Resin composition, electric wire, and electric cable

Abstract

The resin composition of the present invention comprises a copolymer of structural units derived from ethylene and structural units derived from α-olefins having carbonyl groups, a brominated flame retardant, and antimony trioxide. In the resin composition, the copolymer is present in an amount of 20% by mass or more and 60% by mass or less. In the resin composition, the brominated flame retardant is present in an amount of 10% by mass or more and 30% by mass or less. In the resin composition, the antimony trioxide is present in an amount of 2% by mass or more and 15% by mass or less. The resin composition further comprises at least two compounds selected from the group consisting of a first compound, a second compound, and a third compound. In the resin composition, each of the at least two compounds selected from the group consisting of the first compound, the second compound, and the third compound is present in an amount of 0.01% by mass or more and 1.5% by mass or less. The highest absorption peak in the ultraviolet absorption spectrum of the first compound is located in the region of 320 nm or more and 360 nm or less. The highest absorption peak in the ultraviolet absorption spectrum of the second compound is located in the region of 275 nm or more and less than 320 nm. The highest absorption peak in the ultraviolet absorption spectrum of the third compound is located in the region of 240 nm or more and less than 275 nm.

Description

Technical Field

[0001] This disclosure relates to resin compositions, wires, and cables. Background Technology

[0002] In the past, “wires having conductors and a coating covering the conductors” and “cables having core wires and a coating covering the core wires” were used in automobiles and the like. The materials for the coating and the coating were “resin compositions comprising a copolymer of structural units from ethylene and structural units from α-olefins having carbonyl groups, a brominated flame retardant, and antimony trioxide” (Patent Document 1).

[0003] Existing technical documents Patent documents Patent Document 1: International Publication No. 2015 / 159788 Summary of the Invention

[0004] The resin composition disclosed herein comprises a copolymer of structural units derived from ethylene and structural units derived from α-olefins having carbonyl groups, a brominated flame retardant, and antimony trioxide. In the resin composition, the copolymer is present in an amount of 20% by mass or more and 60% by mass or less; the brominated flame retardant is present in an amount of 10% by mass or more and 30% by mass or less; and the antimony trioxide is present in an amount of 2% by mass or more and 15% by mass or less. The resin composition further comprises at least two compounds selected from the group consisting of a first compound, a second compound, and a third compound. In the resin composition, at least two compounds selected from the group consisting of the first compound, the second compound, and the third compound each have a content of 0.01% by mass or more and 1.5% by mass or less, the highest absorption peak in the ultraviolet absorption spectrum of the first compound is located in the region of 320 nm or more and 360 nm or less, the highest absorption peak in the ultraviolet absorption spectrum of the second compound is located in the region of 275 nm or more and less than 320 nm, and the highest absorption peak in the ultraviolet absorption spectrum of the third compound is located in the region of 240 nm or more and less than 275 nm. Attached Figure Description

[0005] Figure 1 This is a schematic perspective view of an electrical wire according to one embodiment of the present disclosure.

[0006] Figure 2 It is along Figure 1 Schematic sectional view of II-II.

[0007] Figure 3 This is a schematic diagram illustrating a part of the evaluation method for heat resistance testing.

[0008] Figure 4 This is a schematic diagram illustrating a part of the evaluation method for flame retardancy testing.

[0009] Figure 5 This is a schematic diagram illustrating a part of the evaluation method for tensile testing.

[0010] Figure 6 This is a schematic cross-sectional view showing the configuration of a cable according to one embodiment of the present disclosure. Detailed Implementation

[0011] [The problem this disclosure aims to solve] When wires and cables are used in applications such as automobiles, the operating conditions can sometimes be very demanding. In particular, considering the high temperatures and susceptibility to weather-related factors (such as sunlight) in these operating conditions, wires and cables are prone to deterioration due to temperature and these factors. Therefore, it is necessary to improve their heat resistance, flame retardancy, and resistance to these factors (in other words, "weather resistance"). Furthermore, excellent elongation is required as a characteristic of wires and cables. Regarding heat resistance and flame retardancy, it is known that resin compositions containing copolymers of structural units from ethylene and structural units from α-olefins having carbonyl groups, brominated flame retardants, and antimony trioxide can improve the heat resistance and flame retardancy of wires and cables. However, while the inclusion of brominated flame retardants and antimony trioxide in the resin composition readily improves the heat resistance and flame retardancy of the wires, sometimes the elongation of the wires and cables becomes insufficient.

[0012] Furthermore, regarding weather resistance, since sunlight contains wavelengths in the ultraviolet (UV) region, it is required that the sheath or coating of the wire readily absorbs UV light with wavelengths below 400 nm to improve weather resistance. As a method to make the sheath or coating of the wire readily absorb UV light with wavelengths below 400 nm, it is known to use carbon black or the like in the raw materials of the sheath or coating to make it black. On the other hand, sometimes it is required that the color of the sheath or coating be other than black. However, it is not yet known to have a UV absorber that can make the color of the sheath or coating other than black and that makes it readily absorb UV light with wavelengths below 400 nm. Therefore, for example, when it is required that the color of the sheath or coating be other than black, it is sometimes difficult to impart excellent weather resistance to the wire or cable. Therefore, it is required to impart excellent weather resistance to the wire or cable using methods other than making the sheath black.

[0013] In summary, it is sometimes difficult to impart excellent heat resistance, excellent flame retardancy, excellent elongation, and excellent weather resistance to wires and cables. Therefore, the object of this disclosure is to provide a resin composition, a wire, and a cable comprising the wire, capable of manufacturing wires possessing excellent heat resistance, excellent flame retardancy, excellent elongation, and excellent weather resistance. It should be noted that, in this disclosure, "weather resistance" refers to durability against weather-related factors (such as sunlight).

[0014] [Effects of this disclosure] According to this disclosure, a resin composition, the wire, and the cable are provided that can manufacture wires and cables with excellent heat resistance, excellent flame retardancy, excellent elongation, and excellent weather resistance.

[0015] [Description of embodiments of this disclosure] First, the implementation plan disclosed herein will be listed for illustration.

[0016] (1) The resin composition of this disclosure comprises a copolymer of structural units from ethylene and structural units from α-olefins having carbonyl groups, a brominated flame retardant, and antimony trioxide, wherein the copolymer is present in an amount of 20% by mass or more and 60% by mass or less, the brominated flame retardant is present in an amount of 10% by mass or more and 30% by mass or less, and the antimony trioxide is present in an amount of 2% by mass or more and 15% by mass or less, and the resin composition further comprises at least two compounds selected from the group consisting of a first compound, a second compound, and a third compound. In the resin composition, at least two of the compounds selected from the group consisting of the first compound, the second compound, and the third compound each have a content of 0.01% by mass or more and 1.5% by mass or less, the highest absorption peak in the ultraviolet absorption spectrum of the first compound is located in the region of 320 nm or more and 360 nm or less, the highest absorption peak in the ultraviolet absorption spectrum of the second compound is located in the region of 275 nm or more and less than 320 nm, and the highest absorption peak in the ultraviolet absorption spectrum of the third compound is located in the region of 240 nm or more and less than 275 nm.

[0017] According to this disclosure, a resin composition, the wire, and the cable are provided that can manufacture wires and cables with excellent heat resistance, excellent flame retardancy, excellent elongation, and excellent weather resistance.

[0018] (2) In (1) above, the first compound may be a compound represented by Formula 1 below, the second compound may be a compound represented by Formula 2 below, and the third compound may be a compound represented by Formula 3 below. Thus, a resin composition, the wire, and the cable that can be provided can be used to manufacture wires and cables with superior heat resistance, superior flame retardancy, superior elongation, and superior weather resistance. In Formula 1, R1 is a hydrogen atom or a halogen atom, R2 is a hydrogen atom or a hydrocarbon group, and R3 is a hydrogen atom or a hydrocarbon group. In Formula 3, R4 is a hydrocarbon group.

[0019] (3) In (2) above, R1 may be a hydrogen atom or a chlorine atom, R2 may be a hydrogen atom, a methyl group or a group represented by Formula 1d below, and R3 may be a hydrogen atom or a group represented by Formula 1e below. Thus, a resin composition, the wire, and the cable that can be provided can be used to manufacture wires and cables with superior heat resistance, superior flame retardancy, superior elongation, and superior weather resistance. (4) In any of (1) to (3) above, the first compound may be at least one compound selected from the group consisting of the compound shown in Formula 1a, the compound shown in Formula 1b, and the compound shown in Formula 1c. Thus, a resin composition, the wire, and the cable that can be provided can be used to manufacture wires and cables with superior heat resistance, superior flame retardancy, superior elongation, and superior weather resistance. (5) In (4) above, the first compound may also be the compound represented by formula 1a. Thus, a resin composition, the wire, and the cable that can be provided can be used to manufacture wires and cables with superior heat resistance, superior flame retardancy, superior elongation, and superior weather resistance.

[0020] (6) In any of (1) to (5) above, R4 may be a hydrocarbon group having 4 or more carbon atoms. Thus, a resin composition, the wire, and the cable that can be provided can be used to manufacture wires and cables with superior heat resistance, superior flame retardancy, superior elongation, and superior weather resistance.

[0021] (7) In any of (1) to (6) above, the R4 may also be a linear -C 16 H 33 Based on this, a resin composition, the wire, and the cable are provided that can be used to manufacture wires and cables with superior heat resistance, superior flame retardancy, superior elongation, and superior weather resistance.

[0022] (8) In any of (1) to (7) above, the resin composition may further comprise a hindered amine light stabilizer, which is a compound having the structure shown in Formula 4 below, wherein the hindered amine light stabilizer is present in a content of 0.1% by mass or more and 1.5% by mass or less in the resin composition. Thus, a resin composition, the wire, and the cable that can be provided for manufacturing wires and cables with superior heat resistance, superior flame retardancy, superior elongation, and superior weather resistance can be provided. (9) In (8) above, the hindered amine light stabilizer may also be a compound composed of structural units represented by the following formula 4a. Thus, a resin composition, the wire, and the cable that can be provided can be used to manufacture wires and cables with superior heat resistance, superior flame retardancy, superior elongation, and superior weather resistance. (10) The wire of the present disclosure has a conductor and a coating covering the conductor, the coating comprising a first layer formed of a resin composition as described in (1) to (9) above.

[0023] This allows for the provision of wires that possess excellent heat resistance, excellent flame retardancy, excellent elongation, and excellent weather resistance.

[0024] (11) The cable of the present disclosure has a core wire and a coating covering the core wire, the core wire including a plurality of wires, the coating including a first A layer located on the surface of the coating, the first A layer being formed of a resin composition as described in (1) to (9) above.

[0025] This allows for the provision of cables that combine excellent heat resistance, excellent flame retardancy, excellent elongation, and excellent weather resistance.

[0026] [Details of the embodiments disclosed herein] Hereinafter, specific examples of a resin composition, wire, and cable according to one embodiment of the present disclosure (hereinafter also referred to as "this embodiment") will be described with reference to the accompanying drawings. In the drawings of this disclosure, the same reference numerals denote the same or equivalent parts. Furthermore, dimensional relationships such as length, width, thickness, and depth have been appropriately modified for clarity and simplification of the drawings and do not necessarily represent actual dimensional relationships.

[0027] In this disclosure, the expression "A~B" refers to the upper and lower limits of the range (i.e., above A and below B). If there is no unit recorded at A but only at B, the unit of A is the same as the unit of B.

[0028] In this disclosure, when compounds are represented by chemical formulas, it is assumed that all previously known atomic ratios are included without particularly limiting the atomic ratios, and it should not be limited to atomic ratios within the stoichiometric range.

[0029] [Embodiment 1: Resin Composition] A resin composition according to one embodiment of the present disclosure will be described.

[0030] One embodiment of this disclosure (hereinafter also referred to as "this embodiment") is a resin composition comprising a copolymer of structural units from ethylene and structural units from α-olefins having carbonyl groups, a brominated flame retardant, and antimony trioxide. In this resin composition, the copolymer is present in an amount of 20% by mass or more and 60% by mass or less; the brominated flame retardant is present in an amount of 10% by mass or more and 30% by mass or less; and the antimony trioxide is present in an amount of 2% by mass or more and 15% by mass or less. The resin composition further comprises a compound selected from a first compound, a second compound, and a third compound. In the resin composition, at least two compounds selected from the group consisting of the first compound, the second compound, and the third compound are present in a content of 0.01% by mass or more and 1.5% by mass or less. The highest absorption peak in the ultraviolet absorption spectrum of the first compound is located in the region of 320 nm or more and 360 nm or less. The highest absorption peak in the ultraviolet absorption spectrum of the second compound is located in the region of 275 nm or more and less than 320 nm. The highest absorption peak in the ultraviolet absorption spectrum of the third compound is located in the region of 240 nm or more and less than 275 nm.

[0031] According to this disclosure, a resin composition, the wire, and the cable can be provided that can manufacture wires and cables possessing excellent heat resistance, excellent flame retardancy, excellent elongation, and excellent weather resistance. The reasons for this are speculated as follows.

[0032] (a) The resin composition of this embodiment comprises a copolymer of structural units from ethylene and structural units from α-olefins having carbonyl groups, a brominated flame retardant, and antimony trioxide. In this resin composition, the copolymer is present in an amount of 20% by mass or more and 60% by mass or less; the brominated flame retardant is present in an amount of 10% by mass or more and 30% by mass or less; and the antimony trioxide is present in an amount of 2% by mass or more and 15% by mass or less. Accordingly, due to the moderate inclusion of the brominated flame retardant and antimony trioxide relative to the copolymer, wires and cables exhibiting excellent heat resistance, excellent flame retardancy, and excellent elongation can be manufactured from this resin composition.

[0033] (b) The resin composition further comprises at least two compounds selected from the group consisting of the first compound, the second compound, and the third compound, wherein the content of each of the at least two compounds selected from the group consisting of the first compound, the second compound, and the third compound is 0.01% by mass or more and 1.5% by mass or less, the highest absorption peak in the ultraviolet absorption spectrum of the first compound is located in the region of 320 nm or more and 360 nm or less, the highest absorption peak in the ultraviolet absorption spectrum of the second compound is located in the region of 275 nm or more and less than 320 nm, and the highest absorption peak in the ultraviolet absorption spectrum of the third compound is located in the region of 240 nm or more and less than 275 nm. Therefore, because it can easily absorb ultraviolet light over a wide range of wavelengths below 400 nm, wires and cables with excellent weather resistance can be manufactured using this resin composition.

[0034] In summary, a resin composition, the wire, and a cable having the wire are provided that can manufacture wires and cables with excellent heat resistance, excellent flame retardancy, excellent elongation, and excellent weather resistance.

[0035] Copolymer The resin composition comprises a copolymer of structural units derived from ethylene and structural units derived from α-olefins having carbonyl groups. In the resin composition, the copolymer is present in an amount of 20% by mass or more and 60% by mass or less. Alternatively, the copolymer may be present in an amount of 22% by mass or more and 55% by mass or less, or 25% by mass or more and 50% by mass or less. Here, "structural unit" refers to a repeating unit constituting the polymer. The polymer, except for its ends, is composed of repeating bonds of the same or different structural units.

[0036] In the resin composition, the content of structural units from ethylene and structural units from α-olefins with carbonyl groups can be determined based on the elemental ratio of organic and inorganic components obtained by EDX (Energy Dispersive X-ray spectroscopy) elemental analysis, chemical structure analysis obtained by Fourier transform infrared spectroscopy (FT-IR), and the heat of melting for crystallization obtained by differential scanning calorimetry (DSC).

[0037] Examples of α-olefins containing a carbonyl group include alkyl (meth)acrylates, aryl (meth)acrylates, vinyl esters, unsaturated acids, vinyl ketones, and (meth)acrylamide. Examples of alkyl (meth)acrylates include methyl (meth)acrylate and ethyl (meth)acrylate. Examples of aryl (meth)acrylates include phenyl (meth)acrylate. Examples of vinyl esters include vinyl acetate and vinyl propionate. Examples of unsaturated acids include (meth)acrylic acid, crotonic acid, maleic acid, and itaconic acid. Examples of vinyl ketones include methyl vinyl ketone and phenyl vinyl ketone. (Meth)acrylic acid refers to acrylic acid or methacrylic acid.

[0038] Compared to the aforementioned copolymers, the proportion of structural units derived from carbonyl α-olefins can be 5% by mass or more and 30% by mass or less. When this proportion is less than 5% by mass, the flexibility of cables having a conductor and a coating covering the conductor is prone to damage. When this proportion exceeds 30% by mass, the mechanical properties of the coating, such as tensile strength, tend to decrease in wires having a conductor and a coating covering the conductor. Furthermore, in cables having a core wire and a coating covering the core wire, the mechanical properties of the coating, such as tensile strength, tend to decrease.

[0039] The proportion of structural units from α-olefins with carbonyl groups relative to the above copolymers can be determined based on the intensity of the absorption peak of the carbonyl group in the infrared absorption spectrum.

[0040] Brominated flame retardants The resin composition contains a brominated flame retardant. The content of the brominated flame retardant in the resin composition is 10% by mass or more and 30% by mass or less. Therefore, the resin composition imparts excellent flame retardancy and excellent mechanical properties to wires and cables. The content of the brominated flame retardant in the resin composition may also be 12% by mass or more and 28% by mass or less, 15% by mass or more and 25% by mass or less, or 17% by mass or more and 20% by mass or less. Examples of brominated flame retardants include ethylene bis(pentabromobenzene) and ethylene bis(tetrabromophthalimide).

[0041] The content of brominated flame retardants in a resin composition can be determined by the following methods. The bromine content can be determined based on elemental analysis such as EDX and ICP (Inductively Coupled Plasma Emission Spectroscopy).

[0042] Antimony trioxide The resin composition contains antimony trioxide (Sb₂O₃). The content of antimony trioxide in the resin composition is 2% by mass or more and 15% by mass or less. Therefore, the resin composition imparts excellent flame retardancy and excellent mechanical properties to wires and cables. The content of antimony trioxide in the resin composition may also be 3% by mass or more and 13% by mass or less, 4% by mass or more and 10% by mass or less, or 5% by mass or more and 8% by mass or less.

[0043] The content of antimony trioxide in the resin composition can be determined by the following methods. It can be determined based on elemental analysis such as EDX and ICP emission spectroscopy.

[0044] Compound I, Compound II, and Compound III The resin composition further comprises at least two compounds selected from the group consisting of the first compound, the second compound, and the third compound. In the resin composition, the content of each of the at least two compounds selected from the group consisting of the first compound, the second compound, and the third compound is 0.01% by mass or more and 1.5% by mass or less. The highest absorption peak in the ultraviolet absorption spectrum of the first compound is located in the region of 320 nm or more and 360 nm or less. The highest absorption peak in the ultraviolet absorption spectrum of the second compound is located in the region of 275 nm or more and less than 320 nm. The highest absorption peak in the ultraviolet absorption spectrum of the third compound is located in the region of 240 nm or more and less than 275 nm. Therefore, the resin composition imparts excellent weather resistance to wires and cables. The content of each of the at least two compounds selected from the group consisting of the first compound, the second compound, and the third compound may also be 0.015% by mass or more and 1.3% by mass or less, 0.01% by mass or more and 1.1% by mass or less, or 0.02% by mass or more and 1.0% by mass or less.

[0045] The total content of at least two compounds selected from the group consisting of the first compound, the second compound, and the third compound can be 0.2% by mass or more and 2.0% by mass or less. This further improves the weather resistance of wires and cables. The total content can also be 0.3% by mass or more and 1.9% by mass or less, or 0.4% by mass or more and 1.8% by mass or less.

[0046] <First Compound> The highest absorption peak in the ultraviolet absorption spectrum of the first compound is located in the region above 320 nm and below 360 nm. This absorption peak can also be located in the region above 325 nm and below 355 nm, and also in the region above 330 nm and below 350 nm.

[0047] In the resin composition, the content of the first compound can be 0.1% by mass or more and 1.2% by mass or less. This further improves the weather resistance of wires and cables. The content of the first compound in the resin composition can also be 0.15% by mass or more and 1.1% by mass or less, or 0.2% by mass or more and 1.0% by mass or less.

[0048] The content of the first compound in the resin composition can be determined by the following method. After the resin composition is finely pulverized by cryogenic grinding, the soluble components are extracted using a solvent such as chloroform. Then, mass spectrometry analysis is performed on the solution to determine the components in the resin composition. Next, ultraviolet absorption spectroscopy is used to determine the compounds in the composition whose highest absorption peak in the ultraviolet absorption spectrum is located in the region above 320 nm and below 360 nm. Then, the content of the first compound can be determined based on the calibration curve of the compound located in the region above 320 nm and below 360 nm and the detection amount of the compound in the mass spectrometry analysis.

[0049] The first compound can be the compound shown in Formula 1 below. This further improves the weather resistance of wires and cables. In Formula 1, R1 is a hydrogen atom or a halogen atom, R2 is a hydrogen atom or a hydrocarbon group, and R3 is a hydrogen atom or a hydrocarbon group.

[0050] Alternatively, R1 can be a hydrogen atom or a chlorine atom, R2 can be a hydrogen atom, a methyl group or a group represented by formula 1d below, and R3 can be a hydrogen atom or a group represented by formula 1e below. This further improves the weather resistance of wires and cables. The first compound can be at least one compound selected from the group consisting of compounds shown in Formula 1a, Formula 1b, and Formula 1c. This further improves the weather resistance of wires and cables. The first compound can be a compound shown in Formula 1a. This further improves the weather resistance of wires and cables. <Second Compound> The highest absorption peak in the ultraviolet absorption spectrum of the second compound is located in the region greater than or equal to 275 nm and less than 320 nm. This absorption peak can also be located in the region above 280 nm and below 315 nm, and also in the region above 285 nm and below 310 nm.

[0051] In the resin composition, the content of the second compound can be 0.01% by mass or more and 0.15% by mass or less. This further improves the weather resistance of wires and cables. The content of the second compound in the resin composition can also be 0.015% by mass or more and 0.13% by mass or less, or 0.02% by mass or more and 0.11% by mass or less.

[0052] The content of the second compound in the resin composition can be determined by the following method. This method is the same as the method for determining the content of the first compound, except that the description of "more than 320 nm and less than 360 nm" in the method for determining the content of the first compound is replaced with "greater than or equal to 275 nm and less than 320 nm" and the description of "first compound" is replaced with "second compound".

[0053] The second compound can be the compound shown in Formula 2 below. This further improves the weather resistance of wires and cables. <The Third Compound> The highest absorption peak in the ultraviolet absorption spectrum of the third compound is located in the region greater than or equal to 240 nm and less than 275 nm. This absorption peak can also be located in the region above 245 nm and below 270 nm, and also in the region above 250 nm and below 265 nm.

[0054] In the resin composition, the content of the third compound can be 0.1% by mass or more and 1.5% by mass or less. This further improves the weather resistance of wires and cables. The content of the third compound in the resin composition can also be 0.12% by mass or more and 1.3% by mass or less, or 0.15% by mass or more and 1.1% by mass or less.

[0055] The content of the third compound in the resin composition can be determined by the following method. This method is the same as the method for determining the content of the first compound, except that the description of "more than 320 nm and less than 360 nm" in the method for determining the content of the first compound is replaced with "greater than or equal to 240 nm and less than 275 nm" and the description of "first compound" is replaced with "third compound".

[0056] The third compound can be the compound shown in Formula 3 below. This further improves the weather resistance of wires and cables. In Formula 3, R4 is a hydrocarbon group.

[0057] R4 can be a hydrocarbon group with 4 or more carbon atoms. This further improves the weather resistance of wires and cables. The lower limit for the number of carbon atoms in R4 can be 6 or more, or 8 or more, or 10 or more, or 12 or more, or 14 or more. There is no particular limit to the upper limit for the number of carbon atoms in R4; for example, it can be less than 30, less than 20, or less than 18.

[0058] R4 can be a linear -C 16 H 33 The base (in other words, the base of -n-C) 16 H 33 (Represented by a group). This further improves the weather resistance of wires and cables.

[0059] Hindered amine light stabilizers The resin composition also includes a hindered amine light stabilizer, which is a compound having the structure shown in Formula 4 below. The hindered amine light stabilizer is present in the resin composition at a concentration of 0.1% by mass or more and 1.5% by mass or less. This further improves the weather resistance of wires and cables. In this resin composition, the content of the hindered amine light stabilizer may be 0.12% by mass or more and 1.3% by mass or less, or 0.15% by mass or more and 1.1% by mass or less.

[0060] The content of hindered amine light stabilizers in a resin composition can be determined by the following method: After the resin composition is finely pulverized by cryogenic grinding, the soluble components are extracted using a solvent such as chloroform. Then, mass spectrometry analysis is performed on the solution to determine the components in the resin composition. Next, the content of the hindered amine light stabilizer can be determined based on the calibration curve of the compound corresponding to the hindered amine light stabilizer in that component and the detection amount of that compound in the mass spectrometry analysis.

[0061] Hindered amine light stabilizers can be compounds composed of structural units shown in Formula 4a. This further improves the weather resistance of wires and cables. The compound composed of the structural unit shown in Formula 4a above can be renamed as poly[[6-[(1,1,3,3-tetramethylbutyl)amino]-1,3,5-triazine-2,4-diyl][(2,2,6,6-tetramethyl-4-piperidinyl)imino]-1,6-hexanediyl[(2,2,6,6-tetramethyl-4-piperidinyl)imino]] (Poly[[6-[(1,1,3,3-tetramethylbutyl)amino]-1,3,5-triazine-2,4-diyl][(2,2,6,6-tetramethyl-4-piperidinyl)imino]-1,6-hexanediyl[(2,2,6,6-tetramethyl-4-piperidinyl)imino]]).

[0062] Other Ingredients The resin composition may also contain other components. Examples of other components include copolymers other than those derived from ethylene structural units and copolymers derived from α-olefin structural units having carbonyl groups (e.g., polyethylene, etc.), flame retardants other than brominated flame retardants, flame retardant additives, antioxidants, lubricants, colorants, reflective agents, masking agents, processing stabilizers, plasticizers, treatment agents, crosslinking agents, etc.

[0063] Methods for manufacturing resin compositions The method for manufacturing the resin composition of this embodiment can be carried out in the same manner as conventionally known methods, except that the above-mentioned components are combined in the manner described above.

[0064] [Implementation Method 2: Electrical Wire] use Figure 1 and Figure 2 The wires of one embodiment of this disclosure will be described. Figure 1 This is a schematic perspective view of an electrical wire according to one embodiment of the present disclosure. Figure 2 It is along Figure 1 Schematic sectional view of II-II.

[0065] One embodiment of this disclosure (hereinafter also referred to as "this embodiment") is an electrical wire having a conductor and a coating covering the conductor, the coating including a first layer formed of the resin composition described in Embodiment 1.

[0066] According to this disclosure, it is possible to provide wires with excellent heat resistance, excellent flame retardancy, excellent elongation, and excellent weather resistance. The reason for this is presumably as described in embodiments (a) and (b) of 1.

[0067] "electric wire" The equivalent circle diameter of the cross-section of wire 1 perpendicular to the longitudinal direction can be 0.1 mm or more and 50 mm or less, 0.2 mm or more and 20 mm or less, or 0.5 mm or more and 10 mm or less. It should be noted that, here, the longitudinal direction can be referred to as the "first direction" as described later.

[0068] The equivalent circle diameter of the cross-section of wire 1 perpendicular to its longitudinal direction can be determined by the following method. First, except that the object of measurement is wire 1, the average cross-sectional area of ​​wire 1 is calculated using the same method as the average cross-sectional area of ​​conductor 2. Next, the equivalent circle diameter is calculated based on this "average cross-sectional area of ​​wire 1," thereby determining the equivalent circle diameter of the cross-section of wire 1 perpendicular to its longitudinal direction.

[0069] It should be noted that as long as the same wire 1 is measured using the above method, the measurement results will not deviate even if the measurement location is arbitrarily changed.

[0070] "conductor" The wire 1 includes a conductor 2. The conductor 2 can be made of a metallic material with high conductivity and high mechanical strength. Examples of such metallic materials include copper, copper alloys, aluminum, aluminum alloys, nickel, silver, soft iron, steel, and stainless steel. The conductor 2 can be a wire formed by shaping a metallic material into a wire shape. Alternatively, the conductor 2 can be a multi-layered conductor formed by further coating the wire with other metals using techniques such as plating. Examples of multi-layered conductors 2 include tin-plated copper wire, nickel-plated copper wire, silver-plated copper wire, copper-plated aluminum wire, and copper-plated steel wire.

[0071] There are no particular restrictions on the shape of conductor 2, and conventionally known shapes can be used. Examples of conductor 2 shapes include circular wire with a circular cross-section, square wire with a square cross-section, flat wire with a rectangular cross-section, and stranded wire formed by twisting multiple wires together.

[0072] The equivalent circle diameter of the cross-section of conductor 2 perpendicular to the longitudinal direction can be 0.05 mm or more and 30 mm or less, 0.1 mm or more and 15 mm or less, or 0.3 mm or more and 8 mm or less. Here, the longitudinal direction can be referred to as the "first direction" as described later.

[0073] The equivalent circular diameter of the cross section of conductor 2 perpendicular to its longitudinal direction can be determined using the same method as the equivalent circular diameter of the cross section of wire 1 perpendicular to its longitudinal direction, except that the object of measurement is conductor 2.

[0074] It should be noted that as long as the same conductor 2 is measured using the above method, the measurement results will not deviate even if the measurement location is arbitrarily changed.

[0075] There are no particular restrictions on the average cross-sectional area of ​​conductor 2; it can be selected appropriately according to the application. The average cross-sectional area of ​​conductor 2 can be 0.0015 mm². 2 Above and 550mm 2 The following can also be 0.006mm 2 Above and 140mm 2 Below that, it can also be 0.05mm 2 Above and 40mm 2 The method for determining the average cross-sectional area of ​​conductor 2 in this disclosure is as follows: A conductor 2 is stretched into a straight line, and the conductor 2 is cut with a plane whose first direction is normal to connect one end of the conductor 2 to the other end, exposing the cross-section for measurement. For a single conductor 2, the conductor 2 is cut with a plane whose first direction is normal at any five arbitrary locations, and the cross-sectional area is measured. The average value is calculated. This average value corresponds to the average cross-sectional area of ​​conductor 2.

[0076] Membrane The wire 1 has a coating 5 covering the conductor 2. The coating 5 includes a first layer 3. The coating 5 may consist of only the first layer 3, or it may include other layers described later in addition to the first layer 3.

[0077] The thickness of the coating 5 can be 0.025 mm or more and 10 mm or less. If the thickness of the coating 5 is less than 0.025 mm, the coating 5 is prone to damage. If the thickness of the coating 5 exceeds 10 mm, the wire 1 becomes stiff and difficult to bend, and the cost increases. The thickness of the coating 5 can also be 0.050 mm or more and 2.5 mm or less, or 0.150 mm or more and 1 mm or less.

[0078] In this disclosure, the thickness of the coating 5 can be determined by the following method: A wire 1 is stretched into a straight line, and the wire 1 is cut with a plane whose first direction is normal to the plane connecting one end of the wire 1 to the other end, exposing the cross-section. For this cross-section, the thickness of the coating 5 is measured at any three locations, and their average value is calculated. The wire 1 is cut with a plane whose first direction is normal at any five locations, and the average value is calculated, thereby determining the thickness of the coating 5.

[0079] It should be noted that as long as the same wire 1 is measured using the above method, the measurement results will not deviate even if the measurement location is arbitrarily changed.

[0080] <Level 1> The first layer 3 is formed from the resin composition described in Embodiment 1. This enables the wire to possess excellent heat resistance, excellent flame retardancy, excellent elongation, and excellent weather resistance.

[0081] The composition of layer 1, 3 can be determined by combining the analysis of chemical bond state using nuclear magnetic resonance (NMR) spectroscopy and infrared absorption spectroscopy obtained by FT-IR with the determination of crystallization melting temperature and melting heat using differential scanning calorimetry.

[0082] The thickness of the first layer 3 can be 0.025mm or more and 10mm or less. This imparts superior weather resistance to the wire 1. Furthermore, it makes it easier to bend the wire 1. The lower limit of the thickness of the first layer 3 can be 0.025mm or more, 0.050mm or more, 0.100mm or more, or 0.200mm or more. The upper limit of the thickness of the first layer 3 can be less than 10mm, less than 2.5mm, less than 1mm, or less than 0.500mm. The thickness of the first layer 3 can be 0.050mm or more and 2.5mm or less, or 0.100mm or more and 1mm or less.

[0083] The thickness of the first layer 3 can be determined using the same method as the thickness of the coating 5, except that the object being measured is the first layer 3.

[0084] It should be noted that as long as the same wire 1 is measured using the above method, the measurement results will not deviate even if the measurement location is arbitrarily changed.

[0085] <Other Layers> The aforementioned coating 5 may also include other layers. Examples of such other layers include a surface layer and an intermediate layer. A surface layer is a layer located on the surface of the coating 5 (not shown). An intermediate layer is a layer located between the conductor 2 and the first layer 3 or between the first layer 3 and the surface layer (not shown).

[0086] Manufacturing Methods of Electrical Wires The method for manufacturing the wire 1 in this embodiment can be carried out in the same way as conventionally known methods, except that the resin composition described in Embodiment 1 is used as the material of the first layer 3.

[0087] [Implementation Method 3: Cable] use Figure 6 A cable according to one embodiment of the present disclosure will be described. Figure 6 This is a schematic cross-sectional view showing the configuration of a cable according to one embodiment of the present disclosure.

[0088] The cable of this embodiment has a core wire and a coating layer covering the core wire. The core wire includes a plurality of wires, and the coating layer includes a first layer A, which is located on the surface of the coating layer and is formed of the resin composition described in Embodiment 1.

[0089] According to this disclosure, a cable with wires exhibiting excellent heat resistance, excellent flame retardancy, excellent elongation, and excellent weather resistance can be provided. The reason for this is presumably as described in embodiments 1(a) and (b).

[0090] Core Wire The core wire comprises multiple wires. In other words, a collection of multiple wires can also be understood as a core wire. For example, a core wire can be a stranded wire formed by twisting multiple wires together. There is no particular limitation on the number of wires constituting the core wire; for example, it can be two, four, or six wires. The diameters (outer diameters) of the multiple wires constituting the core wire can be the same or different from each other. For example, two or more wires each having the same diameter can be twisted together to form a core wire. Here, "same" is not limited to being completely identical, but also includes the concept of being substantially the same. Furthermore, multiple insulated wires with different diameters can also be twisted together to form a core wire. The wire can have a conductor and a coating covering the conductor. Conventionally known wires can be used as the wire, as well as the wire described in Embodiment 2, and combinations thereof can also be used.

[0091] Covering Layer The coating layer includes a first layer A, which is located on the surface of the coating layer. The coating layer may include other layers in addition to the first layer A. Other layers could include a base layer (not shown) located between the core wire and the first layer A. The coating layer may also be composed of the first layer A.

[0092] <Level 1A> Layer 1A is formed from the resin composition described in Embodiment 1. This imparts to the cable excellent heat resistance, excellent flame retardancy, excellent elongation, and excellent weather resistance.

[0093] The composition of layer 1A can be determined by combining the analysis of chemical bond state using nuclear magnetic resonance (NMR) spectroscopy and infrared absorption spectroscopy obtained using FT-IR with the determination of crystallization melting temperature and melting heat using differential scanning calorimetry.

[0094] The thickness of layer 1A can be 0.025mm or more and 10mm or less. This imparts superior weather resistance to the cable. Furthermore, it makes the cable easier to bend. The lower limit of the cable thickness can be 0.025mm or more, 0.050mm or more, 0.100mm or more, or 0.200mm or more. The upper limit of the cable thickness can be less than 10mm, less than 2.5mm, less than 1mm, or less than 0.500mm. The cable thickness can be 0.050mm or more and 2.5mm or less, or 0.100mm or more and 1mm or less.

[0095] The thickness of layer 1A can be determined by the following method: Stretch the cable into a straight line and cut it with a plane whose second direction is normal to the plane connecting one end of the cable to the other, exposing the cross-section. For this cross-section, measure the thickness of layer 1A at any three locations and calculate their average value. Cut the cable at any five locations with a plane whose second direction is normal and calculate the average value, thereby determining the thickness of layer 1A.

[0096] It should be noted that as long as the same cable is measured using the above method, the measurement results will not deviate even if the measurement location is arbitrarily changed.

[0097] Methods for Manufacturing Cables The cable manufacturing method of this embodiment can be carried out in the same way as conventionally known methods, except that the resin composition described in Embodiment 1 is used as the material of the first A layer.

[0098] Example This embodiment will be described in more detail through examples. However, this embodiment is not limited to these examples.

[0099] The wires for samples 1 to 18 and 101 to 110 were produced using the following method.

[0100] <Preparation of Resin Composition> A mixture was obtained by combining the components listed in Tables 3-6 in the manner described in Tables 3-6. Next, the mixture was kneaded using a roller heated to the temperatures described in Tables 1 and 2 for the times described in Tables 1 and 2, thereby producing resin compositions for each sample. It should be noted that the raw materials were prepared by purchasing commercially available products. In Tables 3 and 4, EEA refers to ethylene-ethyl acrylate copolymer (in other words, the "polymer derived from structural units of ethylene and structural units derived from α-olefins having carbonyl groups" of this disclosure). As the EEA, "NUC-6510" (trademark) manufactured by ENEOS NUC Co., Ltd. was used. As the brominated flame retardant, "Saytex 8010" (trademark) manufactured by Albemarle Japan Co., Ltd. was used. As the first compound, "TinuvinP" (trademark) manufactured by BASF Japan Co., Ltd. was used. As the second compound, "KEMISORB 102" (trademark) manufactured by Chemipro Chemical Co., Ltd. was used. As the third compound, "KEMISORB 114" (trademark) manufactured by Chemipro Chemical Co., Ltd. was used. As a hindered amine light stabilizer, "Chimassorb944FDL" (trademark) manufactured by BASF Japan Co., Ltd. was used. In Tables 5 and 6, VLDPE refers to ultra-low density polyethylene (in other words, "polymers other than copolymers derived from ethylene structural units and copolymers derived from carbonyl α-olefin structural units" as disclosed in this disclosure). As a VLDPE, "ENGAGE7467" (trademark) manufactured by Dow Chemical Co., Ltd. was used. As the first antioxidant, zinc oxide (ZnO) was used. As the second antioxidant, "SumilizerMB" (trademark) manufactured by Sumitomo Chemical Co., Ltd. was used. As the third antioxidant, "Irganox1010" (trademark) manufactured by BASF Japan Co., Ltd. was used. As the fourth antioxidant, IrganoxPS802 manufactured by BASF Japan Co., Ltd. was used. As a treatment agent, stearic acid was used. As a crosslinking agent, trimethylolpropane trimethacrylate (TMPTMA) was used. As a flame retardant other than brominated flame retardants, "Saytex BT93" (trademark) manufactured by Albemarle Japan Co., Ltd. was used.

[0101] <Conductor Preparation> The conductor was prepared by purchasing commercially available products. As the conductor, a copper wire with an equivalent circle diameter of 6.0 mm perpendicular to the longitudinal direction was used.

[0102] <Making of Electrical Wires> First, the resin composition of each sample is pressed into an extruder with the head and cylinder set to the temperatures described in Tables 1 and 2. Next, the resin composition of each sample is extruded and coated onto the outer periphery of the conductor, with the thickness of the first layer as described in Tables 7 and 8. Then, the first layer (coating) is formed on the outer peripheral surface of the conductor by irradiating the extruded and coated resin composition of each sample with an electron beam of the dose described in Tables 1 and 2.

[0103] The above steps are used to produce wires of samples 1-18 and 101-110. Evaluation of Electrical Wire Characteristics <Heat Resistance Test> First, eight wires (350 mm in length) for each sample were prepared. Next, the coating between the ends of the wires and the point 25 mm from the end along the long dimension of the wire was stripped. Then, the eight wires (350 mm in length) for each sample were placed in constant temperature baths at 85±2℃, 100±2℃, 125±3℃, 150±3℃, 175±3℃, 200±3℃, 225±4℃, and 250±4℃ for 3000 hours. After removing the wires from the constant temperature baths, they were left at room temperature for 16 hours. Then, a mandrel 11 with a diameter 1.5 times the equivalent circular diameter of the cross-section perpendicular to the long dimension of the wire 12 was wound at a speed of 1 second, with a weight 13 weighing 5 kg. －1 At room temperature, the two sections are wound twice each. Figure 3Next, after visually confirming that the conductor of each wire sample was not exposed, the wire was immersed in salt water (3% by mass) for 10 minutes. Then, a voltage of 1 kV was applied to the wire for 1 minute. Next, the wire was visually inspected to determine whether the coating was damaged. Then, the heat resistance of the wire was evaluated based on the following evaluation criteria. The results were recorded in the "Heat Resistance Test" column of Tables 7 and 8. The closer the evaluation result is to H, the better the heat resistance of the wire.

[0104] (Evaluation Criteria) A: The film was not damaged when the temperature of the constant temperature bath was below 85±2℃. B: The film was not damaged when the temperature of the constant temperature bath was below 100±2℃. C: The film was not damaged when the temperature of the constant temperature bath was below 125±3℃. D: The film was not damaged when the temperature of the constant temperature bath was below 150±3℃. E: The film was not damaged when the temperature of the constant temperature bath was below 175±3℃. F: The film was not damaged when the temperature of the constant temperature bath was below 200±3℃. G: The film was not damaged when the temperature of the constant temperature bath was below 225±4℃. H: The film was not damaged when the temperature of the constant temperature bath was below 250±4℃. <Flame Retardancy Test> First, a 300mm long test piece 21 was collected from the wire of each sample. Then, as... Figure 4 As shown, each test piece 21 was horizontally supported, and the tip of the reducing flame 23 of the burner 22 was brought into contact with the test piece from the lower side of the center of the sample until the first layer of combustion occurred. The time from when the flame was smoothly removed until the flame extinguished was measured. The results were recorded in the "Burning Time [seconds]" column of Tables 7 and 8. It should be noted that a burning time [seconds] of less than 30 seconds indicates excellent flame retardancy of the wire.

[0105] <Tension Test> First, three test pieces were collected from the first layer of the wire (length: 3m) of each sample, at 1m intervals. Then, each of the three test pieces was shaped into a dumbbell shape while maintaining the thickness of the first layer, thus obtaining the No. 3 dumbbell plate 30 specified in 6.1 of JIS K 6251:2004 (refer to...). Figure 5Three dumbbell plates 30 were used. Next, each of the three dumbbell plates 30 was left to stand at room temperature for 1 hour. Each dumbbell plate 30 was stretched at a speed of 200 mm / min from the gripping portions 31 at both ends, and the distance l1 [mm] between the marks when each dumbbell plate 30 was cut was measured (not shown). Then, based on the distance l1 [mm] between the marks when each dumbbell plate 30 was cut, the distance l0 [mm] between the marks before the test, and the formula “ε = {(l1 - l0) / l0} × 100”, the elongation ε [%) was calculated. Next, the elongation ε of the wire in each sample was calculated by averaging the elongation ε of the three dumbbell plates 30. The results were recorded in the “Elongation [%)” column of the “Tension Test” section of Tables 7 and 8. An elongation % of 300% or higher indicates excellent wire elongation.

[0106] <Weathering Resistance Test> First, the portion of the wire corresponding to the first layer of each specimen is punched into a dumbbell shape using a No. 6 dumbbell-shaped die to obtain test pieces for each specimen. Next, the test pieces for each specimen are exposed to a light source under the following conditions, based on ISO 4892-2. Then, for each specimen, the distance between the marks L0 [mm] is measured after exposure and before the tensile test. Next, for each specimen, the distance between the marks L2 [mm] is measured after exposure and after the tensile test. Next, for each specimen, the elongation ε2 [%] of the test piece after exposure and the tensile test is calculated based on the formula “ε2 = {(L2 - L0) / L0} × 100”. The results are recorded in the “Elongation [%]” column of the “Weathering Resistance Test” section in Tables 7 and 8. An elongation ε2 [%] of 50% or more indicates excellent weather resistance of the wire.

[0107] (condition) • Lamp Power: 565W / m 2 • Broadband (300-800nm): 60±2W / m 2 • Filter: Sunlight Black panel temperature: 63±3℃ • Chamber temperature: 38±3℃ Relative humidity: 50±10% • Lamp temperature: 63±3℃ • Water spray duration: 18 minutes • Drying Interval: 102 minutes • Lamp Cycle Time (Lamp On): 120 minutes The wires of samples 1 to 18 correspond to the examples. The wires of samples 101 to 110 correspond to the comparative examples. As can be seen from the results in Tables 7 and 8, compared with the wires of samples 101 to 110, the wires of samples 1 to 18 exhibit the superior effect of having excellent heat resistance, excellent flame retardancy, excellent elongation and excellent weather resistance.

[0108] In summary, the wires of samples 1-18 exhibit excellent heat resistance, excellent flame retardancy, excellent elongation, and excellent weather resistance. It should be noted that only the resin composition and the wire are shown in the above embodiments. However, given the general knowledge of those skilled in the art, it is foreseeable that the same effects can be achieved in cables using the resin composition disclosed herein.

[0109] The embodiments and examples of this disclosure have been described as above. However, it is intended from the outset that the above-described embodiments and examples can be appropriately combined or modified.

[0110] It should be considered that the embodiments and examples disclosed herein are exemplary in all respects and not restrictive. The scope of the invention is not shown by the above embodiments and examples, but by the claims, and is intended to include all modifications within the meaning and scope of the claims.

[0111] Explanation of reference numerals in the attached figures: 1: Wire; 2: Conductor; 3: First layer; 5: Coating; 11: Mandrel; 12: Wire; 13: Weight; 21: Test piece; 22: Burner; 23: Reducing flame; 30: Dumbbell plate; 31: Grip part; 41: Conductor; 42: Coating; 43: Wire; 44: Core wire; 47: First layer A; 48: Coating layer; 50: Cable.

Claims

1. A resin composition comprising a copolymer of structural units derived from ethylene and structural units derived from α-olefins having carbonyl groups, a brominated flame retardant, and antimony trioxide. In the resin composition, the copolymer is present in a concentration of 20% by mass or more and 60% by mass or less. In the resin composition, the content of the brominated flame retardant is 10% by mass or more and 30% by mass or less. In the resin composition, the content of antimony trioxide is more than 2% by mass and less than 15% by mass. The resin composition further comprises at least two compounds selected from the group consisting of the first compound, the second compound, and the third compound. In the resin composition, at least two of the compounds selected from the group consisting of the first compound, the second compound, and the third compound each have a content of 0.01% by mass or more and 1.5% by mass or less. The highest absorption peak in the ultraviolet absorption spectrum of the first compound is located in the region above 320 nm and below 360 nm. The highest absorption peak in the ultraviolet absorption spectrum of the second compound is located in the region greater than or equal to 275 nm and less than 320 nm. The highest absorption peak in the ultraviolet absorption spectrum of the third compound is located in the region greater than or equal to 240 nm and less than 275 nm.

2. The resin composition according to claim 1, wherein, The first compound is the compound represented by Formula 1 below, the second compound is the compound represented by Formula 2 below, and the third compound is the compound represented by Formula 3 below. In Formula 1, R1 is a hydrogen atom or a halogen atom, R2 is a hydrogen atom or a hydrocarbon group, and R3 is a hydrogen atom or a hydrocarbon group. In Formula 3, R4 is a hydrocarbon group.

3. The resin composition according to claim 2, wherein, R1 is a hydrogen atom or a chlorine atom, R2 is a hydrogen atom, a methyl group or a group represented by formula 1d below, and R3 is a hydrogen atom or a group represented by formula 1e below. 。 4. The resin composition according to any one of claims 1 to 3, wherein, The first compound is at least one compound selected from the group consisting of compounds represented by formula 1a, formula 1b, and formula 1c. 。 5. The resin composition according to claim 4, wherein, The first compound is the compound represented by Formula 1a.

6. The resin composition according to any one of claims 1 to 5, wherein, R4 is a hydrocarbon group having 4 or more carbon atoms.

7. The resin composition according to any one of claims 1 to 6, wherein, The R4 is a linear -C 16 H 33 base.

8. The resin composition according to any one of claims 1 to 7, wherein, The resin composition further comprises a hindered amine light stabilizer, which is a compound having the structure shown in Formula 4 below, wherein the hindered amine light stabilizer is present in the resin composition at a concentration of 0.1% by mass or more and 1.5% by mass or less. 。 9. The resin composition according to claim 8, wherein, The hindered amine light stabilizer is a compound composed of structural units represented by the following formula 4a. 。 10. An electrical wire comprising a conductor and a coating covering the conductor, The membrane includes a first layer, The first layer is formed from the resin composition as described in any one of claims 1 to 9.

11. A cable having a core wire and a coating covering the core wire, The core wire includes multiple wires. The coating layer includes layer 1A. The first layer A is located on the surface of the coated layer. The first A layer is formed from the resin composition as described in any one of claims 1 to 9.

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