JP2015053156A - Terminal connection structure of wire terminal and formation method therefor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To form an exterior protective material for water-stopping and reinforcing the terminal connection of a wire terminal simply.SOLUTION: In the terminal connection structure of a wire terminal where a terminal, to be connected by swaging a barrel, is crimped to a core wire exposed in the terminal of a wire by stripping an insulation coating layer, dark curable UV-curing resin is applied from the core wire exposed point in the wire crimp part of the terminal excepting the electric contact part, to the insulation coating layer at the terminal of the wire, and then cured by irradiating with a UV-ray thus providing exterior protective material.

Description

  The present invention relates to a terminal connection structure for an electric wire terminal and a method for forming the structure, and more particularly, to waterproof and reinforce a bolt fastening terminal connected to an electric wire terminal of a wire harness routed in a vehicle such as an automobile. .

Conventionally, out of a group of electric wires constituting a wire harness routed in a vehicle, a so-called thick electric wire having a conductor cross-sectional area of 8 mm ² or more having a large allowable current is used for a power supply circuit or an earth circuit. In many cases, a bolt fastening terminal is crimped to the end of the thick wire. The bolt tightening terminal is fastened with a nut fixed to the bus bar or is fastened with the nut through a bolt hole provided in the bus bar to be electrically connected. When the thick wire W is a ground wire, a bolt fastening terminal as a ground terminal connected to the end of the ground wire is passed through a screw hole or a mounting hole provided in the vehicle body panel and fastened to the nut.

When the ground terminal of the wire terminal is fastened to the vehicle body panel, water is applied to the ground terminal, and water is generated by capillarity in the gap inside the core wire of the wire terminal connected to the ground terminal and the gap between the core wire and the insulation coating. There is. Not only the ground terminal fastened to the vehicle body panel but also the power terminal connected to the bus bar in the electrical connection box, the power terminal may be flooded with water applied to the electrical connection box.
Moreover, in the wire harness mounted on the vehicle, the electric wire is in an environment where the electric wire is shaken by the barrel crimping portion of the terminal as a fulcrum due to vibration during traveling of the vehicle, and the electric wire is easily broken.

  As shown in FIG. 5 in Japanese Patent Application Laid-Open No. 2007-134134, the applicant previously connected the barrel 151 of the bolt terminal 150 to the core wire 140 exposed from the end of the electric wire 130. In addition, a bent portion 154 is provided between the electrical contact portion 153 provided with the bolt hole 152 and the barrel 151, and the electric wire covered with the resin mold portion 160 from the crimped portion by the barrel 151 to the covering portion 141 of the terminal portion of the electric wire 130. Provides a waterproof structure for the terminal.

  As mentioned above, at the connection part of the crimp terminal of the electric wire terminal, since the resin is molded from the exposed position of the core wire of the electric wire to the barrel of the crimp terminal and the covering portion of the electric wire terminal, the water from the core wire of the electric wire is prevented, And it can suppress that the vibration of an electric wire is transmitted to a crimp terminal, and can reduce and prevent that an electric wire breaks in a terminal connection location.

JP 2007-134134 A

  However, in the waterproof structure of the electric wire terminal of Patent Document 1, after the terminal is crimped and connected to the electric wire terminal, the terminal crimping portion is set in a mold for molding of the resin molding machine, and the mold is filled with resin and molded. There is a need to. Thus, if the resin mold part is provided by resin molding, a resin molding machine and a metal mold are required, and costs increase. Further, in the work process in which the terminal crimping part is set on a mold for molding, and after resin molding, the work is taken out and hardened, it takes time and work time, which also increases the cost.

  The present invention is intended to solve the above-mentioned problem, and it is possible to easily and inexpensively waterproof without connecting the connection portion between the electric wire and the terminal, and at the terminal connection portion due to vehicle vibration, the electric wire is disconnected and damaged. It is an object of the present invention to provide a terminal connection structure for an electric wire terminal that can be suppressed and a method for forming the structure.

In order to solve the above problems, the present invention provides a terminal connection structure for an electric wire terminal in which a terminal is crimped and connected to a core wire exposed by peeling off an insulating coating layer at the end of the electric wire,
The exterior protection that is cured by irradiating ultraviolet rays after applying a dark-curing ultraviolet curable resin over the insulating coating layer in contact with the peeled end of the electric wire from the exposed portion of the wire crimping portion excluding the electrical contact portion of the terminal The terminal connection structure of the electric wire terminal characterized by providing the material is provided.

The electric wire is a thick electric wire having a conductor cross-sectional area of 8 mm ² or more used for a power supply circuit and / or a ground circuit arranged in a vehicle, and the terminal to be crimped and connected to the electric wire terminal is an electric contact provided with a bolt hole. It is a bolt fastening terminal which consists of an electroconductive metal plate which provided the electric wire crimping part which protruded the barrel in the part continuously. The bolt terminal is preferably connected to the bus bar and / or the vehicle body panel by bolting.
The bolt fastening terminal connected to the thick wire is often used as a ground terminal that is fastened to a vehicle body panel that is prone to flooding and is susceptible to running vibration of the vehicle, so it can be protected by the exterior protective material. preferable.
In addition, you may provide the waterproof part coat | covered with the said exterior protection material in the terminal connection part of the electric wire terminal whose conductor cross-sectional area is smaller than the said thick wire. Further, the terminal connected to the electric wire terminal may be a female terminal and a male terminal that are fitted and connected to the mating terminal instead of the bolt-clamping terminal, and may be a terminal such as a tuning fork terminal. It may be protected by waterproofing with a material.

  The length of the area | region which covers the insulation coating layer of the electric wire terminal continuing to a terminal crimping part with the said exterior protection material is not specifically limited. The hardness of the exterior protective material is high, and if the long region is covered with the exterior protective material, the flexibility of the electric wire is impaired, and therefore, approximately 10 mm to 30 mm is preferable. In addition, in the part which covers an insulation coating layer, the ratio of the compounding component of the said ultraviolet curable resin may be changed, the hardness after hardening may be made low, and flexibility may be given, and the length of a protection area | region may be enlarged.

  In the dark-curing ultraviolet curable resin forming the exterior protective material, when a part of the applied portion is irradiated with ultraviolet rays from the outside, the irradiated portion is cured, and this curing is chained and the irradiation light is blocked. The entire dark part curable ultraviolet curable resin including the portion to be irradiated, the inside where the irradiation light does not reach, and the back surface opposite to the irradiation side can be cured. Therefore, if a dark-curing UV curable resin is applied to the outer periphery of the insulation coating layer of the electric wire and the entire periphery of the terminal, it is not necessary to irradiate the entire surface with UV light, and only a part of the wire is irradiated with UV light. It can be cured in time.

In the ultraviolet curable resin, a polyisocyanate compound having two or more isocyanate groups has two or more hydroxyl groups of a polyol having two or more hydroxyl groups to form an ester bond with (meth) acrylate. An ultraviolet curing agent (A) whose main component is a polyol (meth) acrylate set to 1 or less,
A chain transfer agent (B) comprising a metal complex compound containing at least one compound selected from a urethane bond, a urea bond and an isocyanate group, and a metal-containing compound; and an ultraviolet polymerization initiator (C). When,
It consists of the composition which mix | blended.

The ultraviolet curable resin layer has a mass ratio of 90:10 to 60:40 of the polyisocyanate compound and the polyol (meth) acrylate in the ultraviolet curing agent (A), and has a hardness after ultraviolet irradiation. It is preferable to make it high.
When it is desired to lower the hardness after UV irradiation and to provide a region where flexibility is desired, the mixing ratio of the polyisocyanate compound and polyol (meth) acrylate in the UV curing agent (A) is 60 by mass. : 40 to 10:90 is preferable.
Further, the dark-curing ultraviolet curable resin has heat resistance that does not melt at 120 ° C. or lower after curing.

The dark part curable ultraviolet curable resin is characterized by blending the chain transfer agent (B). As the ultraviolet curable resin having dark part curable properties, an ultraviolet curable composition described in WO2012 / 102299 related to the prior application of the present applicant is suitably used.
The dark portion curable ultraviolet curable composition is made of an ultraviolet curable resin that can cure a portion that is located in a dark portion where irradiation light does not reach and does not generate radicals.
In addition, the whole can be reliably cured even when an ultraviolet / light transmission inhibitor composed of organic / inorganic fillers, carbon / metal particles, fibers, polymers / oligomers, various modifying additives and the like is blended.

  The UV curable resin having dark portion curable properties does not require heat treatment or moisture curing treatment, and when UV rays are irradiated and a part of the UV curable resin is cured, the dark portions where the ultraviolet rays are blocked are also sequentially transferred by the chain transfer agent. It can be cured, and the entire ultraviolet curable resin can be rapidly cured including the dark part. Specifically, for example, when UV irradiation is performed for 10 seconds with a UV lamp on an ultraviolet curable resin having dark-curing properties, the portion irradiated with the lamp is instantaneously cured and the light from the UV lamp does not reach. The dark part can be cured by leaving it for several tens of seconds.

Moreover, this invention provides the formation method of the terminal connection structure of the said electric wire terminal.
The forming method includes a resin coating container having a top wall and a bottom wall and a peripheral wall, which is composed of first and second divided containers that divide the bottom wall into two equal parts so as to be openable and closable. A jig with a wire insertion hole is provided at the center of the split end of the bottom wall,
With the terminal crimped and connected to the wire terminal, the wire crimping part of the terminal is inserted into the first divided container and the wire connected to the wire crimping part is positioned through the wire insertion hole,
Next, the other second divided container is assembled to the first divided container, the bottom wall and the peripheral wall are closed in an annular shape to form the resin application container,
Next, the dark-curing ultraviolet curable resin is injected from the upper surface opening of the resin coating container, and the lower wire crimping portion is immersed in the ultraviolet curable resin without contacting the upper electrical contact portion of the terminal. Let
Next, the surface of the ultraviolet curable resin is cured by irradiating ultraviolet rays from above the resin coating container, and the whole is cured by chaining the curing to the inner side, and the wire crimping portion of the terminal and the wire crimping The outer protective material is provided on the entire outer peripheral surface of the insulating coating layer of the electric wire in contact with the part,
Next, the second divided container of the resin application container is separated from the first divided container,
There is provided a method for forming a terminal connection structure of an electric wire terminal in which the electric wire covered with the exterior protective material is taken out from the first divided container.

  The method for forming the exterior protective material is not limited to the above method, and a dark portion curable ultraviolet curable resin is applied with a brush or roller from the wire crimping portion side of the terminal to the outer periphery of the terminal of the insulating coating layer of the covered wire. Then, it may be cured by irradiating with ultraviolet rays.

  The resin coating container comprising the first and second divided containers serving as the jig is provided with a release agent coating layer made of a fluorine resin on the inner peripheral surface, and the exterior protection formed by curing the ultraviolet curable resin. The material can be easily removed.

The resin application container used as the jig has a rectangular frame shape with an upper surface opening in a state where the second divided container is assembled to the first divided container.
The first divided container and the second divided container are formed by dividing the resin application container into two equal parts from an intermediate position of the bottom wall to the peripheral wall, or one side of the peripheral wall from a half side portion of the bottom wall of the resin application container. An L-shaped second divided container having an opened shape of the first divided container, a half side portion of the bottom wall closing the opening of the first divided container, and one side of the peripheral wall;
A U-shaped groove at the center of the divided end of the bottom wall of the first divided container is provided, and the U-shaped groove becomes a circular electric wire insertion hole in a state where the bottom wall of the second divided container is assembled.

  In addition, a guide portion for the second divided container is provided below the inner surface of the peripheral wall of the first divided container, and a release layer made of a fluororesin is provided on the inner surfaces of the first divided container and the second divided container. It is preferable that

  As described above, in the terminal connection structure of the electric wire terminal of the present invention, the terminal connection is made with the exterior protective material formed by applying the ultraviolet ray curable resin curable with the dark portion to the terminal connection portion of the electric wire terminal and then curing by irradiating the ultraviolet ray. Since the portion is externally protected, water can be stopped, vibration can be prevented from being directly applied to the terminal connecting portion, and disconnection and damage to the electric wire can be prevented. In addition, since the ultraviolet curable resin is made to be dark portion curable, when a part of the ultraviolet curable resin is irradiated with ultraviolet rays, the whole can be cured in a short time, and an exterior protective material can be formed easily and quickly. As a result, compared with the case where the protective part is formed by conventional molding, the equipment cost is not required, and the exterior protective part can be formed in a short time, so that the cost can be significantly reduced.

The 1st Embodiment of this invention is shown, (A) is a top view of the electric wire which connected the grounding terminal before providing an exterior protection material to the terminal, (B) is a top view in the state where the exterior protection material was provided, (C ) Is a perspective view of (B). (A) is sectional drawing of the electric wire which exposed the core wire, (B) is a front view of the state which crimped | bonded the ground terminal to the electric wire, (C) is a front view of the state which provided the exterior protection material. The jig | tool which consists of a resin application | coating container is shown, (A) is a perspective view of the state which opened the 1st division | segmentation container and the 2nd division | segmentation container, (B) is a right view of a 1st division | segmentation container, (C) is the 1st The top view of a division | segmentation container, (D) is a perspective view of the state which closed and assembled the 1st and 2nd division | segmentation container, (E) is a top view of (D). (A)-(H) are explanatory drawings of the process of making it harden | cure after apply | coating an ultraviolet curable resin to the terminal connection part of an electric wire with a resin application container, and forming an exterior protection material. It is drawing which shows a prior art example.

Hereinafter, embodiments of the present invention will be described with reference to the drawings.
Embodiments are shown in FIGS.
In the present embodiment, as shown in FIG. 1, the ground terminal 2 is connected to the end of the ground circuit wire 1 to be wired to the automobile, and the wire 1 in contact with the peeled end from the wire crimping portion 2 a of the ground terminal 2. A portion of the insulating coating layer that is applied to the outer peripheral surface is externally protected with an external protective material 3 formed by curing the ultraviolet curable resin 5.

The electric wire 1 is a thick electric wire having a conductor cross-sectional area of 8 mm ² or more. As shown in FIG. 2A, the insulation coating layer 1b is peeled off at the end of the electric wire 1 to expose the core wire 1a, and the core wire 1a is exposed. The ground terminal 2 is crimped to.

As shown in FIG. 1 and FIG. 2, the ground terminal 2 has the electric wire crimping portion 2a continuous with a part of the outer periphery of the electric contact portion 2b provided with a bolt hole 2h, and from both sides of the substrate 2k of the electric wire crimping portion 2a. A pair of core wire barrels 2c and insulating coating barrels 2d are provided in the width direction so as to be spaced apart in the length direction.
The ground terminal 2 and the electric wire 1 are connected by placing the exposed core wire 1a and the end of the electric wire on the wire crimping portion 2a of the ground terminal, and caulking and fixing the exposed core wire 1a with the core wire barrel 2c. In 2d, the outer peripheral surface of the insulating coating layer 1b in contact with the peeled end of the electric wire is caulked and fixed.
In addition, the core wire barrel and the insulation coating barrel may be one continuous wire barrel.

An electric wire 1 in which a ground terminal 2 composed of a bolt-tightened crimp terminal is crimped and connected to a terminal is continuous over the outer periphery of the wire crimping portion 2a of the ground terminal 2 and the outer periphery of the insulating coating layer 1b of the electric wire 1 continuous to the wire crimping portion 2a. Then, it is covered with the exterior protective material 3.
Specifically, the outer covering material 3 covers a tip 3a of the core wire 1a protruding from the crimped portion of the core wire barrel 2c, and the crimped portion covering portion 3b of the core wire barrel 2c and the insulating coating barrel 2d from the tip surface, A covering portion 3c on the outer periphery of the insulating coating layer 2b continuous to the crimped portion is included. The length 3L of the covering portion 3c of the electric wire of the exterior protective material 3 is not particularly limited. However, since the hardness of the external protective material 3 is relatively large, if the protection region of the external protective material 3 is increased, the electric wire Since the flexibility of 1 is impaired, it is set to about 10 mm to 30 mm.

  As described above, the exterior protection material 3 protects the exterior of the gap between the end surfaces of the core wire 1a of the electric wire 1 and the gap between the core wire 1a and the insulating coating layer 1b. In addition, since the exterior protective material 3 is formed by curing an ultraviolet curable resin, it is possible to reduce that the vehicle vibration is directly applied to the connection portion between the electric wire 1 and the ground terminal 2, and the electric wire at the connection portion is reduced. It prevents and prevents disconnection and damage.

The dark-curing ultraviolet curable resin 5 that forms the exterior protective material 3 will be described.
The ultraviolet curable resin 5 having dark part curability is made of an ultraviolet curable resin in which an ultraviolet curable material (A), a chain transfer agent (B), and an ultraviolet polymerization initiator (C) are blended.

  The chain transfer agent (B), which is a component of the ultraviolet curable resin 5 having dark part curability, includes (a) a compound containing at least one selected from a urethane bond, a urea bond, and an isocyanate group; b) It consists of a metal complex compound containing a metal-containing compound.

  The chain transfer agent (B) can exhibit intermolecular or intramolecular transmission functions after stabilizing the generated radicals. Therefore, the chain transfer agent (B) can instantaneously transmit the radicals generated in the system to a place where no radicals are generated, and the polymerization reaction can be started to advance the radical polymerization reaction. As a result, when the chain transfer agent (B) is blended with the ultraviolet curable material (A), the inside and the back side (that is, the dark part) where the irradiation light that has conventionally been difficult to cure cannot be surely cured. Can do. In addition, there is no need for an operation step of mixing a curing agent immediately before curing, a step of curing a dark part by heating or moisture curing after irradiation, etc., and the curing operation can be performed in a short time, and the curing workability is excellent. Yes.

In the chain transfer agent (B), the urethane bond, urea bond, and isocyanate group-containing compound of the component (a) are represented by the following (Formula 1) urethane bond part, the following (Formula 2) urea bond part, What is necessary is just to contain at least 1 sort (s) selected from the isocyanate group shown by the following (Formula 3) in 1 molecule or more.
(Formula 1) -NH-COO-
(Formula 2) -NH-CO-NH-
(Formula 3) -N = C = 0

The metal-containing compound (b) constituting the chain transfer agent (B) preferably contains at least one metal selected from tin, copper, zinc, cobalt and nickel. Among these, it is activated at a relatively high temperature (for example, a temperature of about 120 ° C.), and at room temperature, it is difficult to improve the curing rate in the dark part, so that the storage stability of the composition can be increased. From the viewpoint, a zinc-based metal complex compound or a copper-based metal complex compound is more preferable.
Specific examples of the metal-containing compound (b) include metal-containing compounds listed in paragraphs 0010 and 0154 of WO 2012/102299 relating to the prior application of the present applicant.

  In the chain transfer agent (B), the blending ratio of the above (a) and (b) is (a) :( b) = 100: 0.001 to 100: 10, preferably 100: 0.005 in mass ratio. Preferably it is 100: 5.

In the metal complex compound functioning as the chain transfer agent (B) composed of (a) and (b), the tin-based metal complex compound may be bis (2,4-pentanedionato) tin, dibutyltin bis ( Trifluoromethanesulfonate), dibutyltin diacetate, dibutyltin dilaurate, dibutyltin maleate, phthalocyanine tin (IV) dichloride, tetrabutylammonium difluorotriphenyltin, phthalocyanine tin (II), tributyl (2-pyridyl) tin, tributyl ( 2-thienyl) tin, tributyltin acetate, tributyl (trimethylsilylethynyl) tin, trimethyl (2-pyridyl) tin and the like.
Examples of copper-based metal complex compounds include bis (hexafluoroacetylacetonato) copper (II), bis (2,4-pentanedionato) copper (II), and bis (1,3-propanediamine) copper (II). Dichloride, bis (8-quinolinolato) copper (II), bis (trifluoro-2,4-pentanedionato) copper (II), bis (2-hydroxyethyl) dithiocarbamate copper (II), diethyldithiocarbamate copper, Copper (II) dimethyldithiocarbamate, copper (II) ethylenediaminetetraacetate, copper (II) phthalocyanine, copper (II) dichloro (1,10-phenanthroline), copper phthalocyanine, tetra-4-tert-butylphthalocyanine copper, Tetrakis (acetonitrile) copper (I) hexafluorophosphate, copper naphthenate, etc. It can gel.
Zinc-based metal complex compounds include bis [2- (2-benzothiazolyl) phenolato] zinc (II), bis [2- (2-benzoxazolyl) phenolato] zinc (II), bis (2-hydroxyethyl) ) Zinc (II) dithiocarbamate, bis (2,4-pentanedionato) zinc (II), bis (8-quinolinolato) zinc (II), bis (tetrabutylammonium) bis (1,3-dithiol-2- Thion-4,5-dithiolato) zinc complex, disodium zinc ethylenediaminetetraacetate, zinc dibenzyldithiocarbamate (II), zinc dibutyldithiocarbamate (II), zinc diethyldithiocarbamate, zinc dimethyldithiocarbamate, zinc phthalocyanine, naphthenic acid Zinc and the like can be mentioned.
Examples of cobalt-based metal complex compounds include bis (cyclopentadienyl) cobalt (III) hexafluorophosphate, [1,1′-bis (diphenylphosphino) ferrocene] cobalt (II) dichloride, and bis (hexafluoroacetyl). Acetonato) cobalt (II), (1R, 2R) -N, N′-bis [3-oxo-2- (2,4,6-trimethylbenzoyl) butylidene] -1,2-diphenylethylenediaminatocobalt ( II), (1S, 2S) -N, N′-bis [3-oxo-2- (2,4,6-trimethylbenzoyl) butylidene] -1,2-diphenylethylenediaminatocobalt (II), bis ( 2,4-pentanedionato) cobalt (II), bis (trifluoro-2,4-pentandionato) cobalt (II), lid Cyanine cobalt (II), disodium ethylenediaminetetraacetate, hexaamminecobalt (III) chloride, N, N′-disalicylic ethylenediamine cobalt (II), [5,10,15,20-tetrakis (4-methoxy) Phenyl) porphyrinato] cobalt (II), tris (2,4-pentanedionato) cobalt (III), cobalt naphthenate, and the like.
Nickel-based metal complex compounds include [1,2-bis (diphenylphosphino) ethane] nickel (II) dichloride, bis (dithiobenzyl) nickel (II), bis (hexafluoroacetylacetonato) nickel (II) Bis (2,4-pentanedionato) nickel (II), bis (tetrabutylammonium) bis (maleonitriledithiolato) nickel (II) complex, bis (tricyclohexylphosphine) nickel (II) dichloride, bis (tri Phenylphosphine) nickel (II) dichloride, bromo [(2,6-pyridindiyl) bis (3-methyl-1-imidazolyl-2-ylidene)] nickel bromide, disodium nickel (II) ethylenediaminetetraacetate, dibutyldithiocarbamic acid nickel II), such as diethyldithiocarbamate nickel may be mentioned.
The following are mentioned as a commercial item of the said metal complex compound.
BPDZ: [“Bis (2,4-pentanedionato) zinc (II)” manufactured by Tokyo Chemical Industry Co., Ltd.]
-CDEDTC: [Copper (II) diethyldithiocarbamate manufactured by Tokyo Chemical Industry Co., Ltd.]
DBTDL: [“Dibutyltin dilaurate” manufactured by Tokyo Chemical Industry Co., Ltd.]

  The ultraviolet curable material (A) has a hydroxyl group in which two or more hydroxyl groups of a polyol having two or more hydroxyl groups form an ester bond with (meth) acrylate with respect to a polyisocyanate compound having two or more isocyanate groups. It is preferable that the main component is a (meth) acrylate of a polyol whose number is set to 1 or less.

Since the number of hydroxyl groups in the (meth) acrylate of the polyol is set to 1 or less, the urethanization reaction with the polyisocyanate compound is suppressed from proceeding in a state where it is blended with the polyisocyanate compound. Thereby, the storage stability of this composition is improved. The number of hydroxyl groups in the (meth) acrylate of the polyol may be 1 or 0. From the viewpoint of storage stability of the present composition, it is more preferably 0.
Examples of the (meth) acrylate of the polyol include dipropylene glycol diacrylate, tetraethylene glycol diacrylate, 1-acryloyloxy-3-methacryloyloxy-2-propanol (2-hydroxy-3-acryloyloxypropyl methacrylate), and the like. preferable. Specific examples of the (meth) acrylate include those described in paragraph 0131 of the aforementioned WO2012 / 102299.
The following are mentioned as a commercial item of this (meth) acrylate.
・ DPGA: [Dipropylene glycol diacrylate manufactured by Tokyo Chemical Industry Co., Ltd.]
・ TEGDA: [“Tetraethylene glycol diacrylate” manufactured by Tokyo Chemical Industry Co., Ltd.]
AMPOH: [“1-acryloyloxy-3-methacryloyloxy-2-propanol (2-hydroxy-3-acryloyloxypropyl methacrylate)” manufactured by Tokyo Chemical Industry Co., Ltd.]
-IBA: [“Isobornyl acrylate” manufactured by Tokyo Chemical Industry Co., Ltd.]

Specific examples of the polyisocyanate compound having two or more isocyanate groups include aliphatic polyisocyanates, alicyclic polyisocyanates, araliphatic polyisocyanates, and aromatic polyisocyanates. Also, biuret type polyisocyanates obtained by reacting these polyisocyanates with water, adduct type polyisocyanates obtained by reacting these polyisocyanates with polyhydric alcohols such as trimethylolpropane, and some of these polyisocyanates. Examples thereof include liquid prepolymers polymerized with polyesters and polyether derivatives, and multimers obtained by converting these polyisocyanates to isocyanurates. These may be used alone or in combination of two or more.
The following are mentioned as a commercial item of the said polyisocyanate compound.
・ N3600: ["Death Module N3600" manufactured by Sumika Bayer Urethane Co., Ltd.]
・ N3200: ["Death Module N3200" manufactured by Sumika Bayer Urethane Co., Ltd.]
Moreover, the following UP-1 and UP-2 are mentioned as a synthetic | combination product of a urethane prepolymer.

The urethane prepolymer UP-1 is synthesized by the following method.
A reaction vessel equipped with a stirrer was charged with 80 parts by mass of polypropylene glycol having a number average molecular weight of 400, 40 parts by mass of hexamethylene diisocyanate and 0.1 parts by mass of dibutyltin dilaurate, and the liquid temperature was changed from room temperature to 50 ° C. while stirring. Raise over time. Thereafter, a small amount is sampled, and FT-IR is measured, and stirring is continued at 50 ° C. while confirming absorption of isocyanate near 2300 cm −1. The reaction ends when the absorption disappears. This is designated as urethane prepolymer UP-1.
The urethane prepolymer UP-2 is synthesized by the following method.
A reaction vessel equipped with a stirrer was charged with 50 parts by mass of a terminal diol-type polycaprolactone having a number average molecular weight of 1250, 13.5 parts by mass of hexamethylene diisocyanate and 0.1 parts by mass of dibutyltin dilaurate, and the liquid temperature was adjusted to room temperature while stirring. To 50 ° C over 1 hour. Thereafter, a small amount is sampled, and FT-IR is measured, and stirring is continued at 50 ° C. while confirming absorption of isocyanate near 2300 cm −1. The reaction ends when the absorption disappears. This is designated as urethane prepolymer UP-2.

  In the ultraviolet curable material (A), the blending ratio of the polyisocyanate compound and the (meth) acrylate of the polyol is 90:10 to 10:90, preferably 80:20 to 20:80, in terms of mass ratio. When the blending amount of the (meth) acrylate of the polyol exceeds 90 by mass ratio, the amount of the polyisocyanate compound responsible for the curing reaction in the dark part becomes insufficient because the blending amount of the polyisocyanate compound is too large. The curing rate tends to be slow. On the other hand, even if the blending amount of the (meth) acrylate of the polyol is less than 10 by mass ratio, the generation amount of active species for curing the polyisocyanate compound is insufficient, and the curing rate in the dark part tends to be slow.

The hardness of the UV curable resin 5 after UV curing varies depending on the blending ratio of the polyisocyanate compound and the (meth) acrylate of the polyol, and becomes hard when the blending ratio of the polyisocyanate compound is high. ) When the blending ratio of acrylate is high, it becomes soft.
In this embodiment, in order to increase the hardness after ultraviolet curing, the ultraviolet ray curable resin 4A has a mass ratio of 90:10 to 60:40 of the polyisocyanate compound and the polyol (meth) acrylate.

  The blending ratio of the ultraviolet curable material (A) and the chain transfer agent (B) is preferably a mass ratio of (A) :( B) = 90: 10 to 10:90. Specifically, the (meth) acrylate of the ultraviolet curable material (A) is 50 to 70 mass%, preferably 55 to 65 mass%, and the chain transfer agent (B) is 50 to 30 mass%, preferably 45 to 45 mass%. 35% by mass.

The ultraviolet polymerization initiator (C) is used for the purpose of causing radical reaction of (meth) acrylate of polyol. The ultraviolet polymerization initiator (C) is not particularly limited as long as it is a compound that absorbs ultraviolet rays and initiates a radical reaction. Examples of the ultraviolet polymerization initiator (C) include those described in paragraph 0133 of WO2012 / 102299, such as 1-hydroxycyclohexyl phenyl ketone and 2-tail anthraquinone.
Examples of the commercially available ultraviolet polymerization initiator (C) include IRGACURE 184, 369, 651, 500, 907, CGI 1700, CGI 1750, CGI 1850, CG 24-61; (Manufactured by UCB).

  As a compounding quantity of the said ultraviolet-ray polymerization initiator (C), it is preferable to exist in the range of 0.01-10 mass parts with respect to 100 mass parts of said ultraviolet curing materials (A). More preferably, it is the range of 0.1-7 mass parts. When the blending amount of the ultraviolet polymerization initiator is less than 0.01 parts by mass, the amount of the ultraviolet polymerization initiator is too small and the curing reaction by ultraviolet rays is difficult to start. On the other hand, when the blending amount of the ultraviolet polymerization initiator exceeds 10 parts by mass, an insoluble material is generated, and the physical properties of the cured product may be impaired.

  In addition to the various components described above, various compounding agents can be blended with the ultraviolet curable resin 5 as necessary, in a range that does not impair the object of the present invention. As a compounding agent, the stabilizer, plasticizer, softener, pigment, dye, antistatic agent, flame retardant, adhesiveness imparting agent, sensitizer, dispersion described in paragraphs 0117 to 0126 of the above-mentioned WO2012 / 102299 Agents, solvents, antibacterial and antifungal agents. Each compounding agent can be used in combination as appropriate. Moreover, the compounding quantity of a compounding agent can be suitably determined according to a use etc.

  The method for producing the ultraviolet curable resin is not particularly limited, but each of the above components is sufficiently kneaded by using a stirring device such as a mixing mixer under a reduced pressure or an inert gas atmosphere such as nitrogen and uniformly dispersed. The method of making it preferable is.

  A method of forming the exterior protective material 3 at the connection portion between the electric wire 1 and the ground terminal 2 using the dark portion curable ultraviolet curable resin 5 will be described below.

A resin application container 10 shown in FIGS. 3A to 3E is used as a jig.
The resin application container 10 is composed of a first divided container 12 and a second divided container 13 that are connected in an openable / closable manner, and the first and second divided containers 12 and 13 are assembled with the bottom wall and the peripheral wall closed, The resin coating container 10 is a rectangular box having an opening 10a on the upper surface and a bottom wall 10b and a peripheral wall 10c.

The first divided container 12 has a shape in which a half side portion of the bottom wall 10b of the resin coating container 10 and one side of the peripheral wall are opened, and a shape having a bottom wall 12a on the other half side and peripheral walls 12b, 12c, and 12d on three sides. Yes. A U-shaped groove 12e is provided at the center of the divided end of the bottom wall 12a, and a guide projection 12f is provided opposite to the lower inner surfaces of the peripheral walls 12b and 12c sandwiching the bottom wall opening.
On the other hand, the 2nd division container 13 is made into the L shape which covers the one side of the surrounding wall 10c from the half side part of the bottom wall 10b as said opening, and consists of the bottom wall 13a and the surrounding wall 13b.
Release layers 12 s and 13 s made of fluororesin are provided on the bottom walls and the inner surfaces of the peripheral walls of the first and second divided containers 12 and 13.

  Next, the process of providing the exterior holding material 3 on the electric wire whose ground terminal is connected to the terminal will be described with reference to FIGS. The resin application container 10 including the first and second divided containers 12 and 13 is disposed on a work table for wire harness assembly, for example, and an ultraviolet irradiation lamp 15 (see FIG. 4 (G)) is formed on the work table. (Shown) is also arranged.

  First, the resin container 10 is set on the work table with the second container 13 removed from the first container 12.

  In this state, as shown in FIGS. 4 (A) and 4 (B), the ground terminal 2 connected to the end of the electric wire 1 has the electric contact portion 2b as the upper side, the electric wire crimping portion 2a as the lower side, and the first divided container 12 The electric wire 1 that is inserted laterally from the opened peripheral wall and continues to the electric wire crimping portion 2a is passed through the U-shaped groove 12e provided in the bottom wall 12a, and the electric wire 1 is lowered below the first divided container 12.

  Next, as shown in FIGS. 4C and 4D, the second divided container 13 is assembled so that the opening of the first divided container 12 is closed. At that time, both sides of the bottom wall 13a of the second divided container 13 are fitted and inserted into the guide protrusion 12f of the first divided container 12, and the second divided container 13 is inserted into the divided end surface of the bottom wall 12a of the first divided container. The division | segmentation end surface of the bottom wall 13a is abutted. In this state, the opening of the U-shaped groove 12e into which the electric wire 1 is inserted is closed to the divided end surface of the bottom wall 13a of the second divided container 13, and the electric wire insertion hole 10h in which the inner peripheral surface is substantially in close contact with the outer periphery of the electric wire 1; Become. And it fits into the surrounding wall opening of the 1st division container 12 of the surrounding wall 13b of the 2nd division container 13, and a surrounding wall is continued cyclically | annularly.

  As described above, the ground terminal 2 connected to the terminal of the electric wire 1 is inserted into the resin coating container 10 formed by assembling the first and second divided containers, and the electric wire 1 continuous to the ground terminal 2 is inserted. The length of 10 mm to 30 mm is drawn from the bottom wall 10 b with the resin application container 10 inserted.

  Next, as shown in FIG. 4F, the dark-curing ultraviolet curable resin 5 having a viscosity that maintains fluidity but does not easily leak is poured into the resin coating container 10 from the supply container 14. The injection amount is such that the wire crimping portion 2a and the wire 1 of the ground terminal 2 are immersed in the ultraviolet curable resin 5, but are injected to such a height that the ultraviolet curable resin 5 does not contact the electrical contact portion 2b above the ground terminal.

  The UV curable resin 5 having viscosity injected into the resin application container 10 is brought into close contact with the outer peripheral surface of the electric wire 1 passing through the electric wire insertion hole 10h of the bottom wall 10b. The ultraviolet curable resin 5 has a viscosity of almost no fluidity, and the surface tension is increased at a portion surrounding the wire insertion hole 10h. From the end of the wire insertion hole 10h and the bottom walls 12a and 13a, The ultraviolet curing resin 5 is prevented from leaking.

Next, as shown in FIG. 4G, the ultraviolet ray curable resin 5 in the resin coating container 10 is irradiated with ultraviolet rays by an ultraviolet ray irradiation lamp 15. The surface of the ultraviolet curable resin 5 irradiated with ultraviolet rays is cured, and the curing is chained to the inner side to be entirely cured, resulting in a cured ultraviolet curable resin 5H.
As described above, when a part of the dark-curing ultraviolet curable resin 5 is irradiated with ultraviolet rays from the outside, the directly irradiated part is cured, and the curing is transferred in a chain and the irradiated light is blocked. The entire ultraviolet curable resin including the inside where the irradiation light does not reach and the back surface opposite to the irradiation side can be cured. Specifically, the whole can be cured by leaving it alone for several tens of seconds by irradiating a part of the ultraviolet curable resin 5 in the resin coating container 10.

  When the entire ultraviolet curable resin 5 in the ultraviolet coating container 110 is cured and the exterior protective material 3 is formed, the second divided container 13 is moved relative to the first divided container 12 as shown in FIG. Open and remove. At that time, since the release layer 13s is provided on the entire inner surface of the second divided container 13, the second divided container 13 can be smoothly separated and removed from the cured ultraviolet curable resin 5H, that is, the exterior protective material 3. .

Subsequently, the electric wire 1 with the ground terminal protected by the exterior protective material 3 is taken out from the peripheral wall of the first divided container 12 opened by removing the second divided container 13 to the outside.
The drawn-out electric wire with ground terminal 1 is in a state in which the terminal connection portion shown in FIGS. 1B and 1C is externally protected by the external protective material 3.

  The present invention is not limited to the above embodiment, and the resin coating container used as a jig may be divided into two to form the first and second divided containers. Moreover, you may apply | coat the said dark part curable ultraviolet curing resin to the terminal connection part of an electric wire by brush etc., without using a resin application | coating container. And the terminal connected to an electric wire terminal is not limited to the earth terminal of the said bolt fastening.

DESCRIPTION OF SYMBOLS 1 Electric wire 1a Core wire 1b Insulation coating layer 2 Ground terminal 2a Wire crimping part 2b Electrical contact part 3 Exterior protection material 5 Dark part curable ultraviolet curable resin 10 Resin application container 12 First division container 13 Second division container

Claims (4)

In the terminal connection structure of the electric wire terminal where the terminal is crimped and connected by crimping the barrel to the exposed core wire by peeling off the insulating coating layer at the end of the electric wire,
The exterior protection that is cured by irradiating ultraviolet rays after applying a dark-curing ultraviolet curable resin over the insulating coating layer in contact with the peeled end of the electric wire from the exposed portion of the wire crimping portion excluding the electrical contact portion of the terminal The terminal connection structure of the electric wire terminal characterized by providing the material. The electric wire is a thick electric wire having a conductor cross-sectional area of 8 mm ² or more used for a power supply circuit and / or a ground circuit arranged in a vehicle, and the terminal to be crimped and connected to the electric wire terminal is an electric contact provided with a bolt hole. The electric wire terminal according to claim 1, wherein the electric terminal is a bolt fastening terminal in which an electric wire crimping portion protruding from the barrel is continuously provided at the portion, and the bolt fastening terminal is connected to the bus bar or / and the vehicle body panel by bolt fastening. Terminal connection structure. The dark part curable ultraviolet curable resin is:
With respect to a polyisocyanate compound having two or more isocyanate groups, the number of hydroxyl groups was set to 1 or less by forming two or more hydroxyl groups of a polyol having two or more hydroxyl groups to form an ester bond with (meth) acrylate. An ultraviolet curing agent (A) mainly composed of a (meth) acrylate of a polyol;
A chain transfer agent (B) comprising a metal complex compound containing at least one compound selected from a urethane bond, a urea bond and an isocyanate group, and a metal-containing compound; and an ultraviolet polymerization initiator (C). When,
The terminal connection structure of the electric wire terminal of Claim 1 or Claim 2 which consists of a composition which mix | blended. It is a formation method of the terminal connection structure of the electric wire end according to any one of claims 1 to 3,
A resin coating container having a top wall and a bottom wall and a peripheral wall is constituted by first and second divided containers that are bisected and connected to be freely opened and closed, and a divided end of the bottom wall of the divided container A jig with a wire insertion hole is provided in the center of
With the terminal crimped and connected to the wire terminal, the wire crimping part of the terminal is inserted into the first divided container and the wire connected to the wire crimping part is positioned through the wire insertion hole,
Next, the other second divided container is assembled to the first divided container, the bottom wall and the peripheral wall are closed in an annular shape to form the resin application container,
Next, the dark-curing ultraviolet curable resin is injected from the upper surface opening of the resin coating container, and the lower wire crimping portion is immersed in the ultraviolet curable resin without contacting the upper electrical contact portion of the terminal. Let
Next, the surface of the ultraviolet curable resin is cured by irradiating ultraviolet rays from above the resin coating container, and the whole is cured by chaining the curing to the inner side, and the wire crimping portion of the terminal and the wire crimping The outer protective material is provided on the entire outer peripheral surface of the insulating coating layer of the electric wire in contact with the part,
Next, the second divided container of the resin application container is separated from the first divided container,
The formation method of the terminal connection structure of the electric wire terminal which takes out the said electric wire coat | covered with the said exterior protection material from the said 1st division | segmentation container.

Images