JP2020164837A - Ionomer resin-containing electric wire/cable - Google Patents

Abstract

To provide a resin that is excellent in flame retardancy and wear resistance.SOLUTION: A flame retardant resin composition, containing, for 100 pts.wt. of a resin component composed of a polyolefin-based resin (A) by 50 to 99 wt.% and an ionomer resin (B) by 1 to 50 wt.%, a flame retardant (C) by 30 to 300 pts.wt., and in which, characterized, the ionomer resin (B) is substantially linear.SELECTED DRAWING: None

Description

The present invention relates to a flame-retardant resin composition containing a novel ionomer and having excellent wear resistance, and an electric wire / cable using the same.

Electric wires and cables used in electrical equipment are coated to prevent exposure of the conducting wires, and the material used for this coating is flame-retardant to prevent burning and to prevent exposure due to breakage. Physical properties such as wear resistance are required. Conventionally, polyvinyl chloride resin compositions have been used as flame-retardant materials for electric wires and cable coating materials, but polyvinyl chloride resin compositions are toxic halogens when burned during fires or waste incineration. Improvement was required because it generated contained gas. In order to overcome such drawbacks of polyvinyl chloride, a resin composition (non-halogen flame-retardant material) in which a metal hydroxide such as magnesium hydroxide is mixed with a polyolefin resin has been proposed. In order to impart sufficient flame retardancy to such a non-halogen flame-retardant material, it is necessary to add a metal hydroxide of the same weight to the base polyolefin material, but a large amount of metal hydroxide is added. There is a problem that the addition easily causes wear and rubbing whitening of the material.
With regard to improving the wear resistance of the flame-retardant resin composition, attempts have been made to increase the number of layers of electric wires and cables with the aim of improving the coating structure. In this method, a multilayer electric wire in which an outer layer is coated with a polyolefin resin or a polyester resin having a high melting point is known (Patent Documents 1 and 2). In another method, an attempt has been made to study the material, and ultra-high molecular weight polyethylene has been contained (Patent Document 3). In addition, a method by incorporating an ionomer is known (Patent Document 4).

Ionomer is a synthetic resin in which polymers are aggregated with metal ions. Ethylene-based ionomer, which is a resin in which an ethylene-unsaturated carboxylic acid copolymer is used as a precursor resin and intermolecularly bonded with metal ions such as sodium and zinc, is known. (Patent Document 5). Ethylene ionomers are tough, highly elastic, flexible, and have features such as wear resistance and transparency.
Currently, commercially available ethylene ionomers include the ethylene-methacrylic acid copolymer sodium salt and zinc salt "Surlyn (registered trademark)" developed by DuPont, and "Surlyn (registered trademark)" sold by Mitsui-Daupolichem. High Milan (registered trademark) "is known.

However, the ethylene-unsaturated carboxylic acid copolymers of the precursor resins used in these currently commercially available ethylene-based ionomers contain a polar group-containing monomer such as ethylene and unsaturated carboxylic acid in a high-pressure radical weight. A polar group-containing olefin copolymer that has been legally polymerized is used. The high-pressure radical polymerization method has an advantage that it can be polymerized at low cost regardless of the type of the monomer containing a polar group. However, the molecular structure of the polar group-containing olefin copolymer produced by the high-pressure radical polymerization method is a structure having many long-chain branches and short-chain branches irregularly as shown in the image diagram shown in FIG. , There is a drawback that the strength is insufficient.

On the other hand, conventionally, a method for producing a polar group-containing olefin copolymer having a linear molecular structure using a polymerization method using a catalyst has been sought, as shown in the image diagram shown in FIG. Since group-containing monomers are generally catalyst poisons, it is difficult to polymerize using a catalyst. In fact, it is not possible to obtain a polar group-containing olefin copolymer having desired physical properties by an industrially inexpensive and stable method. It was considered difficult for many years.
However, in recent years, by using a new catalyst and a new production method developed by the applicants of the present application and the like, a polar group-containing olefin copolymer having a substantially linear molecular structure can be obtained industrially at low cost and stably. A method has been proposed.
Then, as a method for producing a polar group-containing olefin copolymer to be a precursor resin of an ethylene-based ionomer, a copolymer of ethylene and t-butyl acrylate was produced using a late-period transition metal catalyst, and the obtained polarity was obtained. The applicants of the present application reported that they succeeded in producing a binary ionomer by reacting a group-containing olefin copolymer with an ethylene-acrylic acid copolymer after modifying it into an ethylene-acrylic acid copolymer by heat or acid treatment. (Patent Document 6).

Japanese Unexamined Patent Publication No. 2006-310092 JP-A-2015-201450 Japanese Patent Application Laid-Open No. 5-339437 Patent No. 3779614 U.S. Pat. No. 3,264,272 Japanese Unexamined Patent Publication No. 2016-79408

Various attempts have been made from the viewpoint of achieving both flame retardancy and wear resistance, but the methods described in Patent Documents 1 and 2 have a problem that they are difficult to carry out without a molding machine capable of multi-layer molding. Have. In the method described in Patent Document 3, since the polyethylene used has an ultra-high molecular weight, deterioration of extrusion characteristics due to an increase in viscosity becomes a problem. In addition, there is a concern that poor dispersion may affect the appearance of the cable such as bumps. The ionomer described in Patent Document 4 was prepared by high-pressure radical polymerization, and had insufficient strength as described above. No suitable material is known as a material having flame retardancy and wear resistance.
An object of the present invention is to provide a resin having excellent flame retardancy and abrasion resistance in view of the situation of the prior art.

As a result of repeated studies by the present inventors to solve the above problems, it has been found that a flame-retardant resin composition using a specific ionomer resin has an excellent effect on wear resistance as a coating material for electric wires and cables. I found it.
The ethylene-based ionomer as described in Patent Document 5 or 6 is a novel ethylene-based ionomer that has never existed before, in which the precursor resin has a substantially linear molecular structure and also functions as an ionomer. However, its physical properties were significantly different from those of conventional ethylene ionomers, and its unique properties and suitable applications were unknown. In the present invention, although the ionomer basically does not have flame retardancy, a substantially linear ethylene-based ionomer is blended into the resin for electric wires and cables to make the ionomer surprisingly flame retardant. It is based on the finding that it has an excellent effect on wear resistance while being maintained.

That is, in the first aspect of the present invention, 30 parts by weight of the flame retardant (C) is added to 100 parts by weight of the resin component composed of 50 to 99% by weight of the polyolefin resin (A) and 1 to 50% by weight of the ionomer resin (B). A flame-retardant resin composition containing up to 300 parts by weight, wherein the ionomer resin (B) contains a structural unit (a) derived from ethylene and / or α-olefin having 3 to 20 carbon atoms. At least a part of the carboxyl group and / or the dicarboxylic acid anhydride group in the copolymer (P) containing the structural unit (b) derived from the monomer having a carboxyl group and / or the dicarboxylic acid anhydride group as an essential structural unit. Is converted into a metal-containing carboxylate containing at least one metal ion selected from Group 1, Group 2, or Group 12 of the periodic table, and the absolute value G ^* = of the complex elastic coefficient measured by a rotary leometer. A flame-retardant resin composition which is an ionomer resin having a phase angle δ at 0.1 MPa of 50 degrees to 75 degrees.

According to the present invention, a resin composition having flame retardancy and excellent wear resistance can be obtained. The resin using the ionomer according to the present invention, which has a substantially linear structure, has excellent wear resistance as compared with the conventional flame-retardant resin, and is therefore useful as a material requiring long-term durability such as electric wires and cables. is there.

FIG. 1 is a diagram showing an outline of the molecular structure of a polar group-containing olefin copolymer produced by a high-pressure radical polymerization method. FIG. 2 is a diagram showing an outline of the molecular structure of a polar group-containing olefin copolymer obtained by catalytic polymerization. FIG. 3 is a diagram showing the evaluation of the wear resistance of the resin compositions of Examples 1 and 2 and Comparative Examples 1 to 3 with respect to the blending amount of ionomer. FIG. 4 is a diagram showing the evaluation of the wear resistance of the resin compositions of Example 3 and Comparative Examples 4 and 5 with respect to the blending amount of ionomer. FIG. 5 is a diagram showing the evaluation of the wear resistance of the resin compositions of Example 4 and Comparative Examples 6 and 7 with respect to the blending amount of ionomer. FIG. 6 is a diagram showing the evaluation of the wear resistance of the resin compositions of Examples 5 and 6 and Comparative Examples 8 and 9 with respect to the blending amount of ionomer.

The present invention requires a structural unit (a) derived from ethylene and / or an α-olefin having 3 to 20 carbon atoms and a structural unit (b) derived from a monomer having a carboxyl group and / or a dicarboxylic acid anhydride group. A copolymer (P) containing as a structural unit and copolymerized substantially linearly, preferably randomly copolymerized, is used as a precursor resin, and the carboxyl group and / or dicarboxylic acid anhydride of the structural unit (b) is anhydrous. Difficulty using an ionomer, characterized in that at least a part of the material group is converted into a metal-containing carboxylate containing at least one metal ion selected from Group 1, Group 2, or Group 12 of the periodic table. It is a fuel resin composition.

Hereinafter, ionomers, resin compositions containing ionomers, electric wires or cables using ionomers, uses thereof, and the like according to the present invention will be described in detail for each item. In addition, in this specification, "(meth) acrylic acid" means acrylic acid or methacrylic acid. Further, in the present specification, "~" indicating a numerical range is used to mean that the numerical values described before and after the numerical range are included as the lower limit value and the upper limit value.

1. 1. Polyolefin resin (A)
In addition to the ionomer described above, the flame-retardant resin composition of the present invention contains a polyolefin resin (A). The polyolefin-based resin (A) can be used without particular limitation as long as it is a resin used for electric wires or cables. Examples of the polyolefin-based resin (A) include polyethylenes such as low-density polyethylene, medium-density polyethylene, and high-density polyethylene, single or alternating copolymers of α-olefins having 3 or more carbon atoms such as polypropylene-based resins, and carboxyl groups. Examples thereof include a polar group-containing ethylene-based copolymer, a high-density radical method ethylene (co) copolymer, and a modified polyolefin.

Among the polyolefin-based resins (A), a polar group-containing ethylene-based copolymer is a preferable example. As the polar group-containing ethylene-based polymer, polar group-containing polyethylene is particularly preferable. Specific examples of the polar group-containing ethylene-based copolymer include a copolymer of ethylene and an α, β-unsaturated carboxylic acid ester, and a polyolefin containing an ethylene-vinyl ester copolymer. Typical copolymers of a copolymer of ethylene and α, β-unsaturated carboxylic acid ester include ethylene-methyl acrylate copolymer, ethylene-ethyl acrylate copolymer, ethylene-butyl acrylate copolymer, and ethylene. Ethylene- (meth) acrylate copolymers such as -methyl methacrylate copolymer, ethylene-ethyl methacrylate copolymer, ethylene-vinyl acetate copolymer, ethylene-maleic anhydride-vinyl acetate copolymer, ethylene-maleine anhydride Examples thereof include a binary copolymer such as an acid-methyl acrylate copolymer and an ethylene-maleic anhydride-ethyl acrylate copolymer, or a multi-dimensional copolymer. The content of the other comonomer with respect to ethylene is in the range of 3 to 30% by weight, preferably 5 to 20% by weight, based on the total amount of the other comonomer.

The ethylene / vinyl ester copolymer contains ethylene as a main component, and is used with vinyl ester monomers such as vinyl propionate, vinyl acetate, vinyl caproate, vinyl caprylate, vinyl laurate, vinyl stearate, and vinyl trifluorate. It is a copolymer.
Among these, vinyl acetate can be mentioned as particularly preferable. A copolymer composed of 50 to 99.5% by weight of ethylene, 0.5 to 50% by weight of vinyl ester, and 0 to 49.5% by weight of other copolymerizable unsaturated monomer is preferable. Further, the vinyl ester content is selected in the range of 3 to 30% by weight, particularly preferably 5 to 20% by weight.

Further, as the polar group-containing polyolefin resin, a modified polyolefin resin in which an acid or the like is allowed to act on the polyolefin resin to change its physical properties, particularly an acid-modified polyolefin resin can also be used. The modified polyolefin resin is used to promote the mechanical strength of the flame-retardant resin composition and the formation of a carbonized layer during combustion, and to improve the mechanical strength and flame retardancy. The modified polyolefin resin is (i) unsaturated carboxylic acid or a derivative thereof, (ii) epoxy group-containing compound, (iii) hydroxyl group-containing compound, (iv) amino group-containing compound, (v) organic silane compound, (vi). ) A polyolefin-based resin modified with a functional group-containing compound such as an organic titanate compound can be mentioned.
(I) Examples of the unsaturated carboxylic acid or a derivative thereof include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, furanoic acid, crotonic acid, vinylacetic acid and penthenic acid, maleic acid, fumaric acid, citraconic acid and itaconic acid. Α, β-Unsaturated dicarboxylic acids or anhydrides, or metal salts thereof and the like.
(Ii) Examples of the epoxy group-containing compound include glycidyl acrylate, glycidyl methacrylate, monoglycidyl ester of itaconic acid, monoglycidyl ester of butentricarboxylic acid, diglycidyl ester of butentricarboxylic acid, triglycidyl ester of butentricarboxylic acid, α-chloroallyl, and maleine. Examples thereof include glycidyl esters such as acid, crotonic acid and fumaric acid, vinyl glycidyl ethers, allyl glycidyl ethers, glycidyl oxyethyl vinyl ethers, glycidyl ethers such as styrene-p-glycidyl ethers, and p-glycidyl styrenes, which are particularly preferable. Examples thereof include glycidyl methacrylate and allyl glycidyl ether.
Examples of the (iii) hydroxyl group-containing compound include 1-hydroxypropyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and hydroxyethyl (meth) acrylate.
Examples of the (iv) amino group-containing compound include tertiary amino groups such as dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, and dibutylaminoethyl (meth) acrylate.
Examples of the (v) organic silane compound include vinyltrimethoxylane, vinyltriethoxysilane, vinyltriacetylsilane, vinyltrichlorosilane and the like.
Examples of the (vi) organic titanate compound include tetraisopropyl titanate, tetra-n-butyl titanate, tetrakis (2-ethylhexoxy) titanate, and titanium lactate ammonium.

The modified polyolefin resin is obtained by modifying the polyolefin resin by heating it in the presence of a functional group-containing compound and an organic peroxide. The content of the functional group-containing compound is in a desired range, preferably 0.05 to 10% by weight, more preferably 0.1 to 8.0% by weight, or the modified product is mixed with an unmodified polyolefin resin. Then, the content adjusted to the above range is used.
As the polyolefin-based resin used for modification, olefins such as ethylene, propylene, and butene are generally used, and the type is not particularly limited, but ethylene is more preferable. Preferred examples of the modified polyolefin resin include acid-modified polyolefin resins, particularly polyethylene modified with maleic anhydride.

When the modified polyolefin resin is used, the blending amount thereof is preferably 1 to 30 parts by weight, more preferably 1 to 20 parts by weight, still more preferably 1 to 10 parts by weight based on 100 parts by weight of the total amount of the polyolefin resin (A). It is a part by weight. When the modified polyolefin resin is blended, a coupling effect between the resin component and the flame retardant (C) described later is produced, and the mechanical properties of the flame retardant resin composition are improved. Within the above range, the modifying effect is sufficiently exhibited, flexibility and flexibility are given to the resin composition, and workability when winding the electric wire / cable around the drum is expected to be improved, which is preferable.

The low-density polyethylene resin has a density of 0.91 to 0.935 g / cm ³ , an MFR of 0.05 to 100 g / 10 minutes, and preferably a density of 0.915 to 0.930 g / cm ³ . Those having an MFR in the range of 0.1 to 50 g / 10 minutes are preferably used.
The medium density polyethylene resin has a density of 0.935 to 0.94 g / cm ³ , an MFR of 0.05 to 100 g / 10 minutes, and preferably a density of 0.936 to 0.939 g / cm ³ . Those having an MFR in the range of 0.1 to 50 g / 10 minutes are preferably used.
The high-density polyethylene resin has a density of 0.94 to 0.97 g / cm ³ , an MFR of 0.05 to 100 g / 10 minutes, preferably a density of 0.945 to 0.960 g / cm ³ , Those having an MFR in the range of 0.1 to 50 g / 10 minutes are preferably used.
In addition, as the polyethylene resin, a polyethylene resin produced by ion polymerization or the like can also be used. The polyethylene resin produced by ionic polymerization is described in the literature book "Polyethylene Technology Reader" (edited by Kazuo Matsuura and Naotaka Mikami, published by Kogyo Chosakai, 2001). 123-160, p. It can be produced by the method described in 163 to 196 and the like. That is, using a Ziegler-based catalyst, a single-site-based catalyst, etc., it is possible to produce by various polymerization machines, polymerization conditions, and catalysts in each polymerization mode of the slurry method, the solution method, and the vapor phase method. is there.

Examples of the single or alternating copolymer of an α-olefin having 3 or more carbon atoms include a propylene copolymer, a copolymer of propylene and another α-olefin, for example, a block copolymer of propylene and ethylene, and a random copolymer. Coalescence and the like can be mentioned.

The high-pressure radical method ethylene (co) polymer according to the present invention includes an ethylene homopolymer (low density polyethylene resin) by a high pressure radical polymerization method, an ethylene / vinyl ester copolymer, and ethylene and α, β-unsaturated carboxylic acid. Alternatively, a copolymer with a derivative thereof and the like can be mentioned, and these low-density polyethylene resins and the like are produced by a known high-pressure radical polymerization method, and may be produced by either a tubular method or an autoclave method.

The amount of the polyolefin-based resin in the flame-retardant resin composition is not particularly limited as long as it can be used for electric wires and cables, but it may contain 50 to 99% by weight with respect to the total amount with the ionomer resin described later. preferable. It is more preferably in the range of 80 to 99% by weight, still more preferably in the range of 90 to 99% by weight, based on the total amount with the ionomer resin. Within this range, it is possible to obtain a resin composition that satisfies the required physical properties such as moldability as a resin and has excellent wear resistance.

2. Ionomer The ionomer of the present invention is a structural unit (a) derived from ethylene and / or an α-olefin having 3 to 20 carbon atoms, and a structural unit (b) derived from a monomer having a carboxyl group and / or a dicarboxylic acid anhydride group. ) As an essential structural unit, and a copolymer (P) in which these are copolymerized substantially linearly, preferably randomly copolymerized, is used as a precursor resin, and the carboxyl group of the structural unit (b) and / Alternatively, at least a part of the dicarboxylic acid anhydride group is converted into a metal-containing carboxylate containing at least one metal ion selected from Group 1, Group 2, or Group 12 of the periodic table.

(1) Structural unit (a)
The structural unit (a) is at least one structural unit selected from the group consisting of a structural unit derived from ethylene and a structural unit derived from an α-olefin having 3 to 20 carbon atoms.
The α-olefin according to the present invention is an α-olefin having 3 to 20 carbon atoms represented by the structural formula: CH ₂ = CHR ¹⁸ (R ¹⁸ is a hydrocarbon group having 1 to ¹⁸ carbon atoms and is a straight chain. It may be structural or have branches). The number of carbon atoms of the α-olefin is more preferably 3 to 12.

Specific examples of the structural unit (a) include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 3-methyl-1-butene, and 4-methyl-1-pentene. Etc., and may be ethylene.
Further, the structural unit (a) contained in the ionomer may be one type or a plurality of types. Examples of the combination of the two include ethylene-propylene, ethylene-1-butene, ethylene-1-hexene, ethylene-1-octene, propylene-1-butene, propylene-1-hexene, and propylene-1-octene. Be done. Examples of the three combinations include ethylene-propylene-1-butene, ethylene-propylene-1-hexene, ethylene-propylene-1-octene, propylene-1-butene-hexene, and propylene-1-butene-1-octene. Can be mentioned.

In the present invention, the structural unit (a) preferably contains ethylene as essential, and may further contain one or more α-olefins having 3 to 20 carbon atoms, if necessary.
The amount of ethylene in the structural unit (a) may be 65 to 100 mol% or 70 to 100 mol% with respect to the total mol of the structural unit (a).

(2) Structural unit (b)
The structural unit (b) is a structural unit derived from a monomer having a carboxyl group and / or a dicarboxylic acid anhydride group.

Specific examples of the monomer having a carboxyl group include acrylic acid, methacrylic acid, maleic acid, fumaric acid, tetrahydrophthalic acid, itaconic acid, citraconic acid, crotonic acid, isocrotonic acid, norbornene dicarboxylic acid, and bicyclo [2.2.1]. ] Unsaturated carboxylic acids such as hept-2-ene-5,6-dicarboxylic acid are mentioned, and examples of the monomer having a dicarboxylic acid anhydride group include maleic anhydride, itaconic anhydride, citraconic anhydride, tetrahydrophthalic anhydride, 5-Norbornene-2,3-dicarboxylic acid anhydride, 3,6-epoxy-1,2,3,6-tetrahydrophthalic acid anhydride, tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] Unsaturated dicarboxylic acid anhydrides such as dodeca-9-ene-4,5-dicarboxylic acid anhydride and 2,7-octadien-1-ylsuccinic anhydride can be mentioned.
Specific examples of the compound include acrylic acid, methacrylic acid, and 5-norbornene-2,3-dicarboxylic acid anhydride, and may be acrylic acid in particular.
Further, the monomer having a carboxyl group and / or a dicarboxylic acid anhydride group may be one kind or a plurality of kinds.

The dicarboxylic acid anhydride group may react with water in the air to open a ring and partially become a dicarboxylic acid. However, as long as the gist of the present invention is not deviated, the dicarboxylic acid anhydride group may be used. The ring may be opened.

(3) Other structural units (c)
The copolymer (P) according to the present invention may be referred to as a structural unit (c) other than the structural unit (a) and the structural unit (b) (hereinafter, referred to as “arbitrary monomer (c)”). Yes) may be included. As the monomer giving the structural unit (c), any monomer can be used as long as it is not the same as the monomer giving the structural unit (a) and the structural unit (b). Any monomer that gives the structural unit (c) is not limited as long as it is a compound having one or more carbon-carbon double bonds in the molecular structure, but for example, an acyclic monomer represented by the following general formula (1) or Examples thereof include cyclic monomers represented by the following general formula (2).

・ Acyclic monomer

[In the general formula (1), T ^{1 to} T ³ are independently hydrogen atoms, hydrocarbon groups having 1 to 20 carbon atoms, hydrocarbon groups having 1 to 20 carbon atoms substituted with hydroxyl groups, and 1 carbon group. A hydrocarbon group having 2 to 20 carbon atoms substituted with an alkoxy group of ~ 20, a hydrocarbon group having 3 to 20 carbon atoms substituted with an ester group having 2 to 20 carbon atoms, and a carbon number 1 substituted with a halogen atom. ~ 20 hydrocarbon groups, 1 to 20 carbons alkoxy groups, 6 to 20 carbons aryl groups, 2 to 20 carbons ester groups, 3 to 20 carbons silyl groups, halogen atoms, or It is a substituent selected from the group consisting of cyano groups.
T ⁴ is a hydrocarbon group having 1 to 20 carbon atoms substituted with a hydroxyl group, a hydrocarbon group having 2 to 20 carbon atoms substituted with an alkoxy group having 1 to 20 carbon atoms, and an ester group having 2 to 20 carbon atoms. Substituted hydrocarbon groups with 3 to 20 carbon atoms, hydrocarbon groups with 1 to 20 carbon atoms substituted with halogen atoms, alkoxy groups with 1 to 20 carbon atoms, aryl groups with 6 to 20 carbon atoms, 2 carbon atoms A substituent selected from the group consisting of an ester group of ~ 20, a silyl group having 3 to 20 carbon atoms, a halogen atom, or a cyano group. ]

In the ionomer of the present invention, T ¹ and T ² may be a hydrogen atom, T ³ may be a hydrogen atom or a methyl group, and T ⁴ may be an ester group having 2 to 20 carbon atoms. Good.

The carbon skeleton of a hydrocarbon group, a substituted alkoxy group, a substituted ester group, an alkoxy group, an aryl group, an ester group, or a silyl group for T ^{1 to} T ⁴ may have a branched, ring, and / or unsaturated bond. Good.
The number of carbon atoms of the hydrocarbon groups for T ^{1 to} T ⁴ may be as long as the lower limit is 1 or more, the upper limit may be 20 or less, and may be 10 or less.
The carbon number of the substituted alkoxy group for T ^{1 to} T ⁴ may be as long as the lower limit is 1 or more, the upper limit may be 20 or less, and may be 10 or less.
The carbon number of the substituted ester group for T ^{1 to} T ⁴ may be as long as the lower limit is 2 or more, the upper limit may be 20 or less, and may be 10 or less.
The carbon number of the alkoxy group for T ^{1 to} T ⁴ may be as long as the lower limit is 1 or more, the upper limit may be 20 or less, and may be 10 or less.
The carbon number of the aryl group for T ^{1 to} T ⁴ may be as long as the lower limit is 6 or more, the upper limit may be 20 or less, and may be 11 or less.
The carbon number of the ester group for T ^{1 to} T ⁴ may be as long as the lower limit is 2 or more, the upper limit may be 20 or less, and may be 10 or less.
The carbon number of the silyl group for T ^{1 to} T ⁴ may be as long as the lower limit is 3 or more, the upper limit may be 18 or less, and may be 12 or less. Examples of the silyl group include a trimethylsilyl group, a triethylsilyl group, a trin-propylsilyl group, a triisopropylsilyl group, a dimethylphenylsilyl group, a methyldiphenylsilyl group, and a triphenylsilyl group.

Specific examples of the acyclic monomer include (meth) acrylic acid ester and the like.
The (meth) acrylic acid ester according to the present invention is a compound represented by the structural formula: CH ₂ = C (R ²¹ ) CO ₂ (R ²² ). Here, R ²¹ is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and may have a branched, ring, and / or unsaturated bond. R ²² is a hydrocarbon group having 1 to 20 carbon atoms and may have a branched, ring, and / or unsaturated bond. Furthermore, a heteroatom may be contained at any position in R ²² .
Examples of the (meth) acrylic acid ester include (meth) acrylic acid ester in which R ²¹ is a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms. Further, an acrylic acid ester in which R ²¹ is a hydrogen atom or a methacrylic acid ester in which R ²¹ is a methyl group can be mentioned.
Specific examples of the (meth) acrylic acid ester include, for example, methyl (meth) acrylic acid, ethyl (meth) acrylic acid, n-propyl (meth) acrylic acid, isopropyl (meth) acrylic acid, and n (meth) acrylic acid. -Butyl, isobutyl (meth) acrylate, t-butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, cyclohexyl (meth) acrylate, octyl (meth) acrylate, (meth) 2-ethylhexyl acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, octadecyl (meth) acrylate, phenyl (meth) acrylate, toluyl (meth) acrylate, (meth) ) Benzyl acrylate and the like.
Specific compounds include methyl acrylate, ethyl acrylate, n-butyl acrylate (nBA), isobutyl acrylate (iBA), t-butyl acrylate (tBA), 2-ethylhexyl acrylate and the like. In particular, n-butyl acrylate (nBA), isobutyl acrylate (iBA), and t-butyl acrylate (tBA) may be used.
As the acyclic monomer, one type may be used, or a plurality of types may be used.

・ Cyclic monomer

[In the general formula (2), R ^{1 to} R ¹² may be the same or different, and are selected from the group consisting of a hydrogen atom, a halogen atom, and a hydrocarbon group having 1 to 20 carbon atoms. , R ⁹ and R ¹⁰ , and R ¹¹ and R ¹² may be integrated to form a divalent organic group, respectively, and R ⁹ or R ¹⁰ and R ¹¹ or R ¹² may ring each other. It may be formed.
Further, n indicates 0 or a positive integer, and when n is 2 or more, R ^{5 to} R ⁸ may be the same or different in each repeating unit. ]

Examples of the cyclic monomer include norbornene-based olefins, such as norbornene, vinyl norbornene, etylidene norbornene, norbornadiene, tetracyclododecene, tricyclo [4.3.0.1 ^2,5 ] deca-1-ene, and tricyclo [4]. 3.0.1 ^2,5 ] Compounds having a cyclic olefin skeleton such as deca-3-ene are mentioned, and 2-norbornene (NB) and tetracyclo [6.2.1.1 ^{3, 6} . 0 ^2,7 ] Dodeca-4-en or the like may be used.

(4) The metal ion ionomer contains a metal ion that forms a salt with the carboxyl group and / or the dicarboxylic acid anhydride group of the structural unit (b) of the above (2). Examples of the metal ion of the carboxylic acid base include monovalent or divalent metal ions of the group selected from the group consisting of Group 1, Group 2 and Group 12 of the periodic table, and specifically, lithium ( Ions of Li), sodium (Na), potassium (K), rubidium (Rb), magnesium (Mg), calcium (Ca), zinc (Zn) and the like can be mentioned, and from the viewpoint of ease of handling, sodium in particular. It may be an ion of (Na) or zinc (Zn).
The carboxylic acid base contains, for example, metal ions of Group 1, Group 2, or Group 12 of the Periodic Table after hydrolyzing or thermally decomposing the ester group of the copolymer, or while hydrolyzing or thermally decomposing. It is obtained by converting the ester group moiety in the copolymer into a metal-containing carboxylate by reacting with a compound.
The metal ion may be of one type or a plurality of types.

(5) Copolymer (P)
The copolymer (P) used as the precursor resin of the ionomer used in the present invention contains a structural unit (a) derived from ethylene and / or α-olefin having 3 to 20 carbon atoms, and a carboxyl group and / or an anhydride of dicarboxylic acid. It is characterized in that it contains a structural unit (b) derived from a monomer having a physical group as an essential structural unit, and these are copolymerized substantially linearly, preferably randomly. "Substantially linear" means that the copolymer does not have branches or the branched structure appears infrequently, and the copolymer can be regarded as linear. Specifically, it refers to a state in which the phase angle δ of the copolymer measured under the following conditions is 50 degrees or more.

The copolymer according to the present invention must contain one or more structural units (a) and one or more structural units (b), and must contain a total of two or more monomer units, and the other structural units (c). May include.
The structural unit and the amount of the structural unit of the copolymer according to the present invention will be described.
A structure derived from one molecule each of ethylene and / or an α-olefin (a) having 3 to 20 carbon atoms, a monomer (b) having a carboxyl group and / or a dicarboxylic acid anhydride group, and an arbitrary monomer (c). It is defined as one structural unit in the copolymer.
Then, when the entire structural unit in the copolymer is 100 mol%, the ratio of each structural unit is expressed in mol%, which is the structural unit amount.

Structural unit amount of ethylene and / or α-olefin (A) having 3 to 20 carbon atoms:
The lower limit of the structural unit amount of the structural unit (a) according to the present invention is 60.000 mol% or more, preferably 70.000 mol% or more, more preferably 80.000 mol% or more, still more preferably 85.000 mol% or more, and further. It is more preferably 90.000 mol% or more, particularly preferably 91.200 mol% or more, and the upper limit is 97.999 mol% or less, preferably 97.990 mol% or less, more preferably 97.980 mol% or less, still more preferably 96. It is selected from 980 mol% or less, more preferably 96.900 mol% or less, and particularly preferably 92.700 mol% or less.
If the amount of structural unit derived from ethylene and / or α-olefin (a) having 3 to 20 carbon atoms is less than 60.000 mol%, the toughness of the copolymer is inferior, and if it is more than 97.999 mol%, the copolymer The crystallinity of ethylene is high, and the transparency may deteriorate.

-Structural unit amount of the monomer (b) having a carboxyl group and / or a dicarboxylic acid anhydride group:
The lower limit of the structural unit amount of the structural unit (b) according to the present invention is 2.0 mol% or more, preferably 2.9 mol% or more, more preferably 5.2 mol% or more, and the upper limit is 20.0 mol% or less. It is preferably selected from 15.0 mol% or less, more preferably 10.0 mol% or less, still more preferably 8.0 mol% or less, and particularly preferably 5.4 mol% or less.
If the amount of structural unit derived from the monomer (b) having a carboxyl group and / or a dicarboxylic acid anhydride group is less than 2.0 mol%, the adhesiveness of the copolymer to a highly polar dissimilar material is not sufficient. If it is more than 20.0 mol%, sufficient mechanical properties of the copolymer may not be obtained.

-Structural unit amount of arbitrary monomer (c):
When the structural unit (c) is included, the lower limit of the structural unit amount of the structural unit (c) according to the present invention is 0.001 mol% or more, preferably 0.010 mol% or more, more preferably 0.020 mol% or more. It is even more preferably 0.100 mol% or more, even more preferably 2.000 mol% or more, particularly preferably 1.900 mol% or more, and the upper limit is 20.000 mol% or less, preferably 15.000 mol% or less, more preferably. Is selected from 10.000 mol% or less, more preferably 5.000 mol% or less, and particularly preferably 3.600 mol% or less.
Further, any monomer used may be used alone, or two or more kinds may be used in combination.

-Number of branches per 1,000 carbons of the copolymer (P):
In the molecular structure of polyolefin, short carbon chains such as methyl, ethyl, and butyl having about 1 to 4 carbon atoms may appear as branches. The copolymer of the present invention has a structure that does not have a branch or a branched structure appears infrequently and can be regarded as a linear structure.
In the copolymer of the present invention, the number of methyl branches calculated by ¹³ C-NMR is 50 or less per 1,000 carbons from the viewpoint of increasing the elastic modulus and obtaining sufficient mechanical properties. It may be 5.0 or less, 1.0 or less, or 0.5 or less. The lower limit of the number of methyl branches is not particularly limited, and the smaller the number, the better. Further, the number of ethyl branches may be 3.0 or less, 2.0 or less, 1.0 or less, or 0.5 per 1,000 carbons. It may be less than one. The lower limit of the number of ethyl branches is not particularly limited, and the smaller the number, the better. Further, the number of butyl branches per 1,000 carbons may be 7.0 or less, 5.0 or less, 3.0 or less, 0.5. It may be less than one. The lower limit of the number of butyl branches is not particularly limited, and the smaller the number, the better.

-Method for measuring the amount of structural units derived from the monomer having a carboxy group and / or the dicarboxylic acid anhydride group in the copolymer and the acyclic monomer, and the number of branches:
The amount of structural units derived from the monomer having a carboxy group and / or the dicarboxylic acid anhydride group in the copolymer of the present invention and the acyclic monomer, and the number of branches per 1,000 carbons are ¹³ C-NMR spectra. Obtained using. ¹³ C-NMR is measured by the following method.
Sample 200-300 mg in a mixed solvent (C ₆ H ₄ Cl ₂ / C ₆ D ₅ Br = 2 /) of o-dichlorobenzene (C ₆ H ₄ Cl ₂ ) and benzene dehydride (C ₆ D ₅ Br) 1 (Volume ratio)) 2.4 ml and hexamethyldisiloxane, which is a reference substance for chemical shift, are placed in an NMR sample tube with an inner diameter of 10 mmφ, replaced with nitrogen, sealed, and heat-dissolved to form a uniform solution for NMR measurement samples. And.
The NMR measurement is performed at 120 ° C. using an AV400M type NMR apparatus of Bruker Japan Co., Ltd. equipped with a 10 mmφ cryoprobe.
¹³ C-NMR measures the sample temperature at 120 ° C., the pulse angle at 90 °, the pulse interval at 51.5 seconds, the number of integrations at 512 times or more, and the reverse gate decoupling method.
The chemical shift sets the ¹³ C signal of hexamethyldisiloxane to 1.98 ppm, and the chemical shift of the signal by other ¹³ C is based on this.
In the obtained ¹³ C-NMR, the structural unit amount and the number of branches of each monomer in the copolymer were analyzed by identifying the monomer or the signal peculiar to the branching of the copolymer and comparing the intensities thereof. can do. The position of the signal specific to the monomer or branch can be referred to known data, or can be uniquely identified depending on the sample. Such an analysis method can be generally performed by those skilled in the art.

-Weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn):
The weight average molecular weight (Mw) of the copolymer according to the present invention has a lower limit of usually 1,000 or more, preferably 6,000 or more, and an upper limit of usually 2,000,000 or less, preferably 1. , 500,000 or less, more preferably 1,000,000 or less, particularly preferably 800,000 or less, and most preferably 56,000 or less.
If Mw is less than 1,000, the physical properties such as mechanical strength and impact resistance of the copolymer are not sufficient, and if Mw exceeds 2,000,000, the melt viscosity of the copolymer becomes very high and the copolymer weight is equal. Molding of coalescence may be difficult.

The ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) of the copolymer according to the present invention is usually 1.5 to 4.0, preferably 1.6 to 3.5, and further. It is preferably in the range of 1.9 to 2.3. If Mw / Mn is less than 1.5, various processability including molding of the copolymer is not sufficient, and if it exceeds 4.0, the mechanical properties of the copolymer may be inferior.
Further, in the present invention, (Mw / Mn) may be expressed as a molecular weight distribution parameter.

The weight average molecular weight (Mw) and the number average molecular weight (Mn) according to the present invention are determined by gel permeation chromatography (GPC). Further, for the molecular weight distribution parameter (Mw / Mn), the number average molecular weight (Mn) is further obtained by gel permeation chromatography (GPC), and the ratio of Mw to Mn and Mw / Mn are calculated.

An example of the GPC measuring method according to the present invention is as follows.
(Measurement condition)
Model used: Waters 150C
Detector: MIRAN1A / IR detector manufactured by FOXBORO (measurement wavelength: 3.42 μm)
Measurement temperature: 140 ° C
Solvent: Ortodichlorobenzene (ODCB)
Column: Showa Denko AD806M / S (3)
Flow rate: 1.0 mL / min Injection volume: 0.2 mL
(Sample preparation)
As a sample, prepare a 1 mg / mL solution using ODCB (containing 0.5 mg / mL BHT (2,6-di-t-butyl-4-methylphenol)), and it takes about 1 hour at 140 ° C. And dissolve.
(Calculation of molecular weight (M))
It is performed by the standard polystyrene method, and the conversion from the holding capacity to the molecular weight is performed using a calibration curve prepared in advance using standard polystyrene. The standard polystyrenes used are all brands of (F380, F288, F128, F80, F40, F20, F10, F4, F1, A5000, A2500, A1000) manufactured by Tosoh Corporation. A calibration curve is created by injecting 0.2 mL of a solution dissolved in ODCB (containing 0.5 mg / mL BHT) so that each is 0.5 mg / mL. The calibration curve uses a cubic equation obtained by approximating with the least squares method. The following numerical values are used for the viscosity formula [η] = K × Mα used for conversion to the molecular weight (M).
Polystyrene (PS): K = 1.38 × 10 ^-4 , α = 0.7
Polyethylene (PE): K = 3.92 × 10 ^-4 , α = 0.733
Polypropylene (PP): K = 1.03 × 10 ^-4 , α = 0.78

-Melting point (Tm, ° C):
The melting point of the copolymer according to the present invention is indicated by the maximum peak temperature of the endothermic curve measured by a differential scanning calorimeter (DSC). The maximum peak temperature is the height from the baseline when multiple peaks are shown in the endothermic curve obtained when the vertical axis is the heat flow (mW) and the horizontal axis is the temperature (° C) in the DSC measurement. Indicates the maximum peak temperature, and when there is one peak, it indicates the peak temperature.
The melting point is preferably 50 ° C. to 140 ° C., more preferably 60 ° C. to 138 ° C., and most preferably 70 ° C. to 135 ° C. If it is lower than this range, the heat resistance is not sufficient, and if it is higher than this range, the adhesiveness may be inferior.
For the melting point of the copolymer, for example, using DSC (DSC7020) manufactured by SII Nanotechnology Co., Ltd., about 5.0 mg of a sample is packed in an aluminum pan, and the temperature is raised to 200 ° C. at 10 ° C./min to 200. It can be obtained from the absorption curve when the temperature is kept isothermal at 10 ° C./min for 5 minutes, the temperature is lowered to 20 ° C. at 10 ° C./min, the temperature is kept isothermal at 20 ° C. for 5 minutes, and then the temperature is raised again to 200 ° C. ..

-Molecular structure of copolymer:
The molecular chain terminal of the copolymer according to the present invention may be a structural unit (a) of ethylene and / or an α-olefin having 3 to 20 carbon atoms, and has a carboxyl group and / or a dicarboxylic acid anhydride group. It may be the structural unit (b) of the monomer or the structural unit (c) of any monomer.

Further, the copolymer according to the present invention is a structural unit (a) of ethylene and / or an α-olefin having 3 to 20 carbon atoms, and a structural unit (b) of a monomer having a carboxyl group and / or a dicarboxylic acid anhydride group. , And random copolymers, block copolymers, graft copolymers, etc. of the structural unit (c) of any monomer. Among these, a random copolymer capable of containing a large amount of the structural unit (b) may be used.
An example of the molecular structure (1) of a general ternary copolymer is shown below.
The random copolymer has a structural unit (a) of ethylene and / or α-olefin having 3 to 20 carbon atoms in the molecular structure example (1) shown below, and a carboxyl group and / or a dicarboxylic acid anhydride group. The probability that the structural unit (b) of the monomer and the structural unit (c) of any monomer find each structural unit at a position in an arbitrary molecular chain is a copolymer regardless of the type of the adjacent structural unit. It is a coalescence.
As described below, the molecular structure example (1) of the copolymer is a monomer having a structural unit (a) of ethylene and / or an α-olefin having 3 to 20 carbon atoms and a carboxyl group and / or a dicarboxylic acid anhydride group. The structural unit (b) of the above and the structural unit (c) of any monomer form a random copolymer.

If the molecular structure example (2) of the copolymer into which the structural unit (b) of the monomer having a carboxyl group and / or the dicarboxylic acid anhydride group is introduced by graft modification is also posted for reference, ethylene and / or the number of carbon atoms is 3. A part of the copolymer obtained by copolymerizing the structural unit (a) of α-olefin of ~ 20 and the structural unit (c) of any monomer is a monomer having a carboxyl group and / or a dicarboxylic acid anhydride group. It is graft-modified to the structural unit (b).

Further, the random copolymerizability of the copolymer can be confirmed by various methods, but a method for discriminating the random copolymerizability from the relationship between the comonomer content of the copolymer and the melting point is described in "Japanese Patent Laid-Open No. 2015- It is described in detail in "No. 163691" and "Japanese Patent Laid-Open No. 2016-079408". From the above document, if the melting point (Tm, ° C.) of the copolymer is higher than -3.74 × [Z] +130 (where [Z] is the comonomer content / mol%), it can be judged that the randomness is low. ..

The copolymer according to the present invention, which is a random copolymer, has a melting point (Tm, ° C.) observed by differential scanning calorimetry (DSC) and a structural unit of a monomer having a carboxyl group and / or a dicarboxylic acid anhydride group ( It is preferable that the total content [Z] (mol%) of b) and the structural unit (c) of any monomer satisfies the following formula (I).
50 <Tm <-3.74 × [Z] +130 ... (I)
When the melting point (Tm, ° C) of the copolymer is higher than -3.74 x [Z] +130 (° C), the random copolymerization is low, so the mechanical properties such as impact strength are inferior, and the melting point is higher than 50 ° C. If it is low, the heat resistance may be inferior.

Further, the copolymer according to the present invention is preferably produced in the presence of a transition metal catalyst from the viewpoint of making its molecular structure linear.
It is known that the molecular structure of a copolymer differs depending on the production method, such as polymerization by a high-pressure radical polymerization method process or polymerization using a metal catalyst.
This difference in molecular structure can be controlled by selecting the production method. For example, as described in Japanese Patent Application Laid-Open No. 2010-150532, the complex elastic modulus measured by a rotary rheometer. The molecular structure can also be estimated by.

-Phase angle δ at absolute value G ^* = 0.1 MPa of complex elastic modulus:
In the copolymer of the present invention, the phase angle δ at the absolute value G ^* = 0.1 MPa of the complex elastic modulus measured by the rotary rheometer is preferably 51 degrees or more, and more preferably 54 degrees or more. It is more preferably 56 degrees or higher, and even more preferably 58 degrees or higher. The upper limit of the phase angle δ is not particularly limited, and the closer it is to 75 degrees, the better.
More specifically, when the phase angle δ (G ^* = 0.1 MPa) at the absolute value G ^* = 0.1 MPa of the complex elastic modulus measured by the rotary rheometer is 50 degrees or more, the molecular structure of the copolymer. Is a linear structure that does not contain any long-chain branches or has a substantially linear structure that contains a small amount of long-chain branches that do not affect the mechanical strength. Shown.
Further, when the phase angle δ (G ^* = 0.1 MPa) at the absolute value G ^* = 0.1 MPa of the complex elastic modulus measured by the rotary rheometer is lower than 50 degrees, the molecular structure of the copolymer has a long-chain branch. The structure is excessively contained, and the mechanical strength is inferior.
The phase angle δ at the absolute value G ^* = 0.1 MPa of the complex elastic modulus measured by the rotary rheometer is affected by both the molecular weight distribution and the long chain branching. However, if it is limited to a copolymer having Mw / Mn ≦ 4, more preferably Mw / Mn ≦ 3, it can be an index of the amount of long chain branching, and the more long chain branching contained in the molecular structure, the more δ (G ^*). = 0.1 MPa) The value becomes smaller. If the Mw / Mn of the copolymer is 1.5 or more, the δ (G ^* = 0.1 MPa) value may exceed 75 degrees even if the molecular structure does not include long-chain branches. Absent.

The method for measuring the complex elastic modulus is as follows.
The sample is placed in a 1.0 mm thick heat press mold, preheated in a heat press machine with a surface temperature of 180 ° C. for 5 minutes, and then pressurized and depressurized repeatedly to degas the residual gas in the molten resin. Pressurize at 4.9 MPa and hold for 5 minutes. Then, the sample was transferred to a press machine having a surface temperature of 25 ° C. and cooled by holding at a pressure of 4.9 MPa for 3 minutes to prepare a press plate composed of a sample having a thickness of about 1.0 mm. A press plate made of a sample is processed into a circle with a diameter of 25 mm, and a dynamic viscoelasticity is measured under the following conditions in a nitrogen atmosphere using an ARES type rotary rheometer manufactured by Rheometrics as a measuring device for dynamic viscoelasticity characteristics. Measure.
・ Plate: φ25mm Parallel plate ・ Temperature: 160 ℃
・ Distortion amount: 10%
-Measurement angular frequency range: 1.0 x 10 ^{-2 to} 1.0 x 10 ² rad / s
・ Measurement interval: 5 points / decade
The phase angle δ is plotted against the common logarithm logG ^* of the absolute value G ^* (Pa) of the complex elastic modulus, and the value of δ (degrees) of the point corresponding to logG ^* = 5.0 is δ (G ^* = 0). .1 MPa). When there is no point corresponding to log G ^* = 5.0 in the measurement point, log G ^* = 5.0 with two points before and after obtaining the δ value in log G ^* = 5.0 by linear interpolation. When all the measurement points are logG ^* <5, the δ value at logG ^* = 5.0 is subtracted from the quadratic curve using the values of the three points from the largest logG ^* value.

-Production of Copolymer The copolymer according to the present invention is preferably produced in the presence of a transition metal catalyst from the viewpoint of making its molecular structure linear.

-Polymerization catalyst The type of polymerization catalyst used in the production of the copolymer according to the present invention is that the structural unit (a), the structural unit (b), and any structural unit (c) can be copolymerized. If there is, the present invention is not particularly limited, and examples thereof include Group 5 to 11 transition metal compounds having a chelating ligand.
Specific examples of preferable transition metals include vanadium atom, niobium atom, tantalum atom, chromium atom, molybdenum atom, tungsten atom, manganese atom, iron atom, platinum atom, ruthenium atom, cobalt atom, rhodium atom, nickel atom and palladium atom. , Copper atom and the like. Among these, the transition metal of Group 8 to 11 is preferable, the transition metal of Group 10 is more preferable, and nickel (Ni) and palladium (Pd) are particularly preferable. These metals may be single or in combination of two or more.
The chelating ligand has at least two atoms selected from the group consisting of P, N, O, and S and is either bidentate or multidentate. It contains a ligand and is electronically neutral or anionic. A review by Brookhard et al. Illustrates the structure of chelating ligands (Chem. Rev., 2000, 100, 1169).
Preferred examples of the chelating ligand include bidentate anionic P and O ligands. Examples of the bidentate anionic P and O ligands include phosphorus sulfonic acid, phosphorus carboxylic acid, phosphorus phenol, and phosphorus enolate. Other examples of chelating ligands include bidentate anionic N and O ligands. Examples of the bidentate anionic N and O ligands include salicylic acid and pyridinecarboxylic acid. Other examples of the chelating ligand include a diimine ligand, a diphenoxide ligand, and a diamide ligand.

The structure of the metal complex obtained from the chelating ligand is represented by the following structural formula (c1) or (c2) in which an arylphosphine compound, an arylarcin compound or an arylantimon compound which may have a substituent is coordinated. To.

[In the structural formula (c1) and the structural formula (c2),
M represents a transition metal belonging to any of Group 5 to 11 of the periodic table of elements, that is, various transition metals as described above.
X ¹ represents oxygen, sulfur, -SO _3- , or -CO _2- .
Y ¹ represents carbon or silicon.
n represents an integer of 0 or 1.
E ¹ represents phosphorus, arsenic or antimony.
R ⁵³ and R ⁵⁴ each independently represent a hydrocarbon group that may contain hydrogen or a heteroatom having 1 to 30 carbon atoms.
R ⁵⁵ represents a hydrocarbon group that may independently contain hydrogen, halogen, or a heteroatom having 1 to 30 carbon atoms.
R ⁵⁶ and R ⁵⁷ are each independently a hydrocarbon group which may contain hydrogen, halogen, or a heteroatom having 1 to 30 carbon atoms, OR ⁵² , CO ₂ R ⁵² , CO ₂ M', C (O). N (R ⁵¹ ) ₂ , C (O) R ⁵² , SR ⁵² , SO ₂ R ⁵² , SOR ⁵² , OSO ₂ R ⁵² , P (O) (OR ⁵² ) _2-y (R ⁵¹ ) _y , CN, NHR _{^{52, N (R 52) 2}} , Si (OR 51) 3-x (R 51) x, OSi (OR 51) 3-x (R 51) x, NO 2, SO 3 M ', PO 3 M' 2 , P (O) (OR ⁵² ) ₂ M'or represents an epoxy-containing group.
R ⁵¹ represents hydrogen or a hydrocarbon group having 1 to 20 carbon atoms.
R ⁵² represents a hydrocarbon group having 1 to 20 carbon atoms.
M'represents an alkali metal, alkaline earth metal, ammonium, quaternary ammonium or phosphonium, x represents an integer from 0 to 3, and y represents an integer from 0 to 2.
R ⁵⁶ and R ⁵⁷ may be linked to each other to form an alicyclic ring, an aromatic ring, or a heterocycle containing a heteroatom selected from oxygen, nitrogen, or sulfur. At this time, the number of ring members is 5 to 8, and the ring may or may not have a substituent.
L ¹ represents a ligand coordinated to M.
Further, R ⁵³ and L ¹ may be bonded to each other to form a ring. ]

More preferably, the complex serving as a polymerization catalyst is a transition metal complex represented by the following structural formula (c3).

[In the structural formula (c3),
M represents a transition metal belonging to any of Group 5 to 11 of the periodic table of elements, that is, various transition metals as described above.
X ¹ represents oxygen, sulfur, -SO _3- , or -CO _2- .
Y ¹ represents carbon or silicon.
n represents an integer of 0 or 1.
E ¹ represents phosphorus, arsenic or antimony.
R ⁵³ and R ⁵⁴ each independently represent a hydrocarbon group that may contain hydrogen or a heteroatom having 1 to 30 carbon atoms.
R ⁵⁵ represents a hydrocarbon group that may independently contain hydrogen, halogen, or a heteroatom having 1 to 30 carbon atoms.
R ⁵⁸ , R ⁵⁹ , R ⁶⁰ and R ⁶¹ are hydrocarbon groups, OR ⁵² , CO ₂ R ⁵² and CO ₂ M, which may independently contain hydrogen, halogen and heteroatoms having 1 to 30 carbon atoms, respectively. ', C (O) N (R ⁵¹ ) ₂ , C (O) R ⁵² , SR ⁵² , SO ₂ R ⁵² , SOR ⁵² , OSO ₂ R ⁵² , P (O) (OR ⁵² ) _2-y (R ⁵¹⁾ ) _Y , CN, NHR ⁵² , N (R ⁵² ) ₂ , Si (OR ⁵¹ ) _3-x (R ⁵¹ ) _x , OSi (OR ⁵¹ ) _3-x (R ⁵¹ ) _x , NO ₂ , SO ₃ M' represents _{PO 3 M '2, P (} O) (oR 52) 2 M' or epoxy containing group.
R ⁵¹ represents hydrogen or a hydrocarbon group having 1 to 20 carbon atoms.
R ⁵² represents a hydrocarbon group having 1 to 20 carbon atoms.
M'represents an alkali metal, alkaline earth metal, ammonium, quaternary ammonium or phosphonium, x represents an integer from 0 to 3, and y represents an integer from 0 to 2.
A plurality of groups appropriately selected from R ^{58 to} R ⁶¹ are linked to each other to form an alicyclic ring, an aromatic ring, or a heterocycle containing a hetero atom selected from oxygen, nitrogen, or sulfur. May be good. At this time, the number of ring members is 5 to 8, and the ring may or may not have a substituent.
L ¹ represents a ligand coordinated to M.
Further, R ⁵³ and L ¹ may be bonded to each other to form a ring. ]

Here, as a catalyst of the transition metal compound of Group 5 to 11 having a chelating ligand, a catalyst such as a so-called SHOP-based catalyst and a Drent-based catalyst is typically known.
The SHOP-based catalyst is a catalyst in which a phosphorus-based ligand having an aryl group, which may have a substituent, is coordinated to a nickel metal (see, for example, WO2010-05256).
Further, the Drent-based catalyst is a catalyst in which a phosphorus-based ligand having an aryl group, which may have a substituent, is coordinated with a palladium metal (see, for example, JP-A-2010-20647).

-Polymer polymerization method:
The method for polymerizing the copolymer according to the present invention is not limited.
As a polymerization method, slurry polymerization in which at least a part of the produced polymer becomes a slurry in a medium, bulk polymerization using the liquefied monomer itself as a medium, vapor phase polymerization performed in a vaporized monomer, or liquefaction at high temperature and high pressure Examples thereof include high-pressure ionic polymerization in which at least a part of the produced polymer is dissolved in the monomer.
The polymerization form may be any of batch polymerization, semi-batch polymerization, and continuous polymerization.
Further, the living polymerization may be carried out, or the polymerization may be carried out while causing chain transfer.
Further, at the time of polymerization, a so-called chain shutting agent (CSA) may be used in combination to carry out a chain shutting reaction or a coordinative chain transfer polymerization (CCTP).
Specific manufacturing processes and conditions are disclosed in, for example, JP-A-2010-260913 and JP-A-2010-202647.

-Method of introducing a carboxyl group and / or a dicarboxylic acid anhydride group into the copolymer:
The method for introducing a carboxyl group and / or a dicarboxylic acid anhydride group into the copolymer according to the present invention is not particularly limited.
A carboxyl group and / or a dicarboxylic acid anhydride group can be introduced by various methods as long as the gist of the present invention is not deviated.
The method for introducing a carboxyl group and / or a dicarboxylic acid anhydride group is, for example, a method of directly copolymerizing a comonomer having a carboxyl group and / or a dicarboxylic acid anhydride group, or a method of copolymerizing another monomer and then modifying the carboxyl group. Examples thereof include a method of introducing a group and / or a dicarboxylic acid anhydride group.

As a method of introducing a carboxyl group and / or a dicarboxylic acid anhydride group by modification, for example, in the case of introducing a carboxylic acid, a method of copolymerizing an acrylic acid ester and then hydrolyzing it to change to a carboxylic acid or an acrylic acid t- Examples thereof include a method of copolymerizing butyl and then converting it into a carboxylic acid by thermal decomposition.

A conventionally known acid / base catalyst may be used as an additive that promotes the reaction during the above-mentioned hydrolysis or thermal decomposition. The acid / base catalyst is not particularly limited, but for example, alkali metals such as sodium hydroxide, potassium hydroxide and lithium hydroxide, hydroxides of alkaline earth metals, alkali metals such as sodium hydrogencarbonate and sodium carbonate, and alkaline soil. Carbonates of similar metals, solid acids such as montmorillonite, inorganic acids such as hydrochloric acid, nitrate and sulfuric acid, organic acids such as formic acid, acetic acid, benzoic acid, citric acid, paratoluenesulfonic acid, trifluoroacetic acid and trifluoromethanesulfonic acid. Can be used as appropriate. Sodium hydroxide, potassium hydroxide, sodium carbonate, paratoluenesulfonic acid and trifluoroacetic acid are preferable, and paratoluenesulfonic acid and trifluoroacetic acid are more preferable, from the viewpoints of reaction promoting effect, price, device corrosiveness and the like.

(6) Ionomer In the ionomer according to the present invention, at least a part of the carboxyl group and / or the dicarboxylic acid anhydride group of the structural unit (b) of the copolymer of the present invention is caused by the above-mentioned metal ions in Group 1 of the periodic table. It is an ionomer having a substantially linear structure converted into a metal-containing carboxylate containing at least one metal ion selected from Group 2 or Group 12.

-Structure of ionomer Since the ionomer according to the present invention is a random copolymer having a substantially linear structure like the copolymer according to the present invention, the parameters related to the structure are the same as those of the copolymer. It is preferably in the range. That is, the same preferred embodiments as for the copolymer are applied to the phase angle δ and the melting point (Tm, ° C.) at the absolute value G ^* = 0.1 MPa of the complex elastic modulus measured by the rotary rheometer. The ionomer is obtained by allowing a metal salt to act on the precursor resin as described later, and at that time, a reaction that cleaves the molecular chain of the polymer does not usually occur. For this reason, structural parameters such as comonomer molar ratio, degree of branching, and randomness are usually conserved between the precursor resin and the ionomer.

・ Neutralization degree (mol%)
The content of the metal ion in the ionomer preferably includes an amount that neutralizes at least a part or all of the carboxyl group and / or the dicarboxylic acid anhydride group in the copolymer as the precursor resin, which is preferable neutralization. The degree (average neutralization degree) is 5 to 95 mol%, more preferably 10 to 90 mol%, and further preferably 20 to 80 mol%.
When the degree of neutralization is high, the tensile strength and tensile fracture stress of the ionomer are high, and the tensile fracture strain is small, but the melt flow rate (MFR) of the ionomer tends to be low. On the other hand, when the degree of neutralization is low, an ionomer having an appropriate MFR can be obtained, which is more preferable in terms of moldability, but the tensile elastic modulus and tensile fracture stress tend to be low, and the tensile fracture strain tends to be high.
The degree of neutralization can be calculated from the amount of the carboxyl group and / or the dicarboxylic acid anhydride group and the molar ratio of the added metal ions.

-Method for producing ionomer The ionomer according to the present invention is ethylene and / or α-olefin having 3 to 20 carbon atoms obtained by the method for introducing a carboxyl group and / or a dicarboxylic acid anhydride group into the copolymer as described above. / A conversion step of treating an unsaturated carboxylic acid copolymer with a metal salt containing at least one metal ion selected from Group 1, Group 2, or Group 12 of the Periodic Table to convert it into a metal-containing carboxylic acid salt. It may be obtained by passing. Further, the ionomer according to the present invention heats ethylene and / or an α-olefin / unsaturated carboxylic acid ester copolymer having 3 to 20 carbon atoms, and displays at least a part of the ester groups in the copolymer in the periodic table. It may be obtained by undergoing a heat conversion step of converting into a metal-containing carboxylate containing at least one metal ion selected from Group 1, Group 2, or Group 12.

When an ionomer is produced after introducing a carboxyl group and / or a dicarboxylic acid anhydride group into the polymer, the production method thereof is, for example, as follows. That is, a metal ion supply source is prepared by heating and kneading a metal ion-capturing substance such as an ethylene / methacrylic acid (MAA) copolymer and a metal salt in some cases, and then the metal is used as a precursor resin of ionomer. It can be obtained by adding an ion supply source in an amount having a desired degree of neutralization and kneading.

Further, in the heat conversion step, (i) ethylene and / or an α-olefin / unsaturated carboxylic acid ester copolymer having 3 to 20 carbon atoms is heated, and ethylene and / or carbon atoms are 3 by hydrolysis or thermal decomposition. After forming an α-olefin / unsaturated carboxylic acid copolymer of ~ 20, the ethylene and / or carbon number 3 is formed by reacting with a compound containing a metal ion of Group 1, Group 2, or Group 12 of the periodic table. The carboxylic acid in the α-olefin / unsaturated carboxylic acid copolymer of ~ 20 may be converted to the metal-containing carboxylic acid salt, and (ii) ethylene and / or α-olefin having 3 to 20 carbon atoms. / The unsaturated carboxylic acid ester copolymer is heated, and the ester group of the copolymer is hydrolyzed or thermally decomposed to react with a compound containing metal ions of Group 1, Group 2, or Group 12 of the periodic table. Thereby, the ester group portion in the ethylene and / or α-olefin / unsaturated carboxylic acid ester copolymer having 3 to 20 carbon atoms may be converted into the metal-containing carboxylic acid salt.

Further, the compound containing a metal ion may be a metal oxide, hydroxide, carbonate, bicarbonate, acetate, formate or the like of the metal of Group 1, Group 2, or Group 12 of the periodic table.
The compound containing a metal ion may be supplied to the reaction system in the form of granules or fine powder, or may be supplied to the reaction system after being dissolved or dispersed in water or an organic solvent, and the ethylene / unsaturated carboxylic acid copolymer may be used. A master batch using a polymer or an olefin copolymer as a base polymer may be prepared and supplied to the reaction system. In order to allow the reaction to proceed smoothly, a method of preparing a masterbatch and supplying it to the reaction system is preferable.

Furthermore, the reaction with the compound containing metal ions may be carried out by melt-kneading with various types of devices such as a vent extruder, a Banbury mixer and a roll mill, and the reaction may be carried out by a batch method or a continuous method. Since the reaction can be smoothly carried out by discharging the water and carbon dioxide gas produced by the reaction by the deaerator, it is preferable to continuously carry out the reaction using an extruder equipped with a degassing device such as a bent extruder. ..
When reacting with a compound containing metal ions, a small amount of water may be injected to accelerate the reaction.

The temperature for heating the ethylene and / or α-olefin / unsaturated carboxylic acid ester copolymer having 3 to 20 carbon atoms may be a temperature at which the ester becomes a carboxylic acid, and if the heating temperature is too low, the ester is carboxylic. If it is not converted to an acid and is too high, decarbonylation and decomposition of the copolymer proceed. Therefore, the heating temperature of the present invention is preferably in the range of 80 ° C. to 350 ° C., more preferably 100 ° C. to 340 ° C., still more preferably 150 ° C. to 330 ° C., and even more preferably 200 ° C. to 320 ° C.

The reaction time varies depending on the heating temperature, the reactivity of the ester group portion, etc., but is usually 1 minute to 50 hours, more preferably 2 minutes to 30 hours, further preferably 2 minutes to 10 hours, and further. It is preferably 2 minutes to 3 hours, and particularly preferably 3 minutes to 2 hours.

In the above step, the reaction atmosphere is not particularly limited, but it is generally preferable to carry out the step under an inert gas stream. As an example of the inert gas, a nitrogen, argon or carbon dioxide atmosphere can be used, and a small amount of oxygen or air may be mixed.

The reactor used in the above step is not particularly limited, but is not limited as long as it is a method capable of stirring the copolymer substantially uniformly, and a glass container equipped with a stirrer or an autoclave (AC) is used. Alternatively, any conventionally known kneader such as Brabender plastograph, single-screw or twin-screw extruder, strong screw kneader, Banbury mixer, kneader, roll, etc. can be used.

Whether or not a metal ion was introduced into the precursor resin and became an ionomer was confirmed by measuring the IR spectrum of the obtained resin and examining the decrease in the peak derived from the carbonyl group of the carboxylic acid (dimer). can do. Similarly, the degree of neutralization is calculated from the above-mentioned molar ratio, and by examining the decrease in the peak derived from the carbonyl group of the carboxylic acid (dimer) and the increase in the peak derived from the carbonyl group of the carboxylic acid base. , Can be confirmed.

The amount of ionomer in the flame-retardant resin composition is not particularly limited as long as it can be used for electric wires and cables, but it is preferably contained in an amount of 1 to 50% by weight based on the total amount with the above-mentioned polyolefin resin. .. It is more preferably in the range of 1 to 20% by weight, more preferably in the range of 1 to 10% by weight, based on the total amount with the polyolefin resin. Within this range, it is possible to obtain a resin composition that satisfies the required physical properties such as moldability as a resin and has excellent wear resistance.

3. 3. Flame retardant (C)
The flame retardant resin composition of the present invention contains a flame retardant. A commercially available flame retardant can be used, and the type is not particularly limited as long as it can be uniformly mixed with the polyolefin resin (A) and the ionomer (B). It is preferable to use a metal hydroxide as a flame retardant.

Examples of the metal hydroxide include hydroxyl group or crystalline water such as magnesium hydroxide, aluminum hydroxide, calcium hydroxide, basic magnesium carbonate, hydrated aluminum silicate, hydrated magnesium silicate, basic magnesium carbonate, and hydrotalcite. Can be used alone or in combination of two or more compounds having. Among these metal hydroxides, magnesium hydroxide and aluminum hydroxide are preferable, and magnesium hydroxide is most preferable. Further, these are particularly preferably those subjected to surface treatment.

The magnesium hydroxide is obtained by reacting magnesium hydroxide generally used in a flame-retardant resin composition, that is, magnesium chloride in seawater with calcium hydroxide, and performing steps such as sedimentation, washing, and concentration. Examples of magnesium hydroxide to be used include "Kisuma 5", "Kisuma 5A", "Kisuma 5B", and "Kisuma 5J" (trade name: manufactured by Kyowa Chemical Industry Co., Ltd.).
Further, known substances such as magnesium hydroxide obtained by pulverizing a natural mineral (brucite) containing magnesium hydroxide as a main component can also be used. Furthermore, in recent years, magnesium chloride obtained by treating natural minerals containing magnesium (blue sight, serpentine, dolomite, green mudstone, etc.) with hydrochloric acid is used as a raw material, and for example, it reacts with calcium hydroxide to settle, wash, and so on. In addition to magnesium hydroxide obtained by a step such as concentration, magnesium hydroxide obtained by hydrating magnesium oxide obtained by dissolution, purification, and thermal decomposition can be used. However, the present invention is not limited to these above.
Among these, magnesium hydroxide obtained by calcining magnesium carbonate to obtain magnesium oxide and hydrating it has a large specific surface area of 8 m ² / g or more, and also has the performance of a conventional flame-retardant composition. It is preferable because it is highly flame-retardant, economically inexpensive, has excellent easy-to-cut properties (peeling and cutting processability) of electric wires and cable terminals during electric wire and cable construction, and has good workability. used.

As a preferable method for producing the above-mentioned metal hydroxide, as a natural mineral (magnesite) shown in JP-A-3-60774, JP-A-5-208810, and JP-A-8-67515. Examples thereof include a method in which the produced magnesium carbonate is calcined and pulverized to obtain fine powder of lightly calcined magnesia, which is then subjected to a hydration reaction.
In addition, by using a method of calcining and crushing magnesium carbonate produced as a natural mineral (magnesite) to obtain magnesium hydroxide, the crushing time during the crushing process is used. By controlling the milling speed, pH during the scavenging step, reaction temperature, etc., magnesium hydroxide with optimized average particle size, specific surface area, and aggregated structure can be produced at low cost.

Further, the metal hydroxide is preferably treated with a surface treatment agent in order to improve the dispersion effect in the thermoplastic resin, the suppression of moisture absorption, the deactivation of the metal active site, and the like.
Examples of the surface treatment agent include fatty acids and fatty acid metal salts or mixtures thereof, as well as fatty acid esters, fatty acid amides, waxes or modified products thereof, curable resins, organic silanes, organic titanates, and organic boranes. Further, in recent years, as disclosed in JP-A-2002-167219, JP-A-2002-173682, JP-A-2003-003167, JP-A-2004-337698, etc., polycarboxylic acid-based dispersions Magnesium hydroxide surface-treated with agents, polyglycerin derivatives, N-acyl basic amino acids, or erythritol dibasic acid esters, phosphate esters, phosphite esters, alcohol phosphate esters, phosphorus compounds, etc. is also used. There is. In the present invention, but not particularly limited to these, a combination with a fatty acid and a fatty acid metal salt or a mixture thereof, and a fatty acid ester is particularly preferable from the viewpoint of low cost and effectiveness. These may be surface-treated in advance, or a resin component and magnesium hydroxide may be mixed and used at the same time.

As the fatty acid, saturated acid or unsaturated acid having 8 or more carbon atoms is desirable, and octanoic acid, decanoic acid, myristic acid, behenic acid, palmitic acid, stearic acid, oleic acid, araquinic acid, palm oil, beef fat, and large Examples include soybean oil, palm oil, and hydrogenated oil. Examples of the fatty acid metal salt include metal salts such as stearic acid, oleic acid, palmitic acid, linoleic acid, lauric acid, caprylic acid, behenic acid, and montanic acid, and examples of the metal include Na, K, Al, and Ca. Examples thereof include Mg, Zn, Ba, Co, Sn, Ti and Fe. Examples of the fatty acid ester include methyl laurate, methyl mistylate, methyl palmitate, methyl stearate, methyl oleate, methyl erucate, methyl behenate, butyl laurate, butyl stearate, isopropyl mistylate, and isopropyl palmitate. Monoesters such as octyl palmitate, octyl coconut fatty acid, octyl stearate, octyl steat, lauryl laurate, stearyl stearate, higher alcohol ester of long chain fatty acids, behenyl behenate, cetyl mistylate, etc. Neopentyl polyol long chain fatty acid ester, partial esterified neopentyl polyol long chain fatty acid ester, neopentyl polyol fatty acid ester, neopentyl polyol medium chain fatty acid ester, neopentyl polyol C9 chain fatty acid ester, dipentaerythritol long chain fatty acid ester, Special fatty acid esters such as complex medium chain fatty acid esters can be mentioned.
These surface treatment agents can be used by any treatment method such as a wet method and a dry method. The amount of the surface treatment agent used is preferably in the range of 1 to 10% by mass with respect to the metal hydroxide.

The amount of the flame retardant in the flame-retardant resin composition is not particularly limited as long as it can be uniformly mixed to form the resin composition and can be used for electric wires and cables, but the above-mentioned polyolefin resin and ionomer It is preferable to include 30 to 300 parts by weight with respect to 100 parts by weight of the total amount. It is more preferably in the range of 50 to 200 parts by weight, and further preferably in the range of 80 to 150 parts by weight with respect to 100 parts by weight of the total amount of the polyolefin resin and the ionomer resin. Within this range, the required physical properties such as moldability as a resin can be satisfied, and sufficient flame retardancy can be imparted to the resin composition. If it is less than 30 parts by weight, the flame retardancy becomes insufficient, and if it exceeds 300 parts by mass, the material tends to become brittle and hard, and not only the flexibility and mechanical strength of the product tend to decrease, but also scratches. There is a possibility that the harmful effect of whitening may occur.

In the flame retardant resin composition of the present invention, a flame retardant auxiliary may be blended in order to further improve the performance. As flame retardants, red phosphorus, antimony trioxide, antimony pentoxide, calcium phosphate, zircon oxide, titanium oxide, zinc oxide, magnesium oxide, calcium carbonate, magnesium carbonate, barium sulfate, barium borate, barium borate, boric acid Zinc, zinc metaborate, molybdenum disulfide, clay, caustic soil, kaolinite, montmorillonite, hydrotalcite, talc, silica, white carbon, zeolite, hydromagnetite, organic bentonite and the like may be used in combination. It is desirable that these flame retardants are blended in an amount of up to 50% by weight based on the above metal hydroxide.

4. Flame Retardant Resin Composition The flame retardant resin composition of the present invention is a composition containing the above-mentioned polyolefin resin (A), ionomer resin (B) and flame retardant (C). The flame-retardant resin composition of the present invention can be composed of the above three components, but since a large amount of flame retardant is blended, heat is used to secure the receiving amount and maintain flexibility. A plastic elastomer may be used in combination. The composition ratio can be appropriately set by those skilled in the art and can be a preferable composition for electric wires and cables, but is 0 to 95 weight based on the total weight of the polyolefin resin (A) and the ionomer resin (B). %, More preferably 3 to 80% by weight, and particularly preferably 10 to 50% by weight. By selecting a known flexible resin or an olefin-based elastomer such as EPR and EPDM as the thermoplastic elastomer, high flame retardancy and high moldability can be maintained, and mechanical strength can be improved.

In the flame-retardant resin composition of the present invention, each of the above components is blended in the above-mentioned blending ratio in an arbitrary order, and a uniaxial extruder, a twin screw extruder, a super mixer, a Henschel mixer, a Banbury mixer, a roll mixer, and the like. It can be produced by kneading and granulating using a normal kneader such as a lavender plastograph or a kneader. In this case, it is preferable to select a kneading and granulating method capable of improving the dispersion of each component, and it is particularly preferable to knead and granulate using a twin-screw extruder from the viewpoint of economy and the like. The kneading machine may be a multi-step kneading using a plurality of machines by different kneading methods.

-Additives For ionomers related to the present invention, in addition to the above flame retardant aids, conventionally known antioxidants, ultraviolet absorbers, lubricants, antistatic agents, and colorants, as long as the gist of the present invention is not deviated , Pigments, cross-linking agents, foaming agents, nucleating agents, and additives such as fillers may be blended. Appropriate amounts of these additives can be used by those skilled in the art.

5. Electric wire / cable One aspect of the present invention is an electric wire or cable using the flame-retardant resin composition as a coating material. The flame-retardant resin composition of the present invention comprises an insulating layer and / or a sheath layer such as an electric wire, a power cable, or an optical fiber cable, an internal semi-conductive layer and / or an external semi-conductive layer, or, if desired, an external such as copper, aluminum, or lead. It may be used as a coating layer provided in a usual electric wire / cable such as a metal shielding layer or a water shielding layer wound with aluminum tape. Further, the method for manufacturing the electric wire / cable may be a general method, which may be crosslinked by an organic peroxide or silane crosslink, or may be used in a non-crosslinked state or foamed, or may be used in a thermoplastic resin or metal foil. , Non-woven fabric, woven fabric, and other base materials may be laminated and used, and the present invention is not particularly limited.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples. In the table, no data means unmeasured, and not detected means less than the detection limit.

[material]
The following substances were used as raw materials for the resin compositions prepared in Examples and Comparative Examples.
[Polyolefin-based resin]
(A-1) Ethylene-ethyl acrylate copolymer (acrylic acid content 15% by weight, MFR 0.8 g / 10 minutes)
(A-2) Ethylene-vinyl acetate copolymer (vinyl acetate content 15% by weight, MFR 1.0 g / 10 minutes)
(A-3) Maleic anhydride-modified polyethylene (maleic anhydride graft amount 0.20% by weight, MFR 1.3 g / 10 minutes, density 0.920 g / cm ³ )
(A-4) Ethylene-ethyl acrylate copolymer (acrylic acid content 20% by weight, MFR 0.4 g / 10 minutes)
[Ionomer resin]
(B-1) Ionomer Using an E / AA / NB copolymer as the ionomer resin (B-1), an E / AA / NB ternary ionomer using Na ion as a metal species was produced. Table 1 shows the physical properties of the obtained ionomer. Here, E means ethylene, AA means acrylic acid, and NB means norbornene as constituent units.
As (B-2), an ionomer resin (manufactured by Mitsui Dow Polychemical Co., Ltd., registered trademark: HIMILAN, grade name) which is a copolymer of ethylene, methacrylic acid and Na methacrylate and is produced by a high-pressure radical method process. : HIM1605) was used. Table 1 shows the physical properties of ionomers.
As (B-3), an E / AA copolymer was used to produce an E / AA binary ionomer using Na ions as a metal species. Table 1 shows the physical properties of the obtained ionomer.
[Flame retardants]
(C-1) Commercially available magnesium hydroxide (Kyowa Chemical Industry Co., Ltd., Kisuma 5A)

The physical properties were measured and evaluated in Examples and Comparative Examples by the methods shown below.

<Measurement and evaluation>
(1) Measurement of phase angle δ (G ^* = 0.1 MPa) at absolute value G ^* = 0.1 MPa of complex elastic modulus 1) Preparation and measurement of sample Place the sample in a heat press mold with a thickness of 1.0 mm. After preheating in a hot press machine having a surface temperature of 180 ° C. for 5 minutes, the residual gas in the molten resin was degassed by repeating pressurization and depressurization, further pressurized at 4.9 MPa, and held for 5 minutes. Then, it was transferred to a press machine having a surface temperature of 25 ° C. and cooled by holding it at a pressure of 4.9 MPa for 3 minutes to prepare a press plate composed of a sample having a thickness of about 1.0 mm. A press plate made of a sample is processed into a circle with a diameter of 25 mm, and a dynamic viscoelasticity is measured under the following conditions in a nitrogen atmosphere using an ARES type rotary rheometer manufactured by Rheometrics as a measuring device for dynamic viscoelasticity characteristics. It was measured.
・ Plate: φ25mm (diameter) Parallel plate ・ Temperature: 160 ℃
・ Distortion amount: 10%
-Measurement angular frequency range: 1.0 x 10 ^{-2 to} 1.0 x 10 ² rad / s
・ Measurement interval: 5 points / decade
The phase angle δ is plotted against the common logarithm logG ^* of the absolute value G ^* (Pa) of the complex elastic modulus, and the value of δ (degrees) of the point corresponding to logG ^* = 5.0 is δ (G ^* = 0). .1 MPa). When there is no point corresponding to log G ^* = 5.0 in the measurement point, log G ^* = 5.0 with two points before and after to determine the δ value in log G ^* = 5.0 by linear interpolation. When all the measurement points were logG ^* <5, the δ value at logG ^* = 5.0 was subtracted from the quadratic curve using the values of the three points from the largest logG ^* value.

(2) Measurement of Weight Average Molecular Weight (Mw) and Molecular Weight Distribution Parameter (Mw / Mn) The weight average molecular weight (Mw) was determined by gel permeation chromatography (GPC). The molecular weight distribution parameter (Mw / Mn) was further determined by gel permeation chromatography (GPC) to obtain a number average molecular weight (Mn), and was calculated by the ratio of Mw to Mn and Mw / Mn.
The measurement was performed according to the following procedure and conditions.

1) Pretreatment of the sample When the sample contained a carboxylic acid group, esterification treatment such as methyl esterification using diazomethane or trimethylsilyl (TMS) diazomethane was performed and used for the measurement. When the sample contained a carboxylic acid base, an acid treatment was performed to modify the carboxylic acid base into a carboxylic acid group, and then the above esterification treatment was performed and used for the measurement.

2) Preparation of sample solution Weigh 3 mg of sample and 3 mL of o-dichlorobenzene in a 4 mL vial, cover with a screw cap and a Teflon (registered trademark) septum, and then use a Senshu Scientific SSC-7300 high-temperature shaker. Was shaken at 150 ° C. for 2 hours. After the shaking was completed, it was visually confirmed that there were no insoluble components.

3) Measurement Connect Showa Denko's high-temperature GPC column Showex HT-G x 1 and HT-806M x 2 to the Alliance GPCV2000 type manufactured by Waters, and use o-dichlorobenzene as the eluent at a temperature of 145 ° C. The measurement was performed at a flow rate of 1.0 mL / min.

4) Calibration curve Column calibration is performed by Showa Denko monodisperse polystyrene (S-7300, S-3900, S-1950, S-1460, S-1010, S-565, S-152, S-66.0, S-28.5 and S-5.05, 0.07 mg / ml solutions each), n-icosane and n-tetracontane were measured under the same conditions as above, and the elution time and molecular weight logarithmic values were measured. It was approximated by a quaternary equation. The following formula was used to convert the polystyrene molecular weight ( _MPS ) and the polyethylene molecular weight ( _MPE ).
_{M PE} = 0.468 × M _PS

(3) Melting point The melting point is indicated by the peak temperature of the endothermic curve measured by a differential scanning calorimeter (DSC). A DSC (DSC7020) manufactured by SII Nanotechnology Co., Ltd. was used for the measurement, and the measurement was carried out under the following measurement conditions.
About 5.0 mg of the sample was packed in an aluminum pan, heated to 200 ° C. at 10 ° C./min, held at 200 ° C. for 5 minutes, and then lowered to 30 ° C. at 10 ° C./min. The maximum peak temperature of the absorption curve when the temperature was raised again at 10 ° C./min after holding at 30 ° C. for 5 minutes was defined as the melting point Tm.

(4) Method for measuring the amount of structural unit derived from a monomer having a carboxy group and / or a dicarboxylic acid anhydride group and the amount of structural units derived from an acyclic monomer and the number of branches per 1,000 carbons The carboxy group in the multiple copolymer of the present invention And / or the amount of structural units derived from the monomer having a dicarboxylic acid anhydride group and the acyclic monomer, and the number of branches per 1,000 carbons can be determined using a ¹³ C-NMR spectrum. ¹³ C-NMR was measured by the following method.
Sample 200-300 mg in a mixed solvent (C ₆ H ₄ Cl ₂ / C ₆ D ₅ Br = 2 /) of o-dichlorobenzene (C ₆ H ₄ Cl ₂ ) and benzene dehydride (C ₆ D ₅ Br) 1 (Volume ratio)) 2.4 ml and hexamethyldisiloxane, which is a reference substance for chemical shift, are placed in an NMR sample tube with an inner diameter of 10 mmφ, replaced with nitrogen, sealed, and heat-dissolved to form a uniform solution for NMR measurement samples. And said.
The NMR measurement was performed at 120 ° C. using an AV400M type NMR apparatus of Bruker Japan Co., Ltd. equipped with a 10 mmφ cryoprobe.
¹³ C-NMR was measured by the reverse gate decoupling method at a sample temperature of 120 ° C., a pulse angle of 90 °, a pulse interval of 51.5 seconds, and an integration number of 512 times or more.
The chemical shift was set to 1.98 ppm for the ¹³ C signal of hexamethyldisiloxane, and the chemical shift of the other ¹³ C signals was based on this.

1) Pretreatment of the sample When the sample contained a carboxylic acid base, the carboxylic acid base was denatured into a carboxy group by acid treatment and then used for the measurement. When the sample contains a carboxy group, esterification treatment such as methyl esterification using diazomethane or trimethylsilyl (TMS) diazomethane may be appropriately performed.

2) Calculation of structural unit amount derived from a monomer having a carboxy group and / or a dicarboxylic acid anhydride group and an acyclic monomer <E / tBA>
The quaternary carbon signal of the t-butyl acrylate group of tBA is detected at 79.6-78.8 in the ¹³ C-NMR spectrum. Using these signal intensities, the amount of comonomer was calculated from the following formula.
Total amount of tBA (mol%) = I (tBA) x 100 / [I (tBA) + I (E)]
Here, I (tBA) and I (E) are quantities represented by the following formulas, respectively.
I (tBA) = I _79.6-78.8
I (E) = (I _{180.0 to 135.0} + I _{120.0 to 5.0-} I (tBA) x 7) / 2

<E / tBA / NB>
The quaternary carbon signal of the t-butyl acrylate group of tBA is detected at 79.6 to 78.8 ppm in the ¹³ C-NMR spectrum, and the methine carbon signal of NB is detected at 41.9 to 41.1 ppm. Using these signal intensities, the amount of comonomer was calculated from the following formula.
Total amount of tBA (mol%) = I (tBA) x 100 / [I (tBA) + I (NB) + I (E)]
Total amount of NB (mol%) = I (NB) x 100 / [I (tBA) + I (NB) + I (E)]
Here, I (tBA), I (NB), and I (E) are quantities represented by the following formulas, respectively.
I (tBA) = I _79.6-78.8
I (NB) = (I _41.9-41.1 ) / 2
I (E) = (I _{180.0 to 135.0} + I _{120.0 to 5.0-} I (NB) x 7-I (tBA) x 7) / 2

When the structural unit amount of each monomer is indicated by "<0.1" including the inequality sign, it exists as a structural unit in the multi-dimensional copolymer, but it is less than 0.1 mol% in consideration of significant figures. Means that it is the amount of.

3) Calculation of the number of branches per 1,000 carbons When the multiple copolymer has branches, the isolated type in which the branch exists alone in the main chain and the composite type (branch and branch via the main chain) There are face-to-face types, branched-branch types with branches in the branched chain, and chain types).
The following is an example of the structure of the ethyl branch. In the face-to-face type example, R represents an alkyl group.

The number of branches per 1,000 carbons is obtained by substituting any of the following I (B1), I (B2), and I (B4) into the I (branch) term of the following equation. B1 represents a methyl branch, B2 represents an ethyl branch, and B4 represents a butyl branch. The number of methyl branches is determined by using I (B1), the number of ethyl branches is determined by using I (B2), and the number of butyl branches is determined by using I (B4).
Number of branches (per 1,000 carbons) = I (branches) x 1000 / I (total)
Here, I (total), I (B1), I (B2), and I (B4) are quantities represented by the following equations.
I (total) = I _{180.0 to 135.0} + I _{120.0 to 5.0}
I (B1) = (I _{20.0 to 19.8} + I _{33.2 to 33.1} + I _{37.5 to 37.3} ) / 4
I (B2) = I _{8.6 to 7.6} + I _{11.8 to 10.5}
I (B4) = I _{14.3 to 13.7} -I _{32.2 to 32.0}
Here, I indicates the integrated intensity, and the numerical value of the subscript of I indicates the range of the chemical shift. For example, I _180.0 to 135.0 indicate the integrated intensity of the ¹³ C signal detected between 180.0 ppm and 135.0 ppm.
Attribution was based on the non-patent documents Macromolecules 1984, 17, 1756-1761 and Macromolecules 1979, 12, 41.
When the number of branches is indicated by "<0.1" including the inequality sign, the amount is less than 0.1 mol% in consideration of significant figures, although it exists as a constituent unit in the multiple copolymer. It means that there is. Further, not detected means less than the detection limit.

(5) Infrared absorption spectrum The sample is melted at 180 ° C. for 3 minutes and compression molded to prepare a film having a thickness of about 50 μm. This film was analyzed by Fourier transform infrared spectroscopy to obtain an infrared absorption spectrum.
Product name: FT / IR-6100 Made by JASCO Corporation Measurement method: Transmission method Detector: TGS (Triglycine sulfate)
Number of integrations: 16 to 512 times Resolution: 4.0 cm ^-1
Measurement wavelength: 5000-500 cm ^-1

(6) Tensile test The flame-retardant resin compositions obtained in the following Examples and Comparative Examples were placed in a heat-pressing mold having dimensions: 150 mm × 150 mm and a thickness of 1.0 mm, and placed in a heat-pressing machine having a surface temperature of 180 ° C. 5 After preheating for minutes, the residual gas in the molten resin was degassed by repeating pressurization and depressurization, further pressurized at 9.8 MPa, and held for 5 minutes. Then, it was transferred to a press machine having a surface temperature of 25 ° C. and cooled by holding it at a pressure of 9.8 MPa for 5 minutes to prepare a press plate composed of a sample having a thickness of about 1.0 mm. The state of the obtained molded plate was adjusted for 48 hours or more in an environment of a temperature of 23 ± 2 ° C. and a humidity of 50 ± 5 ° C. Tensile breaking strength at a tensile speed of 200 mm / min based on JIS C3005 (2000) using the dumbbell-shaped No. 3 test piece described in JIS K6251 (2017) produced by punching a press plate after adjusting the state. And the elongation were calculated. A tensile test was carried out under the condition of a temperature of 23 ° C., and the tensile strength at break and the elongation at break were measured.

(7) Measurement of wear amount 1) Method for preparing a wear test sample The obtained flame-retardant resin composition is placed in a heat-pressing mold having dimensions: 150 mm × 150 mm and a thickness of 1 mm, and is placed in a heat-pressing machine having a surface temperature of 180 ° C. After preheating for 5 minutes, the residual gas in the molten resin was degassed by repeating pressurization and depressurization, further pressurized at 9.8 MPa, and held for 5 minutes. Then, it was transferred to a press machine having a surface temperature of 25 ° C. and cooled by holding it at a pressure of 9.8 MPa for 5 minutes to prepare a press plate composed of a sample having a thickness of about 1.0 mm. The state of the obtained molded plate was adjusted for 48 hours or more in an environment of a temperature of 23 ± 2 ° C. and a humidity of 50 ± 5 ° C. The pressed plate after adjusting the state was cut out into a circle with a diameter of about 115 mm, and a hole with a diameter of about 6.5 mm was made in the center to prepare a wear test sample.

2) Wear test conditions Using the above test piece, the amount of wear loss (mg) was measured under the following conditions in accordance with JIS K 7204-1999.
・ Equipment: Taber wear tester (rotary ablation tester) _ manufactured by Toyo Seiki Seisakusho Co., Ltd. ・ Wear wheel: CS-17
・ Rotation speed: 60 rotations / min
・ Number of tests: 1000 rotations ・ Load: 4.9N

(8) Oxygen index The obtained flame-retardant resin composition is placed in a heating press mold having dimensions: 60 mm × 150 mm and a thickness of 3.0 mm, preheated in a heat press machine having a surface temperature of 180 ° C. for 5 minutes, and then pressurized. The residual gas in the molten resin was degassed by repeating the reduced pressure, further pressurized at 9.8 MPa, and held for 5 minutes. Then, it was transferred to a press machine having a surface temperature of 25 ° C. and cooled by holding it at a pressure of 9.8 MPa for 5 minutes to prepare a press plate composed of a sample having a thickness of about 3.0 mm. The state of the obtained molded plate was adjusted for 48 hours or more in an environment of a temperature of 23 ± 2 ° C. and a humidity of 50 ± 5 ° C. Based on the test method of JIS K7201-1 (1999), the oxygen index was measured using a type IV test piece punched from a press sheet having a thickness of 3 mm.

<Synthesis of metal complex>
Synthesis of B-27DM / Ni Complex The B-27DM / Ni complex has the following 2-bis (2,6-dimethoxyphenyl) phosphano-6-penta according to Synthesis Example 4 described in WO 2010/050256. A fluorophenylphenol ligand (B-27DM) was used. B-27DM and Ni (COD) using bis (1,5-cyclooctadiene) nickel (0) (referred to as Ni (COD) 2) according to Example 1 of International Publication No. 2010/050256. A nickel complex (B-27DM / Ni) in which 2 was reacted 1: 1 was synthesized.

Production Example 1: Production of ionomer resin (B-1) <Production of ternary copolymer for ionomer precursor resin>
An ethylene / tBu acrylate / norbornene copolymer was produced using the transition metal complex (B-27DM / Ni complex). The copolymer was produced with reference to Production Example 1 or Production Example 3 described in JP-A-2016-79408. The transition metal complex was 1000 mmol, trioctylaluminum (TNOA) was 225 mmol, toluene was 1000 L, t-butyl acrylate as the copolymer (b) was 230 mmol / L, and 2-norbornene was 210 mmol / L as the copolymer (c). It was introduced at a concentration and polymerized at an ethylene partial pressure of 0.8 MPa and a polymerization temperature of 85 ° C. for 330 minutes to obtain 117 kg of a copolymer. The melting point of the copolymer was 80.5 ° C., the weight average molecular weight was 3.8 × 10 ⁴ , and the value of Mw / Mn was 2.3. Moreover, as a result of quantifying the number of methyl branches by ¹³ C-NMR, it was 0.5 / 1000 C, and it was confirmed that a substantially linear resin was obtained. The resin composition was E / tBA / NB = 92.0 / 5.1 / 2.9. Moreover, when this composition was applied to the formula regarding the randomness of the copolymer, a value of 100.08 was obtained. This is a value larger than the melting point of the obtained resin of 80.5 (° C.) and satisfies the above relational expression 50 <Tm <-3.74 × [Z] +130. I can judge.

<Manufacturing of ionomer precursor resin>
40 g of the obtained E / tBA / NB copolymer, 0.8 g of paratoluenesulfonic acid monohydrate and 185 ml of toluene were placed in a separable flask having a capacity of 500 ml, and the mixture was stirred at 105 ° C. for 4 hours. After adding 185 ml of ion-exchanged water, stirring and allowing to stand, the aqueous layer was extracted. After that, the ion-exchanged water was repeatedly added and extracted until the pH of the extracted aqueous layer became 5 or more. The solvent was distilled off from the remaining solution under reduced pressure, and the mixture was dried until it became constant.
In the IR spectrum of the obtained resin, the peak near 850 cm ^-1 derived from the tBu group disappeared, the peak near 1730 cm ^-1 derived from the carbonyl group of the ester decreased, and the carbonyl of the carboxylic acid (dimer). An increase in the peak around 1700 cm ^-1 derived from the group was observed.
As a result, the decomposition of tBu ester and the formation of carboxylic acid were confirmed, and an ionomer precursor resin was obtained. The resin composition was E / AA / NB = 92.0 / 5.1 / 2.9.

<Manufacturing of ionomers>
1) Preparation of Na ion supply source Labplast mill manufactured by Toyo Seiki Co., Ltd. equipped with a small mixer with a capacity of 60 ml: Ethylene / methacrylic acid (MAA) copolymer (manufactured by Mitsui Dow Polychemical Co., Ltd.) on roller mixer R60 type. Brand: Nucrel N1050H) and 18 g of sodium carbonate were added and kneaded at 180 ° C. and 40 rpm for 3 minutes to prepare a Na ion supply source.

2): Preparation of ionomer Toyo Seiki Co., Ltd. Labplast Mill: Roller Mixer R60 equipped with a small mixer with a capacity of 60 ml was charged with 40 g of resin and kneaded at 160 ° C. and 40 rpm for 3 minutes to dissolve it. Then, the Na ion supply source was added so as to have a predetermined degree of neutralization, and kneading was performed at 250 ° C. and 40 rpm for 5 minutes.
In the IR spectrum of the obtained resin, the peak near 1700 cm ^-1 derived from the carbonyl group of the carboxylic acid (dimer) decreased, and the peak near 1560 cm ^-1 derived from the carbonyl group of the carboxylic acid base increased. Was there. It was confirmed that an ionomer having a desired degree of neutralization could be produced from the amount of decrease in the peak around 1700 cm ^-1 derived from the carbonyl group of the carboxylic acid (dimer).

Production Example 2: Production of ionomer resin (B-3) <Production of binary copolymer for ionomer precursor resin>
An ethylene / acrylic acid tBu copolymer was produced using the transition metal complex (B-27DM / Ni complex). The copolymer was produced with reference to Production Example 1 or Production Example 3 described in JP-A-2016-79408. The transition metal complex was introduced at a concentration of 550 mmol, trioctyl aluminum (TNOA) was introduced at a concentration of 136 mmol, toluene was 1000 L, and t-butyl acrylate was introduced as a comonomer (b) at a concentration of 135 mmol / L. The polymerization was carried out for 200 minutes to obtain 93 kg of a copolymer. Melting point of the copolymer 103.6 ° C., the value of the weight average molecular weight 4.4 × ¹⁰ 4, Mw / Mn was 2.0. Further, as a result of quantifying the number of methyl branches by ¹³ C-NMR, it was 1.1 / 1000 C, and it was confirmed that a substantially linear resin was obtained. The resin composition was E / tBA = 96.5 / 3.5. Moreover, when this composition was applied to the formula regarding the randomness of the copolymer, a value of 116.9 was obtained. This is a value larger than the melting point of the obtained resin 103.6 (° C.) and satisfies the relational expression 50 <Tm <-3.74 × [Z] +130. Therefore, the resin is considered to be a highly random resin. I can judge.

<Manufacturing of ionomer precursor resin>
40 g of the obtained E / tBA copolymer, 0.8 g of paratoluenesulfonic acid monohydrate and 185 ml of toluene were placed in a separable flask having a capacity of 500 ml, and the mixture was stirred at 105 ° C. for 4 hours. After adding 185 ml of ion-exchanged water, stirring and allowing to stand, the aqueous layer was extracted. After that, the ion-exchanged water was repeatedly added and extracted until the pH of the extracted aqueous layer became 5 or more. The solvent was distilled off from the remaining solution under reduced pressure, and the mixture was dried until it became constant.
In the IR spectrum of the obtained resin, the peak near 850 cm ^-1 derived from the tBu group disappeared, the peak near 1730 cm ^-1 derived from the carbonyl group of the ester decreased, and the carbonyl of the carboxylic acid (dimer). An increase in the peak around 1700 cm ^-1 derived from the group was observed.
As a result, the decomposition of tBu ester and the formation of carboxylic acid were confirmed, and an ionomer precursor resin was obtained. The resin composition was E / AA = 96.5 / 3.5.
<Manufacturing of ionomers>
An ionomer resin (B-3) was prepared in the same manner as in Production Example 1 except that the Na ion supply source was adjusted to have a neutralization degree of 20% with respect to the E / AA ionomer precursor resin.

Examples and Comparative Examples <Preparation of flame-retardant resin composition using ionomer>
[Example 1]
Made by blending 100 parts by weight of magnesium hydroxide (C-1) with 100 parts by weight of a resin component consisting of 90% by weight of ethylene-ethyl acrylate copolymer (A-1) and 10% by weight of ionomer resin (B-1). The resin composition was kneaded under the following conditions to obtain a flame-retardant resin composition. Using the obtained flame-retardant resin composition, a press sheet was prepared by the method described below and tested. The evaluation results of the above flame-retardant resin composition are shown in Table 2.

[Kneading conditions for flame-retardant resin composition]
A lab plast mill manufactured by Toyo Seiki Seisakusho Co., Ltd. is used as a kneading device, and kneading is performed at a kneading temperature of 180 ° C., a rotation speed of 50 rpm, and a kneading time of 5 minutes. A resin composition was obtained. An evaluation press sheet was prepared from the obtained flame-retardant resin composition by the method described in <Measurement and Evaluation> above.

[Example 2]
100 parts by weight of magnesium hydroxide (C-1) is blended with 100 parts by weight of a resin component consisting of 80% by weight of ethylene-ethyl acrylate copolymer (A-1) and 20% by weight of ionomer resin (B-1). The resin composition was kneaded under the same conditions as in Example 1 to obtain a flame-retardant resin composition. Using the obtained flame-retardant resin composition, a press sheet was prepared in the same manner as in Example 1 and tested. The evaluation results of the above flame-retardant resin composition are shown in Table 2.

[Example 3]
Hydrohydration of 100 parts by weight of a resin component consisting of 85% by weight of ethylene-ethylacrylate copolymer (A-1), 10% by weight of ionomer resin (B-1), and 5% by weight of maleic anhydride-modified polyethylene (A-3) A resin composition containing 100 parts by weight of magnesium (C-1) was kneaded under the same conditions as in Example 1 to obtain a flame-retardant resin composition. Using the obtained flame-retardant resin composition, a press sheet was prepared in the same manner as in Example 1 and tested. The evaluation results of the above flame-retardant resin composition are shown in Table 2.

[Example 4]
Made by blending 100 parts by weight of magnesium hydroxide (C-1) with 100 parts by weight of a resin component consisting of 90% by weight of an ethylene-vinyl acetate copolymer (A-2) and 10% by weight of an ionomer resin (B-1). The resin composition was kneaded under the same conditions as in Example 1 to obtain a flame-retardant resin composition. Using the obtained flame-retardant resin composition, a press sheet was prepared in the same manner as in Example 1 and tested. The evaluation results of the above flame-retardant resin composition are shown in Table 2.

[Example 5]
Made by blending 100 parts by weight of magnesium hydroxide (C-1) with 100 parts by weight of a resin component consisting of 90% by weight of an ethylene-ethyl acrylate copolymer (A-4) and 10% by weight of an ionomer resin (B-1). The resin composition was kneaded under the same conditions as in Example 1 to obtain a flame-retardant resin composition. Using the obtained flame-retardant resin composition, a press sheet was prepared in the same manner as in Example 1 and tested. The evaluation results of the above flame-retardant resin composition are shown in Table 2.

[Example 6]
Made by blending 100 parts by weight of magnesium hydroxide (C-1) with 100 parts by weight of a resin component consisting of 90% by weight of an ethylene-ethyl acrylate copolymer (A-4) and 10% by weight of an ionomer resin (B-3). The resin composition was kneaded under the same conditions as in Example 1 to obtain a flame-retardant resin composition. Using the obtained flame-retardant resin composition, a press sheet was prepared in the same manner as in Example 1 and tested. The evaluation results of the above flame-retardant resin composition are shown in Table 2.

[Comparative Example 1]
A resin composition obtained by blending 100 parts by weight of an ethylene-ethyl acrylate copolymer (A-1) with 100 parts by weight of magnesium hydroxide (C-1) is kneaded under the same conditions as in Example 1 to form a flame-retardant resin. The composition was obtained. Using the obtained flame-retardant resin composition, a press sheet was prepared in the same manner as in Example 1 and tested. The evaluation results of the above flame-retardant resin composition are shown in Table 3.

[Comparative Example 2]
Made by blending 100 parts by weight of magnesium hydroxide (C-1) with 100 parts by weight of a resin component consisting of 90% by weight of ethylene-ethyl acrylate copolymer (A-1) and 10% by weight of ionomer resin (B-2). The resin composition was kneaded under the same conditions as in Example 1 to obtain a flame-retardant resin composition. Using the obtained flame-retardant resin composition, a press sheet was prepared in the same manner as in Example 1 and tested. The evaluation results of the above flame-retardant resin composition are shown in Table 3.

[Comparative Example 3]
It is made by blending 100 parts by weight of magnesium hydroxide (C-1) with 100 parts by weight of a resin component consisting of 80% by weight of ethylene-ethyl acrylate copolymer (A-1) and 20% by weight of ionomer resin (B-2). The resin composition was kneaded under the same conditions as in Example 1 to obtain a flame-retardant resin composition. Using the obtained flame-retardant resin composition, a press sheet was prepared in the same manner as in Example 1 and tested. The evaluation results of the above flame-retardant resin composition are shown in Table 3.

[Comparative Example 4]
100 parts by weight of magnesium hydroxide (C-1) is blended with 100 parts by weight of a resin component consisting of 95% by weight of ethylene-ethyl acrylate copolymer (A-1) and 5% by weight of maleic anhydride-modified polyethylene (A-3). The resin composition was kneaded under the same conditions as in Example 1 to obtain a flame-retardant resin composition. Using the obtained flame-retardant resin composition, a press sheet was prepared in the same manner as in Example 1 and tested. The evaluation results of the above flame-retardant resin composition are shown in Table 3.

[Comparative Example 5]
Hydrohydration of 100 parts by weight of a resin component consisting of 85% by weight of ethylene-ethyl acrylate copolymer (A-1), 10% by weight of ionomer resin (B-2), and 5% by weight of maleic anhydride-modified polyethylene (A-3). A resin composition containing 100 parts by weight of magnesium (C-1) was kneaded under the same conditions as in Example 1 to obtain a flame-retardant resin composition. Using the obtained flame-retardant resin composition, a press sheet was prepared in the same manner as in Example 1 and tested. The evaluation results of the above flame-retardant resin composition are shown in Table 3.

[Comparative Example 6]
A resin composition obtained by blending 100 parts by weight of ethylene-vinyl acetate copolymer (A-2) with 100 parts by weight of magnesium hydroxide (C-1) is kneaded under the same conditions as in Example 1 to form a flame-retardant resin. The composition was obtained. Using the obtained flame-retardant resin composition, a press sheet was prepared in the same manner as in Example 1 and tested. The evaluation results of the above flame-retardant resin composition are shown in Table 3.

[Comparative Example 7]
Made by blending 100 parts by weight of magnesium hydroxide (C-1) with 100 parts by weight of a resin component consisting of 90% by weight of an ethylene-vinyl acetate copolymer (A-2) and 10% by weight of an ionomer resin (B-2). The resin composition was kneaded under the same conditions as in Example 1 to obtain a flame-retardant resin composition. Using the obtained flame-retardant resin composition, a press sheet was prepared in the same manner as in Example 1 and tested. The evaluation results of the above flame-retardant resin composition are shown in Table 3.

[Comparative Example 8]
A resin composition obtained by blending 100 parts by weight of magnesium hydroxide (C-1) with 100% by weight of an ethylene-ethyl acrylate copolymer (A-4) is kneaded under the same conditions as in Example 1 to form a flame-retardant resin. The composition was obtained. Using the obtained flame-retardant resin composition, a press sheet was prepared in the same manner as in Example 1 and tested. The evaluation results of the above flame-retardant resin composition are shown in Table 3.

[Comparative Example 9]
Made by blending 100 parts by weight of magnesium hydroxide (C-1) with 100 parts by weight of a resin component consisting of 90% by weight of an ethylene-ethyl acrylate copolymer (A-4) and 10% by weight of an ionomer resin (B-2). The resin composition was kneaded under the same conditions as in Example 1 to obtain a flame-retardant resin composition. Using the obtained flame-retardant resin composition, a press sheet was prepared in the same manner as in Example 1 and tested. The evaluation results of the above flame-retardant resin composition are shown in Table 3.

Comparing Examples 1 and 2 of Tables 2 and 3 with Comparative Example 1 and Examples 5 and 6 with Comparative Example 8, a flame-retardant resin composition was prepared by adding ionomer resins (B-1) and (B-3). It can be seen that the amount of wear (Taber wear) is significantly reduced. Further, when Comparative Examples 2 and 3 to which Examples 1 and 2 and the existing ionomer resin (B-2) were added and Comparative Examples 5 and 6 and Comparative Example 9 were compared, the amount of ionomer added was the same. The amount of wear is significantly reduced by adding the ionomers (B-1) and (B-3) of the present application. In addition, comparison of Example 3 and Comparative Examples 4 and 5 to which maleic anhydride-modified polyethylene was added, and Example 4 and Comparative Example 6 using an ethylene-vinyl acetate copolymer (A-2) as a precursor resin. Similarly, in the comparison of Nos. 7 and 7, the amount of wear is reduced by adding the ionomer resin (B-1). This indicates that the abrasion resistance of the flame-retardant resin composition can be remarkably improved by using the ionomer resin (B-1) shown in the present invention.

The flame-retardant resin composition using the ionomer of the present disclosure is excellent in abrasion resistance as compared with the conventional resin. Therefore, the present invention can be used particularly for electric wires and cables.

Claims (9)

It is characterized by containing 30 to 300 parts by weight of the flame retardant (C) with respect to 100 parts by weight of the resin component composed of 50 to 99% by weight of the polyolefin resin (A) and 1 to 50% by weight of the ionomer resin (B). It is a flame retardant resin composition
The ionomer resin (B) has a structural unit (a) derived from ethylene and / or an α-olefin having 3 to 20 carbon atoms and a structural unit (b) derived from a monomer having a carboxyl group and / or a dicarboxylic acid anhydride group. ) As an essential constituent unit, at least a part of the carboxyl group and / or the dicarboxylic acid anhydride group is selected from Group 1, Group 2, or Group 12 of the periodic table. It is characterized by having a phase angle δ of 50 to 75 degrees at an absolute value G ^* = 0.1 MPa of the complex elastic coefficient measured by a rotary leometer after being converted to an ion-containing metal-containing carboxylic acid salt. A flame-retardant resin composition that is an ionomer resin. ¹³ The flame-retardant resin composition according to claim 1, wherein the number of methyl branches of the copolymer (P) calculated by C-NMR is 50 or less per 1,000 carbons. ¹³ The flame-retardant resin composition according to claim 1, wherein the number of methyl branches of the copolymer (P) calculated by C-NMR is 5 or less per 1,000 carbons. The flame-retardant resin composition according to any one of claims 1 to 3, wherein the weight ratio of the ionomer resin (B) to 100 parts by weight of the resin component is 1 to 20% by weight. The flame-retardant resin composition according to any one of claims 1 to 4, wherein the polyolefin-based resin (A) is a polar group-containing polyethylene. The flame-retardant resin according to claim 5, wherein the polar group-containing polyethylene contains at least one of an ethylene-vinyl acetate copolymer, an ethylene-ethyl acrylate copolymer, and an acid-modified polyolefin resin. Composition. The flame-retardant resin composition according to any one of claims 1 to 6, wherein the flame retardant (C) is a metal hydroxide. The flame-retardant resin composition according to claim 7, wherein the metal hydroxide is magnesium hydroxide. An electric wire or cable comprising the flame-retardant resin composition according to any one of claims 1 to 8.