JP2014117075A - Water cut-off agent, electric wire with ground terminal and manufacturing method thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a water cut-off agent which is sufficiently hardened even in a location where there is no light, and capable of easily obtaining water cut-off performance without requiring facilities, time and the like for hardening, the water cut-off agent using a photocurable resin used for water cut-off between a ground terminal of an electric wire with the ground terminal and a ground terminal connection part of an electric wire for grounding, an electric wire with a ground terminal and a manufacturing method thereof.SOLUTION: An electric wire 1 with a ground terminal is manufactured by using a water cut-off agent 13 which can be hardened in a location where there is no light and contains a photocurable resin and a chain transfer agent, applying the water cut-off agent to a ground terminal connection part 11 of the electric wire 1 with a ground terminal connecting a ground terminal 3 to a terminal of an electric wire 2 for grounding, hardening the water cut-off agent 13, and performing water cut-off processing on the ground terminal connection part 11.

Description

  The present invention relates to a water-stopping agent, an electric wire with a ground terminal, and a method for manufacturing the same, and more particularly to a water-stopping agent that is excellent in water-stopping and suitable for in-vehicle use, and an electric wire with a ground terminal and a method for manufacturing the same.

  As for the electric wire with a grounding terminal, the grounding terminal is connected and fixed to the end of the grounding electric wire. The electric wire with the ground terminal is connected to an appropriate ground part (for example, a vehicle body) in a state where the ground terminal fixed to the terminal is exposed. Therefore, it is easy for water to enter from the end of the ground wire through the inside of the wire coating. Therefore, if water enters the circuit through the inside of the covering material, the normal operation of the circuit may be hindered. Therefore, conventionally, a water-stop treatment using a resin water-stopper has been applied to the connection between the wire and the terminal. It had been.

  Use a liquid waterproofing agent for the connection part of the wire with a grounding terminal from the viewpoint of ease of application and handling, and apply it to the relevant part, soak it, and let it harden to maintain its shape. . When the resin used for the water-stopping agent is classified according to the curing mechanism, a thermosetting type, a moisture curable type, an ultraviolet (light) curable type, and the like can be given.

  Among these curing mechanisms, when UV curable resin is used for the grounding terminal connection of the grounding wire, the gap between the wires of the wire does not reach the UV and the resin is uncured, so it stops sufficiently. There is a problem that water cannot be used.

  Therefore, it is known to use a water-stopper having a composite curing mechanism obtained by adding another curing mechanism to ultraviolet curing, such as an ultraviolet curable thermosetting type and an ultraviolet curable anaerobic curing type (for example, patents). Reference 1).

JP 2007-305525 A

  However, when the water stop agent having the conventional composite curing mechanism is used, there is a problem that it takes equipment and time to cure the water stop agent.

  Therefore, the problem to be solved by the present invention is that the irradiation light does not reach the water-stopping agent using the photocurable resin used for water-stopping of the ground terminal of the wire with the ground terminal and the ground terminal connection portion of the ground wire. To provide a water stopping agent, an electric wire with a ground terminal, and a method for manufacturing the same, which can sufficiently cure even at a place and can easily obtain a water stopping performance without requiring equipment or time to be cured. It is in.

In order to solve the above problems, the water-stopping agent of the present invention is
In the photo-curing water-stopping agent used for water-stopping of the ground terminal connection part of the wire with the ground terminal in which the ground terminal is connected to the terminal of the grounding wire,
The gist of the water-stopping agent is that it can be cured at a place where light does not reach and contains a photocurable resin and a chain transfer agent.

  In the water blocking agent, the chain transfer agent comprises (a) a compound containing at least one selected from a urethane bond, a urea bond and an isocyanate group as a component; and (b) a metal-containing compound as a component. It is preferable to have.

  In the water-stopping agent, the component (b) of the chain transfer agent is preferably a metal compound containing at least one metal selected from tin, copper, zinc, cobalt, and nickel.

The electric wire with an earth terminal of the present invention is an electric wire with an earth terminal in which the earth terminal connecting portion of the electric wire with the earth terminal connected to the terminal of the earth wire is covered with a water stop agent.
The gist of the invention is that the ground terminal connecting portion is covered with the water-stopping agent described above.

  The method for manufacturing an electric wire with a ground terminal according to the present invention is capable of curing a portion where light does not reach in the ground terminal connection portion of the electric wire with the ground terminal in which the ground terminal is connected to the end of the grounding wire. The gist of the invention is to use a water-stopping agent containing a water-soluble resin and a chain transfer agent, cure the water-stopping agent, and water-stop the earth terminal connection portion.

  The water-stopping agent of the present invention can be cured at a place where light does not reach, and by containing a photocurable resin and a chain transfer agent, it can be sufficiently cured and cured even at a place where irradiation light does not reach. Therefore, it is possible to easily obtain the water stopping performance without requiring equipment or time.

  An electric wire with an earth terminal according to the present invention is an electric wire with an earth terminal in which an earth terminal connection portion of an electric wire with an earth terminal is covered with a water-stopping agent. Since the part is covered with the water-stopping agent described above, it can be sufficiently cured even in a place where the irradiation light does not reach, and easily obtains water-stopping performance without requiring equipment or time to cure. It is possible.

  The method for manufacturing an electric wire with a ground terminal according to the present invention is capable of curing a portion where light does not reach in the ground terminal connection portion of the electric wire with the ground terminal in which the ground terminal is connected to the end of the grounding wire. By using a water-stopping agent containing a water-soluble resin and a chain transfer agent, and a method of hardening the water-stopping agent and water-stopping the ground terminal connection, it is possible to cure the equipment and time. Therefore, it is possible to easily manufacture an electric wire with a ground terminal that is sufficiently cured even in a place where the irradiation light does not reach, and has a good water stop performance.

FIG. 1 is a plan view showing an example of an electric wire with a ground terminal according to the present invention. FIG. 2 is a front view of the electric wire with the ground terminal of FIG. The figure is a sectional view taken along line BB in FIG.

  Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings. FIG. 1 is a plan view showing an example of an electric wire with a ground terminal of the present invention, and FIG. 2 is a front view of the electric wire with an earth terminal of FIG. In addition, the earth terminal connection part 11 of FIG.1 and FIG.2 is shown in the state which saw through the water stop agent 13. FIG. In the electric wire 1 with an earth terminal shown in FIGS. 1 and 2, the earth terminal 3 is connected and fixed to the end of the earth wire 2.

  The grounding wire 2 has a conductor 4 and a covering material 5 made of an insulator covering the periphery of the conductor 4. One end of the grounding wire 2 is removed by peeling off the covering material 5 and the conductor 4 is exposed. This terminal is fixed by being crimped to the ground terminal 3.

  The ground terminal 3 is formed by bending a metal plate or the like. For example, an earth connection portion 7 used for connection to a vehicle body earth or the like, and an earth wire connected to the earth connection portion 7 are connected. It is comprised from the crimping | compression-bonding part 8 for fixing.

  The crimping portion 8 includes a conductor crimping portion 9 for crimping the conductor of the grounding wire and an insulation barrel 10 for crimping the covering material 5 of the grounding wire. The ground wire 2 is connected and fixed to the ground terminal 3 by crimping the conductor 4 and the covering material 5 of the ground wire 2 to the conductor crimping portion 9 and the insulation barrel of the ground terminal 2, respectively. A connection portion where the ground terminal 3 and the ground wire 2 are in contact is formed as a ground terminal connection portion 11.

  The ground connection portion 7 is provided with a through hole 12 through which a bolt or the like can be inserted. The electric wire 1 with a ground terminal is fastened to an appropriate ground portion of the vehicle by a bolt or the like through the through hole 12. The conductor 4 of the ground wire 2 is connected to the vehicle ground via the ground terminal 3. On the other hand, the other end of the wire 1 with a ground terminal is connected to a circuit or the like for the conductor 4 to be grounded.

  In the grounding wire 2, the conductor crimping part 9 and the insulation barrel 10 are crimped at the crimping part of the grounding terminal 8. In the ground terminal connection portion 11 in which the ground wire 2 is connected to the ground terminal 3, the portion where the conductor-terminal connection portion is exposed is covered with a cured product obtained by curing the water stop agent 13. Processing has been applied.

  The water-stop agent 13 covers at least the gap between the conductor 4 and the covering material 5, and water enters the ground wire 2 from the gap between the conductor 4 and the covering material 5. It is preventing. The water stop agent 13 is cured in a state of being in close contact with the surface of the covering material 5 of the grounding electric wire 2 adjacent to the exposed portion of the conductor 4.

  3 is a cross-sectional view taken along line BB in FIG. As shown in FIG. 3, the water-stopping agent 13 is cured in a state where it penetrates into the conductor 4. Further, the water-stopping agent 13 is cured in a state where it penetrates into the inside of the covering material 5. The length L of the region into which the water-stopping agent 13 has penetrated is preferably 3 mm or more, and more preferably in the range of 10 to 25 mm. Thus, the inside of the conductor 4 in which the water-stopping agent 13 has permeated and the portion inside the coating material are places where the irradiation light for curing does not reach. On the other hand, the water-stopping agent of the present invention can be cured at a place where irradiation light for curing does not reach and is composed of a composition containing a photocurable resin and a chain transfer agent. Therefore, it can be reliably cured. Hereinafter, the water-stopping agent of the present invention will be described in detail.

  The photocurable resin can be used as long as a cured product can be obtained by irradiation with light such as ultraviolet rays. In addition to the ultraviolet rays, the photocurable resin includes those from which a cured product can be obtained by visible light, infrared rays, or the like.

  As the photocurable resin, for example, an ultraviolet curable material can be used. As the ultraviolet curable material, an existing ultraviolet curable material can be used. Specifically, a mixture of a curable monomer such as (meth) acrylate, an oligomer, and the like and a photopolymerization initiator is used as a basic composition, and it can be used if a cured product can be obtained by irradiation with ultraviolet rays. it can. In the present invention, the description of “(meth) acrylate” means acrylate and / or methacrylate.

  The curing principle of the ultraviolet curable material is that the photopolymerization initiator absorbs ultraviolet rays (ultraviolet light) to generate active species such as radical species, and the active species is a carbon-carbon double layer such as (meth) acrylate. The bond is radically polymerized and cured. The UV curable material is uncured in the area where UV rays are shielded by normal UV curing. However, by adding a chain transfer agent, radicals generated by UV irradiation can be shielded from UV rays. The polymerization reaction can be started by transmitting to a portion that is not present, and the portion that is shielded from ultraviolet rays can be cured.

  As said (meth) acrylate compound, if it is a compound which has a 1 or more (meth) acrylate group in a molecule | numerator, it will not restrict | limit in particular and a conventionally well-known thing can be used. Specific examples of the (meth) acrylate compound include isobornyl (meth) acrylate, bornyl (meth) acrylate, tricyclodecanyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, and cyclohexyl. (Meth) acrylate, (meth) acrylic acid, benzyl (meth) acrylate, 4-butylcyclohexyl (meth) acrylate, (meth) acryloylmorpholine, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, octyl (meth) acrylate , Isooctyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, Isostearyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, methoxyethylene glycol (meth) acrylate, ethoxyethyl (meth) acrylate, methoxypolyethylene glycol ( (Meth) acrylate, methoxypolypropylene glycol (meth) acrylate, polyoxyethylene nonylphenyl ether acrylic , Diacetone (meth) acrylamide, isobutoxymethyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, t-octyl (meth) acrylamide, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, Mono (meth) acrylates such as 7-amino-3,7-dimethyloctyl (meth) acrylate, N, N-diethyl (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide, butanediol di (meth) ) Acrylate, hexanediol di (meth) acrylate, nonanediol di (meth) acrylate, decanediol di (meth) acrylate, 2-butyl-2-ethyl-1,3-propanediol di (meth) acrylate, 2-hydroxy − 3-acryloyloxypropyl methacrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, tricyclodecane dimethylol Di (meth) acrylate, 1,4-butanepolyol di (meth) acrylate, 1,6-hexanepolyol di (meth) acrylate, neopentyl glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (Meth) acrylate, 9,9-bis [4- (2-acryloyloxyethoxy) phenyl] fluorene, polyester di (meth) acrylate, tris (2-hydroxyethyl) iso Anurate tri (meth) acrylate, tris (2-hydroxyethyl) isocyanurate di (meth) acrylate, tricyclodecane dimethylol di (meth) acrylate, EO adduct of bisphenol A di (meth) acrylate, EO of hydrogenated bisphenol A Di (meth) acrylate of polyol of adduct or PO adduct, epoxy (meth) acrylate obtained by adding (meth) acrylate to diglycidyl ether of bisphenol A, triethylene glycol divinyl ether, trimethylolpropane tri (meth) Acrylate, pentaerythritol tri (meth) acrylate, trimethylolpropane EO adduct tri (meth) acrylate, trisacryloyloxyethyl phosphate, pentaerythritol tetra (Meth) acrylate, tetrafurfuryl alcohol oligo (meth) acrylate, ethyl carbitol oligo (meth) acrylate, 1,4-butanediol oligo (meth) acrylate, 1,6-hexanediol oligo (meth) acrylate, trimethylolpropane Examples thereof include poly (meth) acrylates such as oligo (meth) acrylate, pentaerythritol oligo (meth) acrylate, (poly) urethane (meth) acrylate, and (poly) butadiene (meth) acrylate. These may be used individually by 1 type and may use 2 or more types together.

  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, ethyl anthraquinone, triphenylamine, carbazole, 3 -Methylacetophenone, 4-chlorobenzophenone, 4,4'-dimethoxybenzophenone, 4,4'-diaminobenzophenone, Michler's ketone, benzoin propyl ether, benzoin ethyl ether, benzyl dimethyl ketal, 1- (4-isopropylphenyl) -2- Hydroxy-2-methylpropan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, thioxanthone, diethylthioxanthone, 2-isopropylthiol 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.

  As the photopolymerization initiator, commercially available products such as IRGACURE 184, 369, 651, 500, 907, CGI 1700, CGI 1750, CGI 1850, CG 24-61; Darocur 1116, 1173, Lucirin TPO (above, manufactured by BASF), Ubekrill P36 (UCB) Etc.) can be used.

  The chain transfer agent is a compound having at least one selected from a urethane bond, a urea bond and an isocyanate group as component (a) in the molecule and having a nitrogen atom and an oxygen atom (hereinafter, one or more urethanes). And a metal-containing compound as a component (b). By adding the chain transfer agent to the radically polymerizable material, the chain transfer agent can be instantaneously transmitted to a place where no radical is generated, and the polymerization reaction can be started and advanced.

The compound containing one or more urethane bonds, urea bonds and isocyanate groups of the component (a) includes a urethane bond part represented by the following (formula 1), a urea bond part represented by the following (formula 2), and the following (formula 3 As long as at least one selected from the isocyanate groups represented by (1) is contained in one molecule, any conventionally known one can be used without any particular limitation.

(Formula 1)
-NH-COO-
(Formula 2)
-NH-CO-NH-
(Formula 3)
-N = C = O

Specific examples of the compound containing one or more urethane bonds, urea bonds, and isocyanate groups as the component (a) include various polyurethanes, various polyureas, and isocyanate-containing compounds. The above-mentioned various polyurethanes and various polyureas are obtained by reacting the following isocyanate-containing compounds, hydroxyl (—OH) -containing compounds, amine (—NH ₂ ) -containing compounds, and the like.

  The isocyanate-containing compound can be used as it is as a compound containing an isocyanate group of the above (formula 3), or it can be used as various polyurethanes or various polyureas by reacting with a hydroxyl group-containing compound or amine-containing compound shown below. it can.

  Examples of the isocyanate-containing compound include the following compounds. Methylene diisocyanate, ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), dodecamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, lysine diisocyanate (LDI), 1,3,6-hexamethylene triisocyanate, etc. Aliphatic isocyanate. Hydrogenated-4,4′-diphenylmethane diisocyanate (hydrogenated MDI), hydrogenated-xylylene diisocyanate (hydrogenated XDI), 1,4-cyclohexane diisocyanate, hydrogenated-2,4-tolylene diisocyanate (hydrogenated TDI) , Cycloaliphatic isocyanates such as isophorone diisocyanate (IPDI) and norbornene diisocyanate (NBDI). Aromatic aliphatic isocyanates such as xylylene diisocyanate (XDI) and tetramethylxylylene diisocyanate (TMXDI); 1,4-diphenyl diisocyanate, 2,4 or 2,6-tolylene diisocyanate (TDI), 2,4 or 4,4-diphenylmethane diisocyanate (MDI), 1,5-naphthalene diisocyanate (NDI), 3,3 ′ -Polyisocyanates such as aromatic isocyanates such as dimethyl-4,4'-diphenylmethane diisocyanate, O-tolidine diisocyanate, polyphenylmethane polyisocyanate (crude MDI), triphenylmethane triisocyanate, tris (isocyanatephenyl) thiophosphate. Examples of the isocyanate-containing compound include biuret-type polyisocyanates obtained by reacting these polyisocyanates with water, adduct-type polyisocyanates obtained by reacting with polyhydric alcohols such as trimethylolpropane, and some of the polyisocyanates are polyesters. Examples include liquid prepolymers polymerized with polyether derivatives, multimers obtained by isocyanuration, and the like. These may be used alone or in combination of two or more.

  Examples of the hydroxyl group-containing compound to be reacted with the isocyanate-containing compound in order to obtain various polyurethanes include alcohols having 1 to 30 carbon chains having a hydroxyl group at the terminal, (poly) ethylene glycol as the terminal diol, (poly) propylene glycol as the terminal diol, (Poly) hexamethylene glycol of terminal diol, (poly) caprolactone of terminal diol, (poly) ester (poly) ol of terminal diol, (poly) amide of terminal diol, (poly) ester of terminal diol, and the like.

  Various polyurethanes need only be dissolved or suspended when finally mixed in the curable material, so it is not always necessary to be in a liquid state. The hydroxyl group-containing compound used at this time is preferably a liquid compound having a molecular weight of 100,000 or less.

  As amine-containing compounds to be reacted with isocyanate-containing compounds to obtain various polyureas, amines having 1 to 30 carbon chains having a primary or secondary amino group at the terminal, (poly) ethylene glycol of terminal diamine, terminal (Poly) propylene glycol of diamine, (poly) hexamethylene glycol of terminal diamine, (poly) caprolactone of terminal diamine, (poly) ester (poly) ol of terminal diamine, (poly) amide of terminal diamine, ( And poly) esters.

  Various polyureas need only be dissolved or suspended when finally mixed with the curable material, so it is not always necessary to be in a liquid state, but it is preferably in a liquid state for ease of mixing, The amine-containing compound used at this time is preferably a liquid compound having a molecular weight of 100,000 or less.

  In addition, the polyurethane and polyurea compounds may have an alkyl group or a terminal group after polymerization by (thio) ether, (thio) ester, amide, (thio) urethane, (thio) urea, N-alkyl bond, etc., if necessary. Sealed with (meth) acrylic group, epoxy group, oxazolyl group, carbonyl group, thiol group, thioether group, thioester group, phosphoric acid (ester) group, phosphonic acid (ester) group, carboxylic acid (ester) group, etc. May be.

  The urethane bond, urea bond, and isocyanate group may be contained in the molecule by combining a plurality of types or by combining terminal groups.

  The metal of the metal-containing compound of component (b) that is combined with the compound containing one or more urethane bonds, urea bonds or isocyanate groups to constitute a chain transfer catalyst includes tin, copper, zinc, cobalt, and nickel. One kind or a plurality of kinds of metals selected from are preferably used. The metal-containing compound of component (b) is not particularly limited as long as one or more of the above metals are contained in the constituent molecules in the form of metal salts or complexes, and those conventionally known are used. Can be used.

  Examples of the metal salt include metal salt forms such as carboxylate, phosphate, sulfonate, hydrochloride, bromate, and (per) (sub) chlorate of the metal species.

  The metal complex is not particularly limited as long as it is coordinated and stabilized with an organic ligand capable of forming a coordination bond with the metal species and 1: 1 to 1: 4 (metal: ligand). A well-known thing can be used without this.

  Specific examples of the metal-containing compound of the component (b) include 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, bis (hexafluoroacetylacetonato) copper (II), bis (2,4-pentanedionato) copper (II), bis (1,3-propanediamine) copper (II) dichloride, bis (8- Quinolinolato) copper (II), bis (trifluoro-2,4-pentanedionato) copper (II), bis (2-hydroxyethyl) dithiocarba Copper (II) phosphate, copper diethyldithiocarbamate, copper (II) dimethyldithiocarbamate, disodium ethylenediaminetetraacetate (II), copper (II) phthalocyanine, dichloro (1,10-phenanthroline) copper (II), phthalocyanine Copper, tetra-4-tert-butylphthalocyanine copper, tetrakis (acetonitrile) copper (I) hexafluorophosphate, copper naphthenate, bis [2- (2-benzothiazolyl) phenolato] zinc (II), bis [2- ( 2-Benzoxazolyl) phenolato] zinc (II), zinc (II) bis (2-hydroxyethyl) dithiocarbamate, bis (2,4-pentanedionato) zinc (II), bis (8-quinolinolato) zinc (II), bis (tetrabutylammonium) bis (1,3-dithiol-2-thione-4,5-dithiolato) zinc complex, disodium zinc ethylenediaminetetraacetate, zinc dibenzyldithiocarbamate (II), dibutyl Zinc rudithiocarbamate (II), zinc diethyldithiocarbamate, zinc dimethyldithiocarbamate, zinc phthalocyanine, zinc naphthenate, bis (cyclopentadienyl) cobalt (III) hexafluorophosphate, [1,1'-bis (diphenyl) Phosphino) ferrocene] cobalt (II) dichloride, bis (hexafluoroacetylacetonato) 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), phthalocyanine cobalt ( II), disodium cobalt ethylenediaminetetraacetate , Hexaamminecobalt (III) chloride, N, N'-disalicylic ethylenediaminecobalt (II), [5,10,15,20-tetrakis (4-methoxyphenyl) porphyrinato] cobalt (II), tris (2 , 4-Pentandionato) cobalt (III), cobalt naphthenate, [1,2-bis (diphenylphosphino) ethane] nickel (II) dichloride, bis (dithiobenzyl) nickel (II), bis (hexafluoroacetyl Acetonato) nickel (II), bis (2,4-pentanedionato) nickel (II), bis (tetrabutylammonium) bis (maleonitriledithiolato) nickel (II) complex, bis (tricyclohexylphosphine) nickel ( II) Dichloride, bis (triphenylphosphine) nickel (II) dichloride, bromo [(2,6-pyridindiyl) bis (3-methyl-1-imidazolyl-2-ylidene)] nickel bromide, ethylenediamine And tetrasodium acetic acid disodium nickel (II), nickel dibutyldithiocarbamate (II), nickel diethyldithiocarbamate and the like. These may be used individually by 1 type and may use 2 or more types together.

  The form of the metal-containing compound of the component (b) is not necessarily required to be highly soluble in organic matter because it only needs to be in a uniform state with the photocurable resin, but it is not necessarily easy to mix or store. In order to prevent precipitation, it is preferably an organic acid salt or a metal complex.

  The metal-containing compound of the component (b) can constitute a chain transfer agent by complexing with the compound containing the urethane bond, urea bond or isocyanate group of the component (a).

  The method for combining the component (a) and the component (b) is not particularly limited as long as both components are mixed at room temperature or under heating conditions. It is preferable to use a method in which the mixture is sufficiently stirred or kneaded and dissolved or uniformly dispersed in an active gas atmosphere at an appropriate temperature using a mixing apparatus such as a mixing mixer.

  The mixing method when adding the chain transfer agent to the photocurable resin is not particularly limited, and using a stirring device such as a mixing mixer at an appropriate temperature under reduced pressure or in an inert gas atmosphere such as nitrogen. A method of sufficiently stirring or kneading and dissolving or uniformly dispersing is preferable.

  The blending amount of the chain transfer agent with respect to the photocurable resin is not particularly limited, and may be appropriately added depending on the type of the photocurable resin, the required dark part curability, and the like.

  The water-stopping agent 13 can contain various additives as necessary within a range not impairing the object of the present invention. Examples of the additive include stabilizers, plasticizers, softeners, pigments, dyes, antistatic agents, flame retardants, sensitizers, dispersants, solvents, antibacterial antifungal agents, and the like.

  Examples of the stabilizer include an anti-aging agent, an antioxidant, and a dehydrating agent. For example, hindered phenol compounds, hindered amine compounds (anti-aging agents), butylhydroxytoluene, butylhydroxytoluene, butylhydroxyanisole, triphenyl phosphate, etc. (antioxidants), maleic anhydride, phthalic anhydride, benzophenone tetracarboxylic Acid chlorides (dehydrating agents) such as acid dihydrate, quicklime, carbodiimide derivatives, stearyl chloride and the like can be mentioned. A small amount of a polymerization inhibitor such as metaquinone can also be used as a stabilizer.

  Examples of the plasticizer include dioctyl adipate, dibutyl sebacate, diethylhexyl sebacate, isodecyl succinate, diethylene glycol dipenzoate, pentaerythritol ester, butyl oleate, methyl acetylricinoleate, tricresyl phosphate, trioctyl phosphate, Examples thereof include propylene glycol adipate polyester, butylene glycol adipate polyester, phenol, lauric acid, stearic acid, docosanoic acid, paraffinic oil, naphthenic oil, and aromatic oil.

  Examples of the softener include vinyl group-containing lactams such as N-vinylpyrrolidone and N-vinylcaprolactam, hydroxybutyl vinyl ether, lauryl vinyl ether, cetyl vinyl ether, 2-ethylhexyl vinyl ether, and the like.

  Examples of the pigment include inorganic pigments such as titanium dioxide, zinc oxide, ultramarine, bengara, lithopone, lead, cadmium, iron, cobalt, aluminum, hydrochloride, sulfate, and organic pigments such as azo pigments and copper phthalocyanine pigments. .

  Examples of the antistatic agent include hydrophilic compounds such as quaternary ammonium salts, polyglycols, and ethylene oxide derivatives.

  Examples of the flame retardant include chloroalkyl phosphate, dimethyl / methylphosphonate, bromine / phosphorus compound, ammonium polyphosphate, neopentyl bromide-polyether, and brominated polyether.

  Examples of the sensitizer include dimethylformamide, N-methylpyrrolidone, triethylamine, diethylamine, N-methyldiethanolamine, ethanolamine, 4-dimethylaminobenzoic acid, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, As isoamyl 4-dimethylaminobenzoate, commercially available products include Ubekryl P102, 103, 104, 105 (above, manufactured by UCB).

  Examples of the dispersant include surfactants such as polyoxyethylene nonylphenyl ether and polyethylene glycol octylphenyl ether.

  The solvent may be any solvent that dissolves the chain transfer agent and lowers the viscosity or increases the compatibility. Specifically, polar solvents such as tetrahydrofuran, dimethylformamide, ethyl acetate, methyl ethyl ketone, dichloroethane, trichlorobenzene, etc. Of chlorinated solvents.

  The aforementioned additives can be used in combination as appropriate.

  The water stopping agent 13 is obtained by mixing the above-described components. The mixing method is not particularly limited, and is sufficiently stirred or kneaded using a stirring device such as a mixing mixer under a reduced pressure or in an inert gas atmosphere such as nitrogen, and dissolved or uniformly dispersed. The method of making it preferable is.

  It is preferable that the water-stopping agent 13 has fluidity that can penetrate and spread between the conductor 4 and the conductor 4 and the covering material 5 in the ground terminal connection portion 11 and fill the gap. . Specifically, the viscosity of the water-stopping agent 13 is preferably in the range of 0.001 to 10 Pa · s, more preferably in the range of 0.006 to 6 Pa · s as the viscosity when measured at the dropping temperature. Is within. An E-type viscometer was used for measuring the viscosity.

  The conductor 4 of the ground wire 2 is made of a stranded wire formed by twisting a plurality of strands. In this case, 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. Further, 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 conductor 4 include copper, a copper alloy, aluminum, an aluminum alloy, or a material obtained by applying various platings to these materials. Examples of the material of the metal strand as the reinforcing wire include copper alloy, titanium, tungsten, and stainless steel. Examples of the organic fiber as the reinforcing wire include aromatic polyamide fibers such as poly- (p-phenylene terephthalamide).

  Examples of the material of the covering material 5 include rubber, polyolefin, PVC, and thermoplastic elastomer. These may be used alone or in combination of two or more. Various additives may be appropriately added to the material of the covering material 5. Examples of the additive include a flame retardant, a filler, a colorant and the like.

  Hereinafter, the manufacturing method of the electric wire with a ground terminal of FIG. 1 is demonstrated. First, the grounding wire 2 and the grounding terminal 3 are prepared with the tip peeled off. The ground terminal 3 before crimping is in a state where the conductor crimping portion 9 and the insulation barrel 10 are open. The grounding wire 2 is in a state in which the conductor 4 is exposed by removing the covering material 5 of the terminal by a predetermined length.

  Next, the conductor 4 and the covering material 5 of the ground wire are set on the conductor crimping portion 9 and the insulation barrel 10 of the ground terminal 3, and the conductor crimping portion 9 and the insulation barrel 10 are crimped. The ground terminal 3 is fixed by crimping to the end of the grounding wire 2.

  Next, as shown in FIG. 1 and FIG. 2, the above-mentioned portion where the light does not reach can be cured to the ground connection portion 7, and a water-stopping agent 13 containing a photocurable resin and a chain transfer agent is supplied. . Specifically, a predetermined amount of water-stopping agent 13 is dropped between the conductor crimping portion 9 of the ground terminal 3 and the insulation barrel 10 using a discharge device (not shown). The dripping of the water stop agent 13 may be performed in a plurality of times.

  Next, the water blocking agent 13 is allowed to penetrate into the conductor 4 of the grounding wire 2. It is preferable that the water-stopping agent 13 penetrates from the portion where the conductor 4 is exposed to the inside of the electric wire covered with the covering material 5. The infiltration of the covering material 4 may be allowed to stand after dropping, and may be allowed to diffuse and infiltrate the gap by the fluidity and wettability of the covering material 13 or may be infiltrated using a differential pressure infiltration method or the like. May be.

  The differential pressure permeation method is a pressure between the ambient pressure of the exposed conductor portion of the ground wire 2 to which the water stop agent 13 is dropped and the pressure of the portion of the ground wire 2 covered with the conductor 4 inside. This is a method in which a difference is generated and the water-stopping agent 13 is sucked and penetrated inside the coating agent by this pressure difference. In order to generate the pressure difference, a method of reducing the inside of the covering material 5 by sucking air from the other end of the grounding wire 2, or a terminal where the water-stopping agent 13 is dropped is placed in a pressurized container, and compressed air is used. For example, a method of press-fitting the water-stopping agent 13 into the inside of the covering material 5 and the like can be used.

  Next, the water-stopping agent 13 is cured by irradiating the water-stopping agent 13 with ultraviolet rays using an ultraviolet irradiation device. Irradiation with ultraviolet rays is performed under irradiation conditions that allow the water-stopper 13 to be cured. The water-stopping agent 13 can be cured at a place where the ultraviolet rays do not reach and contains a chain transfer agent, so that the portion where the ultraviolet rays reach can be cured and the portion where the ultraviolet rays cannot reach can be cured. Therefore, the water-stopping agent 13 that has penetrated into the inside of the conductor 4 where the ultraviolet rays do not reach of the ground connection portion 7 and the inside of the covering material 5 is cured to the inside. As described above, since the entire water-stopping agent 13 can be cured only by light irradiation such as ultraviolet rays, a step of heating and post-curing after light irradiation is unnecessary.

  As the ultraviolet irradiation apparatus used for the ultraviolet irradiation, a light source such as a bulb type UV lamp or an LED-UV lamp in which Hg, Hg / Xe, a metal halide compound, or the like is enclosed can be used. Further, the ultraviolet irradiation device may use a condensing UV irradiation device that collects and irradiates light from the light source with a reflection mirror.

  The dripping (supplying) of the water-stopping agent 13 may be performed at room temperature, or may be performed in a heated state using a heating device or the like so as to easily penetrate into a gap or the like. As such a heating device, for example, a ceramic heater, a hot air jet heater, a pipe electromagnetic heater, a halogen lamp heater, a contact rubber heater, or the like can be used.

  The electric wire with a ground terminal of the present invention is suitable for wiring in a vehicle such as an automobile, and is particularly suitable for wiring in an engine room or a vehicle in a wet area. In such a place, since it is easily affected by heat and water, water easily enters the ground connection portion. According to the electric wire with the ground terminal of the present invention, the water-stopping agent 13 that has penetrated to the inside of the electric wire 2 for earthing can be cured, so that water can be reliably stopped.

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

(1) Waterstop agent adjustment Chain transfer agents 1-12 (B-1 to B-12) used in Examples in Table 1 and Materials 1 and 2 (X-1, X-2) used in Comparative Examples The composition of is shown. A chain transfer agent mix | blends each component with the composition (mass part) shown in Table 1, mixes using a stirrer, melt | dissolves or disperses, and shows 1-12 (B-1 to B-12) shown in Table 1. Each chain transfer agent was obtained. Moreover, the materials 1 and 2 (X-1, X-2) of the comparative example were comprised only from (a) component, without adding a metal-containing compound.

Abbreviations in the table are as follows, and those not specifically labeled by the manufacturer were reagent grades manufactured by Tokyo Kasei Co., Ltd.
(A) Component: Urethane-containing binding compound / UP-1: Synthetic product (Synthesis Example 1 will be described later)
UP-2: synthetic product (Synthesis Example 2 will be described later)
(A) Component: Urea-containing binding compound / UP-3: synthetic product (Synthesis Example 3 will be described later)
(A) Ingredient: Isocyanate-containing compound containing N · N3600: Product name “Desmodur N3600” manufactured by Sumika Bayer Urethane Co., Ltd. (A commercially available product was used as a compound having an isocyanate group).

(Synthesis Example 1) Synthesis of UP-1 In a reaction vessel equipped with a stirrer, 80 g (200 mmol) of polypyrene glycol having a number average molecular weight of 400, 40 g (238 mmol) of hexamethylene diisocyanate
And 0.05 g of dibutyltin dilaurate were added, and the liquid temperature was raised from room temperature to 50 ° C. over 1 hour with stirring. Thereafter, a small amount was sampled, and FT-IR was measured, and stirring was continued at 50 ° C. while confirming absorption of the isocyanate group near 2300 cm ⁻¹ . The content of residual isocyanate groups was calculated from the absorption area of FT-IR, and the reaction was terminated when it decreased to about 15% compared to before the reaction and disappeared, and a colorless transparent viscous liquid was obtained. . This is UP-1. UP-1 is a urethane-containing binding compound having a number average molecular weight of about 3000 and having an isocyanate group at the end.

(Synthesis Example 2) Synthesis of UP-2 In a reaction vessel equipped with a stirrer, 100 g (33 mmol) of UP-1 and 8.29 g (70.6 mmol) of 2-hydroxyethyl acrylate, 0.05 g of dibutyltin dilaurate, 0.02 g of 卜 -tetratetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propioner ピ) was charged, and the liquid temperature was raised from room temperature to 50 ° C. over 1 hour with stirring. . Thereafter, a small amount was sampled, and FT-IR was measured, and stirring was continued at 50 ° C. while confirming absorption of an isocyanate bottle near 2300 cm ⁻¹ . The content of residual isocyanate groups was estimated from the absorption area of FT-IR, and when the absorption disappeared, the reaction was terminated, and a colorless transparent viscous liquid was obtained. This is designated as UP-2. UP-2 is a urethane-containing bonded compound having a number average molecular weight of about 3200 and an acrylate group at the end.

(Synthesis Example 3) Synthesis of UP-3 In a reaction vessel equipped with a stirrer, 40 g (208 mmol) of 1,1,1-diamino-3,6,9-trioxaounde, 42 g (250 mmol) of hexamethylene diisocyanate The liquid temperature was raised from room temperature to 50 ° C. over 1 hour with stirring. Thereafter, a small amount was sampled, and FT-IR was measured, and stirring was continued at 50 ° C. while confirming absorption of the isocyanate group near 2300 cm ⁻¹ . The content of residual isocyanate groups was calculated from the absorption area of FT-IR, and the reaction was terminated when it decreased to about 15% compared to before the reaction and disappeared, and a colorless transparent viscous liquid was obtained. . This is designated as UP-3. UP-3 is a urea-containing binding compound having a number average molecular weight of about 2000 and a terminal isocyanate group.

(B) Component: Metal-containing compound · BPDZ: Bis (2,4-pentandiona 卜) zinc (II)
CDEDTC: Diethyldithiocarbamate copper (II)
DBTDL: dibutyltin dilaurate BPDC: bis (2,4-pentandiona ジ オ) cobalt (II)
BTCN: dibutyldithio force nickel rubamate (II)

(Examples 2-1 to 2-19, Comparative Examples 2-1 to 2-6)
Examples and comparative examples are shown below. In Examples and Comparative Examples, ultraviolet curable materials (A-1 to A-4) shown in Table 2 were used as a photocurable resin for a water-stopping agent. Each component of Table 2 is as follows.
[(Meth) acrylate]
-IBA: isobornyl acrylate-DPGA: dip mouth pyrene glycol diacrylate-UP-2: synthetic product (as described in Synthesis Example 2)
[Ultraviolet (light) polymerization initiator]
HCHPK: 1-hydroxy hexyl phenyl ketone EANT: 2-ethylanthraquinone

  The chain transfer agents B-1 to B-12) of Table 1 were added to the UV curable resins of A-1 to A-4 shown in Table 2 in the amounts shown in Table 3, and Examples 2-1 to 2 A -19 water-stop agent was prepared and tested for curability. For comparison, the materials shown in Table 4 were prepared as Comparative Examples 2-1 to 2-6, and a curability test was performed.

(Comparative Example 2-1)
The test was conducted using only the ultraviolet curable resin shown in A-2 of Table 2.
(Comparative Example 2-2)
The test was conducted using only the chain transfer agent (B-1) of Example 2.
(Comparative Example 2-3)
A test was performed in the same manner as in Example 2-2 except that the material (X-1) of Comparative Example 1 was used instead of the chain transfer agent (B-2) of Example 2-2.
(Comparative Example 2-4)
A test was performed in the same manner as in Example 2-2 except that the material (X-2) of Comparative Example 2 was used instead of the chain transfer agent (B-2) of Example 2-2.
(Comparative Example 2-5)
The test was conducted in the same manner as in Example 2-2 except that 2-mer-powered ptopentimidazole (MBI) was used instead of the chain transfer agent (B-2) in Example 2-2.
(Comparative Example 2-6)
The test was conducted in the same manner as in Example 2-2 except that 2,4-diphenyl-4-methyl-1-pentene (DPMP) was used instead of the chain transfer agent (B-2) of Example 2-2. went.

(2) Production of grounding wire Using a 1 to 2 drop dispenser, the grounding terminal connecting portion 11 shown in FIGS. 1 and ² of the grounding wire having a wire length of 0.5 m and a wire cross-sectional area of 2 mm ² is used. Using an LED irradiator (LED-UV lamp) with a central wavelength of 385 nm, the water-stopper is cured by irradiating it with ultraviolet light at an irradiation light quantity of 1000 mw / cm ² for 10 seconds, Produced.

[Evaluation of water stoppage performance by pressure test]
About the electric wire with an earthing terminal of an example and a comparative example, the pressure resistance test was done and water stop performance was evaluated. In the pressure resistance test, an air pressure of 200 kPa was applied for 1 minute from a terminal on the side where the ground terminal was not crimped, and the presence or absence of air leak was observed in a state where the entire ground terminal connection portion of the wire with the ground terminal was immersed in water. The case where there was no air leak was judged as good (◯), and the case where air leak was confirmed during the pressurization with an air pressure of 200 kPa for 1 minute was judged as bad (×). In addition, the above-mentioned withstand voltage test was also performed on the electric wire with the ground terminal after the entire ground terminal connecting portion was placed in a 120 ° C. constant temperature bath for 120 hours (after heating). Tables 3 and 4 show the results of the test.

  As shown in Table 3, as for the electric wire with a grounding terminal using the water-stopping agent having the composition shown in Examples 2-1 to 2-19, the water-stopping performance was initial (good) after heating. . On the other hand, as shown in Table 4, the electric wire with a ground terminal using the materials of Comparative Examples 2-1 to 2-6 does not cure the internal ultraviolet curable resin that does not reach the irradiation light. It was bad (x).

  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.

  In the above embodiment, only a part of the portion where the conductor of the electric wire is exposed is covered with the water-stopping agent, but the entire portion where the conductor of the electric wire is exposed may be covered with the water-stopping agent.

  In the above embodiment, the water-stopping agent was used as a water-stopping agent for the ground connection portion of the ground terminal. However, the water-stopping agent of the present invention is applied to water-stopping at the connection portion between the terminal other than the ground terminal and the conductor of the electric wire. May be.

DESCRIPTION OF SYMBOLS 1 Electric wire with a ground terminal 2 Ground wire 3 Ground terminal 4 Conductor 5 Cover material 7 Ground connection part 8 Crimp part 11 Ground terminal connection part 13 Water stop agent

Claims (5)

In the photo-curing water-stopping agent used for water-stopping of the ground terminal connection part of the wire with the ground terminal in which the ground terminal is connected to the terminal of the grounding wire,
The water-stopping agent can be cured at a place where light does not reach, and contains a photocurable resin and a chain transfer agent.   The chain transfer agent has a compound containing at least one selected from a urethane bond, a urea bond and an isocyanate group as the component (a) and a metal-containing compound as the component (b). The water-stopping agent according to claim 1.   The water-stopping agent according to claim 2, wherein the component (b) of the chain transfer agent is a metal compound containing at least one metal selected from tin, copper, zinc, cobalt, and nickel. In the wire with a ground terminal in which the ground terminal connection part of the wire with the ground terminal in which the ground terminal is connected to the terminal of the ground wire is covered with a water stop agent,
The said grounding terminal connection part is coat | covered with the water stop agent of any one of Claims 1-3, The electric wire with a grounding terminal characterized by the above-mentioned. In the grounding terminal connection part of the grounding wire, where the grounding terminal is connected to the end of the grounding wire, it is possible to harden the place where light does not reach, and it contains a photocurable resin and a chain transfer agent. A method for producing an electric wire with a ground terminal, wherein a water agent is used to cure the water-stop agent and water-stop the ground terminal connection portion.

Images