JP6036641B2 - Anticorrosive, coated electric wire with terminal and wire harness - Google Patents

Description

  The present invention relates to an anticorrosive agent, a coated electric wire with a terminal, and a wire harness, and more specifically, an anticorrosive agent excellent in the anticorrosive property of an electrical connection portion that is a contact portion between an electric wire conductor and a terminal fitting, a coated electric wire with a terminal, and a wire harness It is about.

  2. Description of the Related Art Conventionally, a covered electric wire formed by covering an outer periphery of a conductor made of a soft material of tough pitch copper or the like as an electric wire routed in a vehicle such as an automobile is widely used. In the terminal of this kind of covered electric wire, a terminal fitting is connected to a conductor exposed by peeling off an insulator. The terminal fitting electrically connected to the end of the covered electric wire is inserted and locked to the connector.

  A plurality of such covered electric wires with terminals are bundled to form a wire harness. In vehicles such as automobiles, wiring is usually performed in the form of a wire harness. When the wire harness is routed in an engine room, some indoor environments, etc., rust is likely to be generated at the electrical connection portion where the wire conductor and the terminal fitting come into contact with each other due to the influence of heat and water. Therefore, when wiring a wire harness in such an environment, it is necessary to prevent corrosion in the electrical connection portion.

  A technique for injecting grease into a connector in which a terminal fitting connected to a wire conductor is inserted and locked in order to prevent corrosion at the electrical connection portion is known (see, for example, Patent Document 1).

  In recent years, the movement to improve fuel efficiency has been accelerated by reducing the weight of vehicles such as automobiles, and there is a demand for reducing the weight of the wire material constituting the wire harness. Therefore, the use of aluminum for the wire conductor has been studied. The terminal fitting is generally made of copper or a copper alloy having excellent electrical characteristics. Therefore, it is often used in a combination of an aluminum electric wire and a copper terminal fitting. If the material of the wire conductor and the terminal fitting are different, corrosion due to contact with different metals occurs at the electrical connection portion. This type of corrosion is more likely to occur than when the wire conductor and the terminal fitting are the same material. For this reason, an anticorrosive capable of reliably preventing the electrical connection portion is required.

  The above-mentioned conventional covered electric wire with a terminal using grease has a problem that the anticorrosion effect cannot be enhanced by sufficiently preventing water from entering unless the grease is injected into the connector densely. However, if the filling amount of grease is increased in order to enhance the anticorrosion effect, the grease will be applied even to a portion that does not need to be anticorrosive. Furthermore, excessive filling causes stickiness of the connector and the electric wire, and deteriorates handling.

  Therefore, as an alternative to grease, an anticorrosive capable of exhibiting high anticorrosion performance and a coated electric wire with a terminal have been proposed (for example, see Patent Document 2). The anticorrosive described in Patent Document 2 and the coated electric wire with terminal eliminate the disadvantages of the grease.

Japanese Patent Application Laid-Open No. 5-159646 JP 2011-111632 A

  However, when used for automobiles and the like, in addition to requiring durability against high-temperature deterioration, durability such as a cooling / heating cycle is required. When a thermal cycle is applied to a coated electric wire with a terminal treated with an anticorrosive agent, it is necessary that the anticorrosive agent does not crack and has anticorrosive performance. That is, it is important that the anticorrosive agent maintains flexibility and does not become hard even at low temperatures.

  The object of the present invention is to solve the above-mentioned problems of the prior art, and is excellent in the anticorrosion performance of the wire connection portion between the covered wire and the terminal fitting, does not become hard at low temperatures, and even when a cooling cycle is applied. An object of the present invention is to provide an anticorrosive agent, a coated electric wire with a terminal, and a wire harness that do not cause a crack in the anticorrosive agent.

In order to solve the above problems, the anticorrosive agent of the present invention comprises:
An anticorrosive agent used for a coated electric wire with a terminal in which a contact portion between the electric wire conductor of the covered electric wire and the terminal fitting is covered with an anticorrosive agent,
The said anticorrosive used the curable resin which has the following composition as a main component.
40 to 90 parts by mass of isobornyl (meth) acrylate and 10 to 40 alkyl (meth) acrylate represented by the following formula 1 with respect to 100 parts by mass of the (meth) acrylate monomer polymer having two or more (meth) acrylate groups. A composition comprising parts by weight. R1 in Formula 1 is H or _CH 3, R2 is an alkyl group having 2 to 4 carbon atoms.

  In the anticorrosive agent, the composition of the curable resin further contains 1 to 15 masses of alkyl (meth) acrylate having 8 to 13 carbon atoms in the alkyl group based on 100 parts by mass of the (meth) acrylate monomer polymer. It is preferable to include within the range of part.

  In the anticorrosive agent, the curable resin can be configured as an ultraviolet curable resin. In that case, it is preferable that the said curable resin contains a photoinitiator and this photoinitiator has absorption in the wavelength range of 320-420 nm.

  In the anticorrosive, the curable resin can be configured as a thermosetting resin.

  The coated electric wire with a terminal of the present invention is a coated electric wire with a terminal in which the contact portion between the electric wire conductor of the coated electric wire and the terminal fitting is coated with an anticorrosive agent, and the anticorrosive agent is used as the anticorrosive agent. Is a summary.

  In the covered electric wire with a terminal, it is preferable that the electric wire conductor of the covered electric wire is aluminum, the terminal fitting is made of a copper-based metal, and the contact portion is constituted as a dissimilar metal connecting portion.

  The wire harness of this invention makes it a summary to have said covered electric wire with a terminal.

  The anticorrosive agent of the present invention is an anticorrosive agent used for a coated electric wire with a terminal in which a contact portion between a wire conductor of a covered electric wire and a terminal fitting is covered with an anticorrosive agent, and the anticorrosive agent is a (meth) acrylate group. 40 to 90 parts by mass of isobornyl (meth) acrylate, an alkyl (meth) having 2 to 4 carbon atoms represented by the above formula 1 with respect to 100 parts by mass of a (meth) acrylate monomer polymer having 2 or more of By using a curable resin whose main component is a composition containing 10 to 40 parts by mass of acrylate, it has excellent anticorrosion performance, does not become hard at low temperatures, and cracks occur in the anticorrosion agent even when a cooling cycle is applied. There is no fear.

  That is, by making the blending amount of the above isobornyl (meth) acrylate within the above specified range, the heat resistance is improved, the decrease in elongation due to high temperature deterioration is small, the flexibility is not lowered, the thermal shock resistance is good, and after the test There is little risk of cracking in the anticorrosive.

  The coated electric wire with a terminal of the present invention is a coated electric wire with a terminal in which the contact portion between the electric wire conductor of the coated electric wire and the terminal fitting is coated with an anticorrosive agent, and the anticorrosive agent is used as the anticorrosive agent. Thereby, the thing excellent in the corrosion resistance of the said contact part is obtained. In particular, when the wire conductor of the covered wire is aluminum, the terminal fitting is made of a copper-based metal, and the contact portion is formed as a dissimilar metal connection portion, it is possible to exert a particularly excellent effect. .

  The wire harness of this invention is excellent in the anticorrosion performance of the contact part of a covered electric wire and a terminal metal fitting.

FIG. 1 is an external perspective view showing an embodiment of a covered electric wire with a terminal according to the present invention. 2 is a cross-sectional view taken along line AA in FIG.

  Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings. FIG. 1 is an external perspective view showing an embodiment of a covered electric wire with a terminal of the present invention, and FIG. 2 is a cross-sectional view taken along line AA of FIG. As shown in FIG.1 and FIG.2, as for the covered electric wire 1 with a terminal of a present Example, the edge part of the covered electric wire 2 is crimped | bonded to the edge part of the terminal metal fitting 5 made from brass. In the covered electric wire 2, an electric wire conductor 3 made of an aluminum alloy is covered with an insulator 4 made of polyvinyl chloride resin. The crimping part of the electric wire conductor 3 and the terminal metal fitting 5 becomes the contact part 6, and both are electrically connected. The contact portion 6 is covered with an anticorrosive agent 7. FIG. 1 shows the coating film of the anticorrosive 7 seen through.

  The present invention is greatly characterized in that the anticorrosive 7 uses a curable resin whose main component is a composition containing the following components (A) to (C). Hereinafter, the curable resin of the anticorrosive 7 will be described.

(A) 100 parts by mass of (meth) acrylate monomer polymer having a main skeleton having two or more (meth) acrylate groups,
(B) 40 to 90 parts by mass of isobornyl (meth) acrylate,
(C) 10 to 40 parts by mass of the alkyl (meth) acrylate represented by Formula 1, wherein R1 is H or CH ₃ , and R2 is an alkyl group having 8 to 13 carbon atoms. Hereinafter, the component (C) may be referred to as an alkyl (meth) acrylate having an alkyl group having 2 to 4 carbon atoms.

(A) (Meth) acrylate monomer polymer:
The component (A) is a polymer of a (meth) acrylate monomer, and after polymerization of a (meth) acrylate monomer having one (meth) acrylate group, two or more (meth) acrylate groups were given. An acrylic oligomer is used.

  The monofunctional (meth) acrylate monomer having one (meth) acrylate group is not particularly limited, and (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, (meth) acrylic acid- n-propyl, (meth) acrylic acid isopropyl, (meth) acrylic acid-n-butyl, (meth) acrylic acid isobutyl, (meth) acrylic acid-t-butyl, (meth) acrylic acid-n-pentyl, (meta ) Acrylic acid-n-hexyl, (meth) acrylic acid cyclohexyl, (meth) acrylic acid-n-heptyl, (meth) acrylic acid-n-octyl, (meth) acrylic acid-2-ethylhexyl, (meth) acrylic acid Nonyl, Decyl (meth) acrylate, Dodecyl (meth) acrylate, Phenyl (meth) acrylate, Benth (meth) acrylate , (Meth) acrylic acid-2-methoxyethyl, (meth) acrylic acid-3-methoxybutyl, (meth) acrylic acid-2-hydroxyethyl, (meth) acrylic acid-2-hydroxypropyl, (meth) acrylic Stearyl acid, glycidyl (meth) acrylate, trifluoromethyl methyl (meth) acrylate, 2-perfluoroethyl (meth) acrylate, perfluoromethyl (meth) acrylate, 2-perfluorohexyl (meth) acrylate Examples thereof include ethyl and 2-perfluorodecylethyl (meth) acrylate. These may be used individually by 1 type and may use 2 or more types together.

  The (A) (meth) acrylate monomer polymer is preferably a polymer of a monofunctional (meth) acrylate monomer. The degree of polymerization of the (meth) acrylate monomer polymer is preferably in the range of 5 to 500.

  In the present invention, the description of “(meth) acrylate” means methacrylate and acrylate.

(B) Isobornyl (meth) acrylate:
The said (B) component is a monomer of isobornyl (meth) acrylate, and it can make adhesiveness and heat resistance compatible by using 40-90 mass parts with respect to 100 mass parts of said (A) component. When the isobornyl (meth) acrylate is less than 40 parts by mass, the heat resistance of the anticorrosive agent is low, and the decrease in elongation due to high temperature deterioration becomes large, and practical performance as an anticorrosive agent cannot be obtained. On the other hand, if the isobornyl (meth) acrylate is more than 90 parts by mass, the hardness of the anticorrosive agent becomes too hard and the flexibility is lowered, and cracking is likely to occur in the endurance test of the thermal shock.

(C) C2-C4 alkyl (meth) acrylate:
The component (C) is an alkyl (meth) acrylate monomer containing an alkyl group having 2 to 4 carbon atoms (C2 to C4), and 10 to 40 parts by mass are used with respect to 100 parts by mass of the component (A). Thereby, the glass transition temperature of hardened | cured material falls and it can improve thermal shock resistance. If the blending amount of the C2 to C4 alkyl (meth) acrylate is less than 10 parts by mass, the effect of improving the low temperature characteristics of the anticorrosive agent that is a resin cured product cannot be sufficiently exerted, and if it exceeds 40 parts by mass, the heat aging resistance decreases. Thus, the hardness when the cured product is heated also decreases.

  Specific examples of the C2-C4 alkyl (meth) acrylate monomer used as the component (C) include ethyl acrylate and ethyl methacrylate having an alkyl group of C2, isobutyl acrylate, n-butyl acrylate and t-butyl having an alkyl group of C4. Examples include acrylate, isobutyl methacrylate, n-butyl methacrylate, and t-butyl methacrylate. Moreover, the C2-C4 alkyl (meth) acrylate may be used alone or in combination of two or more. As the C2 to C4 alkyl (meth) acrylate monomer, it is preferable to contain a large amount of C4 from the viewpoint of low Tg and good cooling characteristics.

(D) C8-C13 alkyl (meth) acrylate:
In the composition, as the component (D), an alkyl (meth) acrylate having an alkyl group having 8 to 13 carbon atoms (C8 to C13) of the alkyl group is added to 1 part by mass of the component (A). It can mix | blend within the range of -15 mass parts. By adding C8-C13 alkyl (meth) acrylate, compatibility with the processing oil is improved, and oil surface adhesion is obtained. Even when the processing oil adheres to the terminal fitting or the like, good adhesion between the anticorrosive and the terminal fitting can be obtained. On the other hand, when the alkyl group exceeds C13, the glass transition point of the monomer becomes too high, and the hardness at low temperature becomes so hard that heat aging resistance (low temperature tensile test after heat aging) may not be satisfied.

  When the amount of the C8 to C13 alkyl (meth) acrylate is less than 1 part by mass with respect to 100 parts by mass of the component (A), the effect of addition may not be sufficiently exhibited, and when the amount exceeds 15 parts by mass. In addition, the hydrophobicity becomes too high, and the adhesiveness with the metal surface or the like may be lowered.

  Specific examples of the C8 to C13 alkyl (meth) acrylate monomer used as the component (D) include isooctyl acrylate, 2-ethylhexyl methacrylate, alkyl group C9 isononyl acrylate, and alkyl group C12. Lauryl acrylate, lauryl methacrylate, tridecyl acrylate having an alkyl group of C13, tridecyl methacrylate, and the like. Moreover, the C8-C13 alkyl (meth) acrylate may use the said monomer independently, and may mix and use 2 or more types. As C8-C13 alkyl (meth) acrylate monomer, C10 or more is preferable from the viewpoint of oil surface adhesion.

(E) Polymerization initiator:
A polymerization initiator may be added to the anticorrosive as the component (E). It is preferable that content of a polymerization initiator exists in the range of 0.1-10 mass% of the whole composition of an anticorrosive. Specific examples of the polymerization initiator include a photopolymerization initiator and a thermal polymerization initiator.

  The anticorrosive curable resin is preferably configured as an ultraviolet curable resin capable of ultraviolet curing from the viewpoint that the curing time can be shortened. When the curable resin is configured as an ultraviolet curable resin, it is preferable to add an ultraviolet polymerization initiator (sometimes referred to as a photopolymerization initiator or photoinitiator) as a polymerization initiator. The photoinitiator is preferably a compound having absorption within a wavelength range of 320 to 420 nm. By using such a photoinitiator, it is possible to cure the anticorrosive using an ultraviolet irradiation device or the like using an LED light source.

  The photopolymerization initiator is not particularly limited as long as it is a compound that absorbs ultraviolet rays to initiate radical polymerization, and a conventionally known photopolymerization initiator can be used. Specific examples of the photopolymerization initiator include 1-hydroxycyclohexyl phenyl ketone, 2,2-dimethoxy-2-phenylacetophenone, xanthone, fluorenone, benzaldehyde, fluorene, anthraquinone, ethylanthraquinone, triphenylamine, and carbazole. 3-methylacetophenone, 4-chlorobenzophenone, 4,4′-dimethoxybenzophenone, 4,4′-diaminobenzophenone, Michler's ketone, benzoin propyl ether, benzoin ethyl ether, benzyldimethylketal, 1- (4- Isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, thioxanthone, diethylthioxanthone, 2-isopropylthio Xanthone, 2-chlorothioxanthone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propan-1-one, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis- (2, 6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide and the like. These may be used individually by 1 type and may use 2 or more types together.

  In addition, the anticorrosive agent can be constituted by using a curable resin as a thermosetting resin. When the curable resin is configured as a thermosetting resin, it is preferable to add a thermal polymerization initiator as a polymerization initiator.

  The thermal polymerization initiator is not particularly limited as long as it is a compound capable of generating radicals by heating to initiate radical polymerization, and conventionally known organic peroxides, azo compounds, etc. are used. Can do. Examples of the organic peroxide include dialkyl peroxide, dicumyl peroxide, t-butylcumyl peroxide, and dialkyl such as 2,5-dimethyl-2,5-bis (t-butylperoxy) hexane. And peroxyketals such as peroxide and n-butyl 4,4-di (t-butyl peroxide) valerate. Examples of the azo compound include azobisisobutyronitrile.

  In addition to the components (A) to (D) and the polymerization initiator (E), other components may be added to the curable resin as necessary within the range not impairing the object of the present invention. Examples of the other components include anti-aging agents, adhesion imparting agents, corrosion inhibitors, thixotropic agents, liquid preparation agents such as leveling agents, pigments, dyes, inorganic fillers, and the like.

  Hereinafter, the covered electric wire with a terminal of the present invention will be described. In the covered electric wire with terminal 1 shown in FIGS. 1 and 2, the contact portion 6 is in contact with the aluminum alloy of the electric wire conductor 3 and the tin-plated brass of the terminal fitting 5. The contact portion 6 is configured as a dissimilar metal connecting portion in a state where dissimilar metals of aluminum and copper-based metal are in contact with each other.

  The metal terminal 5 is made of a metal plate whose surface is tin-plated with brass as a base material. The terminal metal 5 is punched into a predetermined shape in which the terminal metal is developed, and a barrel portion or the like is bent. The terminal fitting 5 has a tab-like connection part 51 as a male terminal connected to the mating female terminal, and a barrel part 54 that extends from the base end of the connection part 51 and crimps the covered electric wire. . The barrel portion 54 is composed of two crimping portions including a wire barrel 52 provided on the connection portion 51 side and an insulation barrel 53 provided on the wire conductor 2 side.

  In the covered electric wire 1 with a terminal, the electric wire conductor 3 in a state where the electric wire terminal is peeled off and exposed is crimped by a wire barrel 52 and is crimped. Further, the insulation barrel 53 of the terminal fitting 5 is crimped around the insulator 4 of the covered electric wire 2 and crimped. The crimp portion of the insulation barrel 53 is an electric wire fixing portion for fixing and holding the terminal fitting 5 to the end of the covered electric wire 2.

  The coated electric wire with terminal 1 is coated with the anticorrosive composition 7 in which the wire conductor 3 of the coated electric wire 2 and the contact portion 6 of the terminal fitting 5 are coated with the anticorrosive composition made of the curable resin. Has been. At least the anticorrosive 7 needs to cover a portion of the contact portion 6 where the wire conductor 3 is exposed, a contact interface between the wire conductor 3 and the terminal fitting 6, and the like. The anticorrosive 7 has a function as a protective film that prevents moisture or the like from entering the dissimilar metal contact portion 6 between the wire conductor 3 and the terminal metal fitting 5 from the outside and corroding the metal portion.

  In the covered electric wire with terminal 1 shown in FIG. 1 and FIG. As shown in FIG. 2, the anticorrosive 7 is coated with a predetermined thickness along the outer peripheral shape of the terminal fitting 5 and the covered electric wire 2. The bottom surface is not covered with the anticorrosive 7 and the metal of the terminal fitting 5 is exposed to the outside.

  The anticorrosive 7 is such that at least the exposed portion of the wire conductor 2 is completely covered so that it is not exposed to the outside. The anticorrosive 7 coats the end side of the covered wire 4 so that it protrudes slightly from the tip of the wire conductor 2 to the connecting portion 51 side of the terminal fitting 5. Further, the end side of the terminal metal fitting 5 is covered so as to slightly protrude toward the insulator 4 side. Further, the bottom of the terminal fitting 5 of FIG. 2 is not covered with the anticorrosive coating film 7, and the metal is exposed.

  The covered electric wire 1 with a terminal of the present invention is not limited to the above-mentioned form in which the portion covered with the anticorrosive agent 7 is sufficient, as long as at least the electric wire conductor 3 is not exposed to the outside. Furthermore, it is preferable that the contact portion between the wire conductor 3 and the anticorrosive 7 is also covered with the anticorrosive. Moreover, as shown in FIG. 1, you may coat | cover so that the anticorrosive 7 may protrude outward from the barrel part 54, and you may coat | cover the bottom face of the terminal metal fitting 5 with the anticorrosive 7, although it does not show in particular. Moreover, the side surface of the terminal metal fitting 5 may be either coated with the anticorrosive 7 or not.

  The electric wire conductor 3 is composed of a stranded wire formed by twisting a plurality of strands 3a. The stranded wire may be composed of one type of metal strand, or may be composed of two or more types of metal strand. Moreover, the twisted wire may contain the strand etc. which consist of organic fibers other than a metal strand. Note that “consisting of one type of metal strand” means that all the metal strands constituting the stranded wire are made of the same metal material, and “consisting of two or more types of metal strands” This means that the wire contains metal wires made of different metal materials. The stranded wire may include a reinforcing wire (tension member) for reinforcing the covered electric wire.

  Examples of the material of the metal wire constituting the wire conductor 3 include copper, copper alloy, aluminum, or materials obtained by applying various platings to these materials in addition to the aluminum alloy. Moreover, as a material of the metal strand as a reinforcement wire, a copper alloy, titanium, tungsten, stainless steel etc. can be illustrated. Examples of the organic fiber as the reinforcing wire include Kevlar. As a metal strand used for the electric wire conductor 3, it is preferable to use aluminum or aluminum alloy from points, such as weight reduction of an electric wire.

  The material of the insulator 4 used for the covered electric wire 2 is not particularly limited, and examples thereof include rubber, polyolefin, vinyl chloride resin (PVC), and thermoplastic elastomer. These may be used alone or in admixture of two or more. Various additives may be appropriately added to the material of the insulator 4. Examples of the additive include a flame retardant, a filler, a colorant and the like.

  As a material (material for the base material) used for the terminal fitting 5, various copper alloys, copper, and the like can be used in addition to brass. Moreover, the terminal metal fitting 5 may be plated with various metals, such as tin, nickel, and gold, on a part of the surface (for example, a contact) or the whole.

  The anticorrosive 7 is preferably applied so that the thickness is in the range of 0.01 to 3 mm. If the thickness of the anticorrosive 7 is too thick, it may be difficult to insert the terminal fitting 5 into the connector of the mating terminal. Moreover, when the thickness of the anticorrosive 7 becomes too thin, there exists a possibility that anticorrosion performance may become inadequate.

  Hereinafter, the manufacturing method of the covered electric wire with a terminal is demonstrated. In order to manufacture the covered electric wire 1 with a terminal, first, the insulator 4 at the end of the covered electric wire 2 is peeled to expose the electric wire conductor 2 by a predetermined length. Next, the plated base material is punched at the end of the covered electric wire 2, the terminal fitting 5 formed by bending or the like is crimped and crimped, and the wire conductor 3 and the terminal fitting 5 are connected. For crimping, the wire conductor 3 is crimped to the wire barrel 52 of the terminal fitting, and the insulator 4 is crimped to the insulation barrel 53. Subsequently, the composition of the anticorrosive agent 7 is apply | coated to the predetermined range of the contact part 6 of the electric wire conductor 3 and the terminal metal fitting 5, and the covered electric wire 1 with a terminal is obtained by making it harden | cure on predetermined conditions.

  The method for applying the composition of the anticorrosive agent 7 to the contact portion 6 is not particularly limited, and known means such as a dropping method, a coating method, and an extrusion method can be used. Moreover, when applying the composition of the anticorrosive agent 7, the temperature of the composition of the anticorrosive agent 7 may be adjusted by heating, cooling, or the like.

  A curing device such as an ultraviolet irradiation device or a heating device can be used for curing the anticorrosive composition.

  Hereinafter, the wire harness of the present invention will be described. The wire harness of the present invention is formed by bundling a plurality of covered electric wires including the above-described covered electric wire with terminal 1. In the wire harness, a part of the covered electric wire may be the covered electric wire 1 with a terminal of the present invention, or all may be the covered electric wire 1 with a terminal of the present invention.

  In the wire harness, the plurality of covered electric wires may be bundled by tape winding, or may be bundled by being covered by an exterior part such as a round tube, a corrugated tube, or a protector. .

  The wire harness of the present invention is suitable for being routed in a vehicle such as an automobile, and is particularly suitable for being routed in an engine room or a vehicle in a wet area. When the wire harness is routed in such a place, rust is likely to occur at the electrical connection portion between the wire conductor 3 and the terminal fitting 5 due to the influence of heat and water. Since the contact part 6 of the wire conductor 3 and the terminal metal fitting 5 in the covered electric wire 1 with a terminal is covered with the anticorrosive agent 7, the wire harness of this invention can suppress generation | occurrence | production of rust effectively.

  Examples of the present invention and comparative examples are shown below. In addition, this invention is not limited by these Examples.

Examples 1-13
Each component such as a (meth) acrylate polymer, a monomer, a photoinitiator, and a thermal initiator is blended in the composition of the anticorrosive shown in Table 1 and Table 2, and mixed uniformly to provide anticorrosion of Examples 1 to 13. An agent was prepared. The obtained anticorrosive was tested for adhesion, hardness, heat aging resistance, Tg, thermal shock resistance, and the like. The test results are shown in Tables 1 and 2.

Comparative Examples 1-9
For comparison, the composition shown in Table 3 was mixed in the same manner as in the examples to prepare the anticorrosives of Comparative Examples 1 to 9, and the adhesiveness, hardness, heat aging resistance, Tg, as in the examples. In addition, tests were conducted for thermal shock resistance and the like. The test results are shown in Table 3. The details of each component used in the composition of the anticorrosive and the test methods are as follows.

((Meth) acrylate monomer polymer]
CN820: (Meth) acrylate oligomer, manufactured by Sartomer, trade name “CN820”
EBECRYL767: manufactured by Daicel Cytec Co., Ltd., linear acrylic oligomer, trade name “EBECRYL767”, a mixture of oligomer and isobornyl acrylate, with a mixing ratio (mass ratio) of oligomer: IBA = 70: 30

〔monomer〕
Isobornyl acrylate: manufactured by Sartomer, trade name “SR506”
・ Butyl acrylate (C = 3): manufactured by Mitsubishi Chemical Corporation, trade name “butyl acrylate”
・ Ethyl acrylate (C = 2): Mitsubishi Chemical Co., Ltd., trade name “ethyl acrylate”
・ Lauryl acrylate (C = 12): manufactured by Sartomer, trade name “SR335”
Dodecyl acrylate (C = 13): manufactured by Sartomer, trade name “SR489”
Stearyl acrylate (C = 18): manufactured by Sartomer, trade name “SR257”

[Photoinitiator]
Irgacure 184: 1-hydroxy-cyclohexyl-phenyl ketone, manufactured by BASF, trade name “Irgacure 184”

(Thermal initiator)
Perbutyl O: t-butyl-peroxy-2-ethylhexanoate, manufactured by NOF Corporation, trade name “Perbutyl O”

[Adhesion test method]
About the anticorrosive of an Example and a comparative example, the shear adhesion test prescribed | regulated to JISK6850 was done. Using a tin-plated plate as the adherend, placing a ring with an inner diameter of 6 mm and a height of 2 mm on the tin-plated plate, filling the ring with an anticorrosive, and curing it to a thickness of 2 mm under the following prescribed conditions Created a piece. Test specimens were prepared with the surface of the tin-plated plate in a state of a cleaning surface and an oil surface, respectively. As for the cleaning surface, the surface of the tin plating plate was cleaned with ethanol. The oil surface was applied to the surface of the tin-plated plate so that the mineral processing oil was 1 mg / cm ² .

The test pieces of Examples 1 to 12 and Comparative Examples 1 to 9 were UV cured by irradiating the anticorrosive with 1 J / cm ² of UV in the atmosphere. As the ultraviolet irradiation lamp, a mercury xenon lamp having a light amount of 500 mW / cm ² and a dominant wavelength of 365 nm was used. The test piece of Example 13 was heated and cured at 120 ° C. for 1 hour.

[Adhesiveness of cleaned surface]
The adhesion test on the cleaned surface was conducted by pulling the ring of the test piece in parallel with the tin-plated plate (pulling speed 100 m / min) and performing a tensile test. As a result of the test, an adhesive strength of 1 MPa or more was evaluated as good (◯), and an adhesive strength of less than 1 MPa was evaluated as poor (x).

[Oil surface adhesion]
In the oil surface adhesion test, a tensile test was performed in the same manner as the cleaning surface tensile test, and the state of destruction of the anticorrosive agent after the tensile test was observed. As a result, the overall cohesive failure of the anticorrosive agent was evaluated as excellent (◎), the partial cohesive failure of the anticorrosive agent was determined as good (◯), and the case of interfacial failure between the anticorrosive agent and the tin plated plate was determined as poor (×).

〔Hardness〕
The hardness of the anticorrosive was measured using a durometer type A hardness meter defined in JIS K6253. As a result of the measurement, a case where the hardness was 50 or less was evaluated as good (◯), and a case where the hardness was more than 50 was determined as poor (X).

[Heat aging resistance]
The test piece was left at a high temperature of 120 ° C. for 120 hours and then subjected to a tensile test at 0 ° C. in accordance with JIS K6249 to measure the elongation at break. The test piece for the tensile test was prepared by punching out a JIS No. 4 dumbbell from a cured sheet obtained by applying an anticorrosive agent to a sheet having a thickness of 2 mm and irradiating it with ultraviolet rays. The ultraviolet irradiation during the curing was performed under the same conditions (mercury xenon lamp, 500 mW / cm ² , 365 nm) as in the preparation of the test piece for shear bond strength. As a result of the tensile test, a case where the elongation was 10% or more was judged as good (◯), and a case where the elongation was less than 10% was judged as bad (x).

[Tg]
The Tg of the cured product was measured by DSC method. The cured product was cured by applying the composition to a thickness of 1 mm and irradiating with ultraviolet rays in the atmosphere. Irradiation with ultraviolet rays was performed under the same conditions (mercury xenon lamp, 500 mW / cm ² , 365 nm) as in the preparation of the test piece for shear bond strength. The case where Tg was less than 0 ° C. was judged as good (◯), and the case where Tg was 0 ° C. or higher was judged as defective (×).

(Cool thermal shock)
Similar to the measurement of Tg, a test piece coated with the composition to a thickness of 1 mm and cured by irradiation with ultraviolet rays in the atmosphere was treated at −40 ° C. for 1 hour, and then 1 at + 120 ° C. The time treatment was defined as one cycle, and the surface of the test piece after 500 cycles was observed. The case where cracks did not occur on the surface of the test piece was evaluated as good (◯), and the case where cracks were observed was evaluated as poor (x).

  As shown in Tables 1 and 2, Examples 1 to 13 all had good test results for adhesion, hardness, heat aging resistance, Tg, and thermal shock resistance. On the other hand, as shown in Table 3, Comparative Examples 1 to 9 could not satisfy all of adhesiveness, hardness, heat aging resistance, Tg, and thermal shock resistance.

  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.

  Although the covered electric wire 1 with a terminal of the said Example showed the example which used the tab-shaped male terminal as a terminal metal fitting, it is not limited to this. For example, a covered electric wire with a terminal may use a female terminal as a terminal fitting. A tuning fork terminal or the like may be used as the terminal fitting.

  Moreover, you may comprise the barrel part 54 of the terminal metal fitting 5 only from the wire barrel which does not have an insulation barrel.

  Moreover, you may comprise the barrel part 54 only from an insulation barrel. In that case, the method of connecting the wire conductor and the terminal fitting may be a method such as pressure welding, ultrasonic welding, or soldering.

  Moreover, although the twisted wire was used as the electric wire conductor 3 in the said Example, the electric wire conductor 3 may use a single core wire.

DESCRIPTION OF SYMBOLS 1 Coated electric wire with a terminal 2 Coated electric wire 3 Electric wire conductor 4 Insulator 5 Terminal metal fitting 51 Terminal metal fitting connection part 54 Barrel part 6 Contact part 7 Anticorrosive

Claims (7)

An anticorrosive agent used for a coated electric wire with a terminal in which a contact portion between the electric wire conductor of the covered electric wire and the terminal fitting is covered with an anticorrosive agent,
The said anticorrosive used the curable resin which has the following composition as a main component.
40 to 90 parts by mass of isobornyl (meth) acrylate and 10 to 40 alkyl (meth) acrylate represented by the following formula 1 with respect to 100 parts by mass of the (meth) acrylate monomer polymer having two or more (meth) acrylate groups. A composition comprising parts by weight. R1 in Formula 1 is H or _CH 3, R2 is an alkyl group having 2 to 4 carbon atoms.

The anticorrosive agent according to claim 1 , wherein the curable resin is configured as an ultraviolet curable resin. The anticorrosive agent according to claim 2 , wherein the curable resin contains a photoinitiator, and the photoinitiator has absorption within a wavelength range of 320 to 420 nm. The anticorrosive agent according to claim 1 , wherein the curable resin is configured as a thermosetting resin. A covered electric wire with a terminal in which a contact portion between the electric wire conductor of the covered electric wire and the terminal fitting is covered with an anticorrosive agent,
A coated electric wire with a terminal, wherein the anticorrosive agent according to any one of claims 1 to 4 is used as the anticorrosive agent. 6. The covered electric wire according to claim 5 , wherein the electric wire conductor of the covered electric wire is aluminum, the terminal fitting is made of a copper-based metal, and the contact portion is constituted as a dissimilar metal connecting portion. A wire harness comprising the coated electric wire with a terminal according to claim 5 or 6 .

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