wt. %) *1 (A1) Ethylene-vinyl 20 20 20 20 acetate copolymer (VA amount 28 wt. %) *2 (A2) Other (A2) Ethylene-butane 40 40 40 40 polymer copolymer *3 (A2) Ethylene-octane copolymer *4 (B) Flame (B) Aluminum (B1) Silane treated 4 64 4 retardant hydroxide (B2) Fatty-acid 80 76 16 36 treated (B3) Untreated Other (C) Cross trimethylolpropane 2 2 2 2 components lining aid trimethacrylate (D) Antioxidant (D1) Phenol-based 0.6 0.6 0.6 0.6 antioxidant (D2) Sulfur-based 1.2 1.2 1.2 1.2 antioxidant (E) Copper Heavy metal deactivator 0.5 0.5 0.5 0.5 inhibitor (F) Lubricant Amide-based lubricant 1 1 1 1 (G) Colorant (G1) Carbon black *5 5 5 5 5 (G2) (Yellow) color masterbatch *6 (G3) (Green) color masterbatch *7 Blend Ratio of (B) Flame retardant per 100 parts by mass of (A) 80 80 80 40 ratio Base polymer Ratio of (B1) Silane-treated aluminum hydroxide per 100 0 5 80 10 parts by mass of (B) Flame retardent Evaluation Property (1) Whitening by Friction on Uncross-linked Electric Wire X X Surface after Reeling Up on Drum (observed) (observed) (not (not observed) observed) (2) Oxygen index (Evaluation on sheet) X (23.6) (23.8) (23.8) (19.8) (3) Tensile strength in 100% Tensile (MPa) X (3.6) (3.9) (6.6) (3.1) Determination X X X X Comparative Comparative Comparative Blend example 5 example 6 example 7 (A) Base (A1) Polymer (A1) Ethylene-vinyl 40 40 polymer having polar acetate copolmer group (VA amount 15 wt. %) *1 (A1) Ethylene-vinyl 20 20 acetate copolymer (VA amount 28 wt. %) *2 (A2) Other (A2) Ethylene-butane 40 40 40 polymer copolymer *3 (A2) Ethylene-octane 40 copolymer *4 (B) Flame (B) Aluminum (B1) Silane treated 3 2 8 retardant hydroxide (B2) Fatty-acid 57 38 72 treated (B3) Untreated Other (C) Cross trimethylolpropane 2 2 2 components lining aid trimethacrylate (D) Antioxidant (D1) Phenol-based 0.6 0.6 0.6 antioxidant (D2) Sulfur-based 1.2 1.2 1.2 antioxidant (E) Copper Heavy metal deactivator 0.5 0.5 0.5 inhibitor (F) Lubricant Amide-based lubricant 1 1 1 (G) Colorant (G1) Carbon black *5 5 5 5 (G2) (Yellow) color masterbatch *6 (G3) (Green) color masterbatch *7 Blend Ratio of (B) Flame retardant per 100 parts by mass of (A) 60 40 80 ratio Base polymer Ratio of (B1) Silane-treated aluminum hydroxide per 100 5 5 10 parts by mass of (B) Flame retardent Evaluation Property (1) Whitening by Friction on Uncross-linked Electric Wire X X Surface after Reeling Up on Drum (observed) (slightly (observed) observed) (2) Oxygen index (Evaluation on sheet) X (21.5) (19.6) (22.1) (3) Tensile strength in 100% Tensile (MPa) (3.1) (3.0) (2.9) Determination X X X *1 MFR (g/10 min@190 C., 2.16 kgf): 0.8, Melting point: 89 C. *2 MFR (g/10 min@190 C., 2.16 kgf): 6.0, Melting point: 72 C. *3 MFR (g/10 min@190 C., 2.16 kgf): 3.6, Melting point: 66 C. *4 MFR (g/10 min@190 C., 2.16 kgf): 0.5, Melting point: 49 C. *5 Thermal carbon, Average Particle Diameter: 80 nm *6 Masterbatch blended with Condensed Azo-base Pigment *7 Masterbatch blended with Phthalocyanine-Blue- and Monoazo-Yellow-base Pigment Mixture PGPubs, use the Gap Bulletin per PTO.
(73) TABLE-US-00004 TABLE 4 Working Working Working Working example example example example Blend 9 10 11 12 (A) Base (A1) Polymer (A1) Ethylene-vinyl 40 40 40 40 polymer having polar acetate copolmer group (VA amount 15 wt. %) *1 (A1) Ethylene-vinyl 20 20 20 20 acetate copolymer (VA amount 28 wt. %) *2 (A2) Other (A2) Ethylene-butane 40 40 40 40 polymer copolymer *3 (A2) Ethylene-octane copolymer *4 (B) Flame (B) Aluminum (B1) Silane treated 8 8 8 8 retardant hydroxide (B2) Fatty-acid 72 72 72 72 treated (B3) Untreated Other (C) Cross trimethylolpropane 2 2 2 2 components lining aid trimethacrylate (D) Antioxidant (D1) Phenol-based 0.6 0.6 0.6 0.6 antioxidant (D2) Sulfur-based 1.2 1.2 1.2 1.2 antioxidant (E) Copper Heavy metal deactivator 0.5 0.5 0.5 0.5 inhibitor (F) Lubricant Amide-based lubricant 1 1 1 1 (G) Colorant (G1) (White) color 5 masterbatch *5 (G2) (Red) color 5 masterbatch *6 (G3) (Black) color 5 masterbatch *7 Blend Ratio of (B) Flame retardant per 100 parts by mass of (A) 80 80 80 80 ratio Base polymer Ratio of (B1) Silane-treated aluminum hydroxide per 100 10 10 10 10 parts by mass of (B) Flame retardent Evaluation Property (1) Whitening by Friction on Uncross-linked Electric Wire Surface after Reeling Up on Drum (not (not (not (not observed) observed) observed) observed) (2) Oxygen index (Evaluation on sheet) (23.3) (23.9) (23.7) (23.9) (3) Tensile strength in 100% Tensile (MPa) (3.8) (4.2) (4.0) (4.2) Determination *1 MFR (g/10 min@190 C., 2.16 kgf): 0.8, Melting point: 89 C. *2 MFR (g/10 min@190 C., 2.16 kgf): 6.0, Melting point: 72 C. *3 MFR (g/10 min@190 C., 2.16 kgf): 3.6, Melting point: 66 C. *4 MFR (g/10 min@190 C., 2.16 kgf): 0.5, Melting point: 49 C. *5 Masterbatch blended with Titanium Oxide, produced by Dainichiseika Color & Chemicals Mfg. Co., Ltd. *6 Masterbatch blended with Mono-Azo-Red- and Quinacridone-Red-base Pigment, produced by Dainichiseika Color & Chemicals Mfg. Co., Ltd. *7 Masterbatch blended with Carbon Black, produced by Toyo Ink Co., Ltd.
(74) As shown in the tables 2 and 4, the working examples 1 to 12 passed all (1) the fraction whitening property, (2) the oxygen index (flame retardancy) and (3) the tensile strength in 100% tension (flexibility), and were evaluated as (passed). On the other hand, as shown in the table 3, the comparative examples 1 to 7 were evaluated as X (failed). Specifically, the comparative examples 1, 2, 5 and 7 failed (1) the fraction whitening property, the comparative examples 4 and 6 failed (2) the oxygen index (flame retardancy), and the comparative example 3 failed (3) the tensile strength in 100% tension (flexibility).
(75) Each sample of the working examples 1 to 12 contains (A1) the polymer having the polar group as (A) the base polymer, contains (B) the flame retardant, a content of which is more than 40 parts by mass and equal to or less than 80 parts by mass per 100 parts by mass of (A) the base polymer, and contains (B1) the aluminum hydroxide, a surface of which is treated with a silane coupling agent and a content of which is equal to or more than 10 parts by mass and equal to or less than 70 parts by mass per 100 parts by mass of (B) the flame retardant. In this manner, it has been found that the resin composition having the excellent whitening resistance, flame retardancy and flexibility in the uncross-linked state can be obtained. It has been found that, when the insulating layer of the insulated electric wire is made of this resin composition, the insulated electric wire having the excellent whitening resistance, flame retardancy and flexibility in the uncross-linked state can be obtained. And, it has been found that the insulated electric wire having the excellent whitening resistance, flame retardancy and flexibility in the uncross-linked state can be manufactured by the method of manufacturing the insulated electric wire according to the present embodiment.
(76) More specifically, from the results of the working examples 1 to 12 and the comparative examples 1, 2, 5 and 7, it has been found that, in order to meet the requirement of the whitening resistance, it is necessary that the resin composition should contain (B1) the aluminum hydroxide, a surface of which is treated with a silane coupling agent and a content of which is equal to or more than 10 parts by mass per 100 parts by mass of (B) the flame retardant, and contain (A1) the polymer having the polar group as (A) the base polymer.
(77) Particularly, as shown in the comparative example 7, it has been found as follow. Even when (B1) the aluminum hydroxide, a surface of which is treated with a silane coupling agent, is used, if (A) the base polymer does not contain (A1) the polymer having the polar group, the requirement of the whitening resistance cannot be met. As shown in the comparative example 1, it has been found that the requirement of the whitening resistance cannot be met even when (B2) the aluminum hydroxide, a surface of which is treated with a fatty acid, is used instead of (B1) the aluminum hydroxide, a surface of which is treated with a silane coupling agent.
(78) As shown in the comparative example 6, note that it has been found as follow. When the content of (B) the flame retardant of the resin composition is less than 40 parts by mass, even if the content of (B1) the aluminum hydroxide, a surface of which is treated with a silane coupling agent, is not equal to or more than 10 parts by mass per 100 parts by mass of (B) the flame retardant, the sample passes the whitening resistance test.
(79) From the results of the working examples 1 to 12 and the comparative examples 4 and 6, it has been found that, in order to meet the requirement of the flame retardancy, it is necessary that the resin composition should contain (B) the flame retardant, a content of which is more than 40 parts by mass per 100 parts by mass of (A) the base polymer.
(80) From the results of the working examples 1 to 12 and the comparative example 3, it has been found that, in order to meet the requirement of the flexibility, it is necessary that the resin composition should contain (B1) the aluminum hydroxide, a surface of which is treated with a silane coupling agent and a content of which is less than 70 parts by mass per 100 parts by mass of (B) the flame retardant.
(81) Meanwhile, from the results of the working examples 1 and 6, it has been found that the resin composition may contain not only (B1) the aluminum hydroxide, a surface of which is treated with a silane coupling agent, but also whether (B2) the aluminum hydroxide, a surface of which is treated with a fatty acid or (B3) the aluminum hydroxide, a surface of which is untreated, as the component making up (B) the flame retardant. From this result, it is considered that (B2) the aluminum hydroxide, a surface of which is treated with the fatty acid and (B3) the aluminum hydroxide, a surface of which is untreated, can be blended in an any ratio.
(82) From the results of the working examples 1, 7, 8 and 10 to 12, at least in black-hue, white-hue, red-hue, yellow-hue and green-hue insulating layers of the insulated electric wires, it has been found that the insulated electric wire having the excellent whitening resistance, flame retardancy and flexibility in the uncross-linked state can be manufactured without change in the blend ratio of the materials except for (G) the colorant regardless of a type of (G) the colorant. From the result of the working example 9, it has been found that, even when (G) the colorant is not added, the insulated electric wire having the excellent whitening resistance, flame retardancy and flexibility in the uncross-linked state can be manufactured.
(83) The present invention is not limited to the foregoing embodiments and working examples, and various alterations can be made within the scope of the present invention.