JP2008161824A - Dispersant and polymer composition as well as coated electric cable and wire harness - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a dispersant capable of improving material characteristics such as mechanical properties of a polymer composition containing a filler and a polymer composition. <P>SOLUTION: The dispersant is a compound having a long-chain alkyl group and a chelate structure obtained by bonding a chelating ligand such as an amino alcohol, an aminocarboxylic acid, or the like to a functional terminal of a functional group-containing long-chain alkyl compound such as a long-chain alkyl carboxylic acid, a long-chain alkyl alcohol, or the like by ester bond or amide bond. The polymer composition contains this dispersant, an organic polymer, and a filler. The content of the dispersant is preferably in a range of 0.1 to 20 pts.wt. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a dispersant and a polymer composition, and a covered electric wire and a wire harness.

  Conventionally, polymer compositions containing resins, rubbers, elastomers and the like have been used in various fields. In many cases, a filler is added to the polymer composition for the purpose of imparting various functions, depending on the application.

  For example, in the field of electric wires used as wirings for vehicle parts such as automobiles and electric / electronic equipment parts, polymer compositions are used for wire covering materials and the like. In this case, various fillers such as plasticizers, stabilizers, flame retardants, etc. are used for the coating material, etc., depending on the properties required for the electric wires, such as mechanical properties such as wear resistance, flexibility, workability, and flame resistance. May be added.

  By the way, when a filler is added to the polymer composition, material properties such as mechanical properties may be impaired depending on the type, material, and amount of the filler.

  For example, in the case of electric wires, organic polymers such as olefin-based resins that do not emit harmful halogen-based gases during combustion have come to be used as covering materials, etc. from the viewpoint of suppressing the burden on the global environment. Yes.

  In this case, in order to ensure sufficient flame retardancy, it is effective to add a large amount of flame retardant. On the other hand, it is known that when a large amount of a flame retardant is added, mechanical properties such as wear resistance are remarkably lowered (Patent Document 1).

Japanese Patent No. 3280099

  Here, it is speculated that the reason why the material properties such as mechanical properties are deteriorated is that the filler is not sufficiently dispersed in the polymer composition. Although various studies have been made to increase the dispersibility of fillers in order to suppress such deterioration of material properties such as mechanical properties in polymer compositions known in the past, material properties such as mechanical properties have been studied. There was room for improvement.

  Therefore, the problem to be solved by the present invention is to provide a dispersant and a polymer composition capable of improving material properties such as mechanical properties of a polymer composition containing a filler. Another object is to provide a covered electric wire and a wire harness that are excellent in mechanical properties such as wear resistance.

  As a result of intensive studies, the present inventors have found that if a material having both a structure excellent in affinity with a filler and a structure excellent in affinity with an organic polymer such as an olefin resin is used, the filler is contained. However, it has been found that material properties such as mechanical properties can be improved.

  That is, the gist of the dispersant according to the present invention is to have a chelate structure at the terminal of the functional group of the long-chain alkyl compound having a functional group.

  In this case, the long-chain alkyl compound is preferably a long-chain alkyl carboxylic acid, a derivative thereof, or a long-chain alkyl alcohol.

  The chelate structure includes polyphosphate, aminocarboxylic acid, 1,3-diketone, hydroxycarboxylic acid, polyamine, amino alcohol, aromatic heterocyclic base, phenols, oximes, Schiff base, tetrapyrroles, Desirably, it is derived from one or more chelating ligands selected from sulfur compounds, synthetic macrocycles, phosphonic acids, and hydroxyethylidenephosphonic acids.

  At this time, the chelate structure may be bonded to the functional group of the long-chain alkyl compound by one or more selected from an ester bond, an ether bond, a thioester bond, a thioether bond, and an amide bond. .

  The gist of the dispersant according to the present invention is that the dispersant can be obtained by bringing a long-chain alkyl compound having a functional group into contact with a chelate ligand.

  On the other hand, the polymer composition according to the present invention is characterized in that it contains the dispersant, an organic polymer, and a filler.

  In this case, the content of the dispersant is preferably in the range of 0.1 to 20 parts by weight.

  And the covered electric wire which concerns on this invention makes it a summary to use the said polymer composition for the coating | covering material.

  Furthermore, the wire harness which concerns on this invention makes it a summary to have used the said polymer composition.

  The dispersant according to the present invention has a chelate structure at the end of the functional group of the long-chain alkyl compound having a functional group. Therefore, when added to a polymer composition containing a filler, its material properties, particularly mechanical properties, can be improved. This is because the chelate structure in the dispersant is excellent in affinity with the filler, so that it strongly binds to the filler and prevents the fillers from aggregating with each other, and the filler is highly dispersed in the polymer composition. Presumed to be.

  In this case, when the long-chain alkyl compound is a long-chain alkyl carboxylic acid, a derivative thereof, or a long-chain alkyl alcohol, it is easy to introduce a chelate structure at the end of the functional group of the long-chain alkyl compound.

  The chelate structure is a polyphosphate, aminocarboxylic acid, 1,3-diketone, hydroxycarboxylic acid, polyamine, amino alcohol, aromatic heterocyclic base, phenols, oximes, Schiff base, tetrapyrroles, Those derived from one or more chelate ligands selected from sulfur compounds, synthetic macrocycles, phosphonic acids, and hydroxyethylidenephosphonic acids are excellent in improving material properties such as mechanical properties. .

  At this time, the chelate structure can be reliably bonded to the functional group of the long-chain alkyl compound by one or more selected from an ester bond, an ether bond, a thioester bond, a thioether bond, and an amide bond. it can. Moreover, various chelate structures can be easily introduced.

  The dispersant according to the present invention can be obtained by bringing a long-chain alkyl compound having a functional group into contact with a chelate ligand. Therefore, when it adds to the polymer composition containing a filler, material characteristics, such as a mechanical characteristic, can be improved.

  On the other hand, the polymer composition according to the present invention contains the dispersant, an organic polymer, and a filler. Therefore, material characteristics such as mechanical characteristics are improved.

  In this case, when the content of the dispersant is in the range of 0.1 to 20 parts by weight, the above effect is further improved.

  And the covered electric wire which concerns on this invention uses the said polymer composition for a coating | covering material. Moreover, the wire harness which concerns on this invention uses the said polymer composition. Therefore, it is excellent in mechanical properties such as wear resistance. Thereby, deterioration of a material is suppressed and high reliability can be ensured over a long period of time.

  Next, an embodiment of the present invention will be described in detail.

  The dispersant according to the present invention has a chelate structure at the end of the functional group of the long-chain alkyl compound having a functional group.

  The long-chain alkyl compound described above has a long-chain alkyl group and a functional group. The long chain alkyl group may be linear or branched. The long chain alkyl group may contain a carbon-carbon unsaturated bond, an amide bond, an ether bond, an ester bond, and the like. Although it does not specifically limit as carbon number of a long-chain alkyl group, It is preferable that it is 6-50. More preferably, it has 8 to 30 carbon atoms.

  Examples of the functional group possessed by the long-chain alkyl compound include a carboxyl group, a thiocarboxyl group, a hydroxyl group, a thiol group, and an amino group. One or more functional groups may be contained in the long-chain alkyl compound described above. These functional groups may have one kind or two or more kinds.

  The long-chain alkyl compound is not particularly limited. For example, a long-chain alkyl carboxylic acid, a long-chain alkyl carboxylic acid derivative such as a long-chain alkyl carboxylic acid ester, a long-chain alkyl carboxylic acid amide, a long-chain alkyl alcohol, a long-chain alkyl Examples include alkyl thiols, long chain alkyl aldehydes, long chain alkyl ethers, long chain alkyl amines, long chain alkyl amine derivatives, and long chain alkyl halogens. Among these, a long-chain alkyl carboxylic acid, a long-chain alkyl carboxylic acid derivative, a long-chain alkyl alcohol, and a long-chain alkyl amine are preferable in that a chelate structure is easily introduced.

  More specifically, for example, dodecylcarboxylic acid, hexadecylcarboxylic acid, octadecylcarboxylic acid, dodecyl alcohol, hexadecyl alcohol, octadecyl alcohol, dodecylamine, hexadecylamine, octadecylamine, dodecylcarboxylic acid chloride, hexadecylcarboxylic acid Examples include chloride and octadecylcarboxylic acid chloride. Of these, octadecylcarboxylic acid, dodecyl alcohol, octadecyl alcohol, and octadecylamine are preferable in that they are easily available.

  The chelate structure is formed at the terminal of the functional group of the long-chain alkyl compound described above, and imparts a chelate function that easily binds to the filler to the long-chain alkyl compound. The form in which the chelate structure is formed at the terminal of the functional group of the long-chain alkyl compound is not particularly limited, but the chelate structure and the terminal of the functional group of the long-chain alkyl compound are an ester bond, an ether bond, a thioester bond, It is preferable that a chelate structure is formed at the terminal of the functional group of the long-chain alkyl compound by bonding with a thioether bond or an amide bond. One or two or more of the above-described bonds such as an ester bond may be included.

  In order to form such a bond, for example, a chelate ligand having a functional group that forms the above bond with the functional group of the long-chain alkyl compound may be used. The chelate ligand has a plurality of unshared electron pairs capable of coordinating bonds.

  For example, when the functional group of the long-chain alkyl compound is a carboxyl group, if the chelate ligand has a hydroxyl group, the chelate ligand is introduced into the end of the functional group of the long-chain alkyl compound by an ester bond. be able to. Further, if the chelate ligand has an amino group, the chelate ligand can be introduced to the end of the functional group of the long-chain alkyl compound by an amide bond.

  Examples of the chelate ligand include polyphosphate, aminocarboxylic acid, 1,3-diketone, hydroxycarboxylic acid, polyamine, amino alcohol, aromatic heterocyclic base, phenols, oximes, Schiff base, and tetrapyrrole. , Sulfur compounds, synthetic macrocycles, phosphonic acids, hydroxyethylidenephosphonic acids, and the like. These compounds have a plurality of unshared electron pairs capable of coordinating bonds.

  More specifically, examples of the polyphosphate include sodium tripolyphosphate and hexametaphosphoric acid. As aminocarboxylic acid, ethylenediaminediacetic acid, ethylenediaminedipropionic acid, ethylenediaminetetraacetic acid, N-hydroxymethylethylenediaminetriacetic acid, N-hydroxyethylethylenediaminetriacetic acid, diaminocyclohexyltetraacetic acid, diethylenetriaminepentaacetic acid, glycol etherdiaminetetraacetic acid, N, N-bis (2-hydroxybenzyl) ethylenediaminediacetic acid, hexamethylenediamine N, N, N, N-tetraacetic acid, hydroxyethyliminodiacetic acid, iminodiacetic acid, diaminopropanetetraacetic acid, nitrilotriacetic acid, nitrilotri Examples include propionic acid, triethylenetetramine hexaacetic acid, poly (p-vinylbenzyliminodiacetic acid), and the like.

  Examples of the 1,3-diketone include acetylacetone, trifluoroacetylacetone, thenoyltrifluoroacetone, aminopropyl acetoacetate, hydroxypropyl acetoacetate and the like. Examples of the hydroxycarboxylic acid include N-dihydroxyethyl glycine, ethylene bis (hydroxyphenyl glycine), diaminopropanol tetraacetic acid, tartaric acid, citric acid, gluconic acid and the like. Examples of the polyamine include ethylenediamine, triethylenetetramine, triaminotriethylamine, and polyethyleneimine. Examples of amino alcohols include triethanolamine, N-hydroxyethylethylenediamine, polymetalloylacetone and the like.

  Examples of the aromatic heterocyclic base include dipyridyl, o-phenanthroline, oxine, 8-hydroxyquinoline and the like. Examples of phenols include 5-sulfosalicylic acid, salicylaldehyde, disulfopyrocatechol, chromotropic acid, oxinesulfonic acid, disalicylic aldehyde and the like. Examples of oximes include dimethylglyoxime and salicyladoxime. Examples of the Schiff base include dimethylglyoxime, salicyladoxime, disalicylic aldehyde, and 1,2-propylene dimine.

  Examples of tetrapyrroles include phthalocyanine and tetraphenylporphyrin. Examples of the sulfur compound include toluene dithiol, dimercaptopropanol, thioglycolic acid, potassium ethylxanthate, sodium diethyldithiocarbamate, dithizone, diethyldithiophosphoric acid, and the like. Examples of synthetic macrocyclic compounds include tetraphenylporphyrin and crown ethers. Examples of the phosphonic acid include ethylenediamine N, N-bismethylenephosphonic acid, ethylenediaminetetrakismethylenephosphonic acid, nitrilotrismethylenephosphonic acid, and hydroxyethylidene diphosphonic acid.

  A hydroxyl group or an amino group can be appropriately introduced into the chelate ligand. By introducing a hydroxyl group or an amino group, a chelate structure may be able to be introduced at the end of the functional group of the long-chain alkyl compound. Some of the chelating ligands can exist as salts. In this case, it may be used in the form of a salt. Moreover, you may use the hydrate and solvate of the said chelate ligand or its salt. Further, the chelate ligand includes an optically active compound, but any stereoisomer, a mixture of stereoisomers, a racemate, and the like may be used.

  The dispersant according to the present invention is not particularly limited, and can be obtained, for example, by bringing the long-chain alkyl compound having a functional group into contact with the chelate ligand. At this time, a solvent may be used or stirring may be performed. Further, for the purpose of increasing the reaction rate, heating may be performed or a catalyst may be added. Furthermore, the target product may be obtained in a high yield by removing the by-products and biasing the equilibrium reaction to the production system.

  When the long-chain alkyl compound having a functional group is brought into contact with the chelate ligand, a chemical bond is formed by a reaction between the functional group of the long-chain alkyl compound and the functional group of the chelate ligand. For example, when a long-chain alkylcarboxylic acid is reacted with a chelate ligand having a hydroxyl group, an ester bond is formed and the dispersant according to the present invention is obtained. In addition, when a long-chain alkylcarboxylic acid is reacted with a chelate ligand having an amino group, an amide bond is formed and the dispersant according to the present invention is obtained.

  When an example of the dispersant according to the present invention described above is represented by a structural formula, for example, the formula (1) is obtained.

ただし、式（１）中、Ｒ１は長鎖アルキル基を示し、Ｒ２は酸素原子、窒素原子、硫黄原子を持つエステル結合、エーテル結合、チオエステル結合、チオエーテル結合、またはアミド結合を示し、Ｒ３はキレート構造部位を示している。

In the formula (1), R1 represents a long-chain alkyl group, R2 represents an ester bond having an oxygen atom, a nitrogen atom, or a sulfur atom, an ether bond, a thioester bond, a thioether bond, or an amide bond, and R3 represents a chelate. The structural site is shown.

  Among the dispersants represented by the structural formula of formula (1), particularly preferred examples will be described below. In the following formulas (2) to (7), R1 represents either an octadecyl group, a hexadecyl group, or a dodecyl group. The dispersant according to the present invention is not limited to the following compounds.

  Formula (2) is a dispersant having a diethylenetriaminepentaacetic acid group at the terminal of the hydroxyl group of the long-chain alkyl alcohol, and chelate coordination is possible by this diethylenetriaminepentaacetic acid group.

  Formula (3) is a dispersant having an ethyliminodiacetic acid group at the terminal of the carboxyl group of the long-chain alkylcarboxylic acid, and chelate coordination is possible by this ethyliminodiacetic acid group.

  Formula (4) is a dispersant having a diaminopropanetetraacetic acid group at the end of the carboxyl group of the long-chain alkylcarboxylic acid, and chelate coordination is possible by this diaminopropanetetraacetic acid group.

  Formula (5) is a dispersant having an N-methyleneethylenediaminetriacetic acid group at the terminal of the carboxyl group of the long-chain alkylcarboxylic acid, and chelate coordination is possible by this ethylenediaminetriacetic acid group.

  Formula (6) is a dispersant having an ethylidene diphosphonic acid group at the terminal of the carboxyl group of the long-chain alkylcarboxylic acid, and chelate coordination is possible by this diphosphonic acid group.

  Formula (7) is a dispersant having an acetoacetate group at the end of the hydroxyl group of a long-chain alkyl alcohol, and chelate coordination is possible by this acetoacetate group.

  Next, the polymer composition according to the present invention will be described. The polymer composition according to the present invention contains the dispersant, an organic polymer, and a filler.

  It is preferable that the content rate of the said dispersing agent exists in the range of 0.1-20 weight part. More preferably, it is in the range of 0.5 to 10 parts by weight. If the amount is less than 0.1 part by weight, the amount of the dispersant is small, so that the effect of improving the material properties such as mechanical properties tends to decrease. On the other hand, if the amount exceeds 20 parts by weight, the cost increases. Therefore, if it exists in the said range, it is further excellent in the effect which improves material characteristics, such as a mechanical characteristic.

  Although it does not specifically limit as an organic polymer, Resin, an elastomer, and rubber | gum can be shown. These may be used alone or in combination of two or more.

  Examples of the resin include polypropylene (PP), polyethylene (PE), ethylene-methyl acrylate (EMA), ethylene-ethyl acrylate (EEA), ethylene-butyl acrylate (EBA), ethylene-methyl methacrylate (EMMA), Olefin resins such as ethylene-vinyl acetate (EVA), polyamide resins (PA), polyester resins such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polysulfone resins, polyarylate resins, polyphenylene sulfide resins Examples thereof include engineering plastics such as resin, thermoplastic polyurethane resin, and polycarbonate (PC).

  As the elastomer, olefin elastomer (TPO), styrene elastomer (SEBS, etc.), amide elastomer, ester elastomer, urethane elastomer, ionomer, fluorine elastomer, 1,2-polybutadiene, trans-1,4-poly A thermoplastic elastomer such as isoprene can be exemplified.

  Examples of rubber include ethylene-propylene rubber (EPR), butadiene rubber (BR), and isoprene rubber (IR).

  In order to improve various physical properties, functional groups can be introduced into the resins, elastomers, and rubbers as necessary within a range that does not interfere with the physical properties. Examples of functional groups that can be introduced include carboxylic acid groups, acid anhydride groups, epoxy groups, hydroxyl groups, amino groups, alkenyl cyclic imino ether groups, and silane groups. These may be used alone or in combination of two or more.

  The filler is added according to the required characteristics of the material. The amount added is determined according to the type of filler, the required characteristics of the material, etc., but it is preferably contained in an amount of 30 to 250 parts by weight per 100 parts by weight of the polymer component in the composition. More preferably, it is 50-200 weight part. If the amount is less than 30 parts by weight, the effect of addition as a filler is small. On the other hand, if the amount exceeds 250 parts by weight, the characteristics of the polymer are easily canceled by the filler.

  The filler is not particularly limited. For example, metal powder, carbon black, graphite, carbon fiber, silica, alumina, titanium oxide, iron oxide, zinc oxide, magnesium oxide, tin oxide, antimony oxide, barium ferrite , Strontium ferrite, aluminum hydroxide, magnesium hydroxide, calcium sulfate, magnesium sulfate, barium sulfate, talc, clay, mica, calcium silicate, calcium carbonate, magnesium carbonate, glass fiber, calcium titanate, lead zirconate titanate, nitriding Aluminum, silicon carbide, wood fiber, fullerene, carbon nanotube, melamine cyanurate and the like can be exemplified. These may be used alone or in combination of two or more.

  In the present invention, additives generally used in a polymer composition may be blended in addition to the dispersant, organic polymer and filler as long as the characteristics of the present invention are not impaired. Such additives include antioxidants, metal deactivators (copper damage inhibitors), UV absorbers, UV masking agents, flame retardants, flame retardant aids, processing aids (lubricants, waxes, etc.), Examples thereof include coloring pigments.

  The polymer composition according to the present invention may be cross-linked as necessary. Examples of the crosslinking means include peroxide crosslinking, silane crosslinking, electron beam crosslinking, and the like, but the means is not particularly limited.

  It does not specifically limit as a manufacturing method of the polymer composition which concerns on this invention mentioned above, A well-known manufacturing method can be used. For example, a dispersant, an organic polymer, a filler, and other additives as necessary are blended, and these are dry blended with a normal tumbler or the like, or a Banbury mixer, a pressure kneader, a kneading extrusion The composition can be obtained by melt-kneading with a normal kneader such as a machine, a twin-screw extruder, or a roll and uniformly dispersing.

  At this time, the addition method of the component which comprises a composition is not specifically limited. For example, after kneading a dispersant and a filler, the organic polymer or other additives may be added and kneaded, or all components constituting the composition may be added and kneaded.

  The temperature at the time of kneading is preferably a temperature at which the viscosity of the organic polymer is lowered to such an extent that the filler is easily dispersed in the composition. Specifically, it is preferably in the range of 100 to 300 ° C. If heat is generated by shearing the organic polymer during kneading, the temperature may be adjusted to an optimum temperature in consideration of the temperature rise due to heat generation.

  After kneading, the composition is taken out from the kneader. At that time, the composition may be formed into pellets with a pelletizer or the like.

  The use of the polymer composition according to the present invention described above is not particularly limited. For example, covering materials for coated wires used as wiring for vehicle parts such as automobiles and electrical / electronic equipment parts, wire harness protective materials covering wire bundles, connector parts such as connector housings, medical instruments, artificial organs, Examples include materials to which fillers such as molecular paints and building materials are added.

  Next, the covered electric wire and the wire harness according to the present invention will be described.

  The covered electric wire according to the present invention uses the above-described polymer composition as a covering material. As a configuration of the covered electric wire, the outer periphery of the conductor may be directly covered with the covering material, and other intermediate members such as other insulators and shield conductors may be provided between the conductor and the covering material. It may be interposed. A plurality of coating materials may be formed.

  The conductor is not particularly limited, such as the diameter of the conductor or the material of the conductor, and can be appropriately determined according to the application. Further, the thickness of the covering material is not particularly limited, and can be appropriately determined in consideration of the conductor diameter and the like.

  The above-mentioned covered electric wire is, for example, a polymer composition according to the present invention kneaded using a commonly used kneader such as a Banbury mixer, a pressure kneader, or a roll, on the outer periphery of the conductor using a normal extruder or the like. It can be produced by extrusion coating. Alternatively, a method may be used in which the outer periphery of the conductor is extrusion coated while the polymer composition is kneaded and formed with a single screw extruder or twin screw extruder.

  On the other hand, the wire harness according to the present invention uses the above-described polymer composition. The wire harness according to the present invention may include a covered electric wire according to the present invention using the above-described polymer composition as a covering material, or a plurality of the above-described polymer compositions. What was used as a material of the wire harness protective material which coat | covers the electric wire bundle which consists of this covered electric wire may be used. The wire bundle when used as a material for the wire harness protective material may or may not include the covered electric wire according to the present invention. The number of electric wires can be determined arbitrarily and is not particularly limited.

  A wire harness protective material has a role which covers the outer periphery of the electric wire bundle in which the several covered electric wire was bundled, and protects an internal electric wire bundle from the external environment. Although it does not specifically limit as a base material which comprises a wire harness protective material, Olefin type polymer compositions, such as polyethylene and a polypropylene, are preferable.

  For wire harness protection materials, for example, those with adhesive applied to at least one surface of a tape-shaped substrate, or those having a substrate formed in a tube shape, sheet shape, etc. It can be appropriately selected and used accordingly.

  EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited thereto. In this example, as one of the material characteristics, the wear resistance of the covered electric wire was evaluated.

(Test material and manufacturer)
The test materials used in the present examples and comparative examples are shown together with the manufacturer, product name, and the like.

(A) Organic polymer / polyethylene (PE) [manufactured by Prime Polymer Co., Ltd., trade name “Hi-Zex 5000S”]
・ Polypropylene (PP) [manufactured by Prime Polymer Co., Ltd., trade name “Prime Polypro E-150GK”]
・ Ethylene-vinyl acetate copolymer (EVA) [Mitsui / DuPont Polychemical Co., Ltd., trade name “Evaflex EV360”]
・ Ionomer [Mitsui / DuPont Polychemical Co., Ltd., trade name “Himiran 1706”]
・ Olefin-based thermoplastic elastomer (TPO) [manufactured by Prime Polymer Co., Ltd., trade name “T310E”]
-Styrenic thermoplastic modified elastomer (modified SEBS) [Clayton Polymer Japan Co., Ltd., trade name "KRATON G FG1901X"]
・ Polyamide (PA6) [DuPont Co., Ltd., trade name “Zytel FN727”]
Polycarbonate (PC) [Mitsubishi Engineering Plastics Co., Ltd., trade name “Iupilon S-2000”]
・ Polybutylene terephthalate (PBT) [manufactured by Toray Industries, Inc., trade name “Trecon 1401X06”]
・ Ethylene-propylene rubber (EPR) [manufactured by JSR Corporation, trade name “EP51”]
・ Butadiene rubber (BR) [trade name “BR01” manufactured by JSR Corporation]
-Isoprene rubber (IR) [manufactured by JSR Corporation, trade name “IR2200”]

(B) Filler / metal inorganic hydrate (magnesium hydroxide) [manufactured by Martinsberg, trade name “Magnifine H10”]
・ Melamine cyanurate [DSM Japan Co., Ltd., trade name “melapurMC15”]
・ Clay [product name "Opti White", manufactured by Shiraishi Calcium Co., Ltd.]
・ Calcium carbonate [Shiraishi Calcium Co., Ltd., trade name “Shiraka Hana CCR”]
・ Talc [Nippon Talc Co., Ltd., trade name “MS-P”]
・ Zinc oxide [manufactured by Hakusuitec Co., Ltd., trade name “Zinc Hana 2”]

(C) Other additives / antioxidants [manufactured by Ciba Specialty Chemicals Co., Ltd., trade name “Irganox 1010”]
・ Metal deactivator [Ciba Specialty Chemicals, trade name “Irganox MD1024”]

(D) Dispersant-Compounds A to B below

(Synthesis of Compound A (Compound of Formula (2), R1 = Octadecyl Group))
5 g (17 mmol) of diethylenetriaminepentaacetic acid is dissolved in 50 ml of toluene, and further 3 g (18.9 mmol) of octadecyl alcohol is dissolved. The mixture is heated to 105 ° C. with stirring, and reacted for 2 hours while removing by-products in the Dean-stark trap. After completion of the reaction, the mixture was concentrated under reduced pressure to obtain a white wax-like composition. After 20 ml of cold water was added and solidified, it was collected by filtration to obtain the desired product (yield 32%). ¹ H-NMR (DMSO) σ ppm (TMS): 0.86 (t, 3H), 1.25 (m, 30H), 1.57 (t, 2H), 2.49 (s, 10H); 79 (s, 8H), 3.41 (s, 6H), 3.48 (s, 2H), 4.03 (t, 2H). IR: 2910, 1735, 1634, 1315, 1225, 1060.

(Synthesis of Compound B (Compound of Formula (7), R1 = Octadecyl Group))
It was synthesized in the same manner as Compound A except that 5 g (18.5 mmol) of t-butyl acetoacetate was used in place of diethylenetriaminepentaacetic acid (yield 45%). ¹ H-NMR (CDCl ₃ ) σ ppm (TMS): 0.88 (t, 3H), 1.26 (m, 30H), 1.64 (m, 2H), 2.27 (s, 2H), 3 .42 (s, 2H), 4.13 (t, 2H). IR: 2924, 1710, 1622, 1422, 1001.

(Production of polymer composition and coated electric wire)
First, each component shown in Table 1 or Table 2 described below is put into a twin-screw kneader, kneaded for about 5 minutes at a suitable temperature at which the organic polymer flows (for example, 220 ° C. for polypropylene), and then pelletized by a pelletizer. The polymer compositions according to the examples and comparative examples were obtained respectively. Next, each of the obtained compositions was extruded and coated at a thickness of 0.20 mm on the outer periphery of an annealed copper twisted wire conductor (cross-sectional area 0.5 mm ² ) obtained by twisting 7 annealed copper wires with a φ50 mm extruder. The covered electric wire which concerns on an example and a comparative example was produced.

  A wear resistance test was performed on each of the coated electric wires produced as described above. The test method and evaluation method will be described below. Table 1 shows the results of the examples and Table 2 shows the results of the comparative examples. The polymer composition of each comparative example differs from the polymer composition of each example of the same number in that (D) it does not contain a dispersant, and (A) an organic polymer, (B ) The types and contents of fillers and (C) other additives are the same. The amounts of (A) organic polymer, (B) filler, (C) and other additives shown in Tables 1 and 2 are expressed in parts by weight. Further, the amount of the (D) dispersant is expressed in terms of% by weight based on the total amount of the polymer composition.

(Abrasion resistance test)
In accordance with JASO D611-94, the blade reciprocation method was used. That is, the coated electric wire was cut into a length of 750 mm to obtain a test piece. Next, at a room temperature of 25 ° C., the blade was reciprocated over a length of 10 mm in the axial direction on the coating material surface of the test piece fixed on the table, and the number of reciprocations until the blade contacted the conductor due to the abrasion of the coating material Was measured. At this time, the load applied to the blade was 7 N, and the blade was reciprocated at a speed of 50 times per minute. Next, the test piece was moved 100 mm, rotated 90 degrees clockwise, and the above measurement was repeated. This measurement was performed a total of three times for the same test piece, and the lowest value was taken as the evaluation value. The number of times of wear was 500 or more.

  According to Table 1 and Table 2, it turns out that the covered electric wire which concerns on the comparative example which does not contain the dispersing agent according to this invention is inferior to abrasion resistance. On the other hand, the covered electric wire which concerns on the Example containing the dispersing agent which concerns on one Example of this invention confirmed that it was excellent in abrasion resistance. This is because the chelate structure in the dispersant strongly binds to the filler and prevents the fillers from aggregating with each other, and the long-chain alkyl group portion in the dispersant is compatible with the organic polymer, thereby increasing the filler. This is presumed to be highly dispersed in the molecular composition.

  Therefore, if the covered wire shown in this embodiment is a wire harness including the wire bundle, the covering material will be significantly worn even if it is used in contact with other covered wires in the wire bundle. High reliability is ensured over a long period of time.

  In this example, the wear resistance, which tends to be reduced by filler addition, is evaluated among the wire characteristics, but other wire characteristics that are reduced due to the dispersibility of the filler are also considered to have an improving effect. It is done. Moreover, it is considered that not only the electric wires but also other materials such as molding materials in general or other materials have an effect of improving material properties such as mechanical properties which are reduced due to filler dispersibility.

  Although the embodiments of the present invention have been described in detail above, the present invention is not limited to the above-described embodiments, and various modifications can be made without departing from the gist of the present invention.

Claims (9)

  A dispersant having a chelate structure at the end of a functional group of a long-chain alkyl compound having a functional group.   The dispersant according to claim 1, wherein the long-chain alkyl compound is a long-chain alkyl carboxylic acid, a derivative thereof, or a long-chain alkyl alcohol.   The chelate structure includes polyphosphate, aminocarboxylic acid, 1,3-diketone, hydroxycarboxylic acid, polyamine, amino alcohol, aromatic heterocyclic base, phenols, oximes, Schiff base, tetrapyrroles, and sulfur compounds. The dispersant according to claim 1, wherein the dispersant is derived from one or two or more chelating ligands selected from synthetic macrocycles, phosphonic acids, and hydroxyethylidenephosphonic acids.   The chelate structure is bonded to the functional group of the long-chain alkyl compound by one or more selected from an ester bond, an ether bond, a thioester bond, a thioether bond, and an amide bond. The dispersant according to claim 1 or 2.   A dispersant, which can be obtained by bringing a long-chain alkyl compound having a functional group into contact with a chelate ligand.   A polymer composition comprising the dispersant according to any one of claims 1 to 5, an organic polymer, and a filler.   The polymer composition according to claim 6, wherein the content of the dispersant is in the range of 0.1 to 20 parts by weight.   A covered electric wire using the polymer composition according to claim 6 or 7 as a covering material.   A wire harness using the polymer composition according to claim 6.