JP2014116195A - Anticorrosive, covered wire with terminal, and wire harness - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photocurable anticorrosive which can cure even a portion in which irradiation light does not reach; a covered wire with a terminal using the same; and a wire harness.SOLUTION: The covered wire with the terminal is formed by covering an electric connection part at which an electric wire conductor of the covered wire and a terminal metal fitting are electrically connected, by using the anticorrosive which can cure the portion in which the irradiation light does not reach and contains a photocurable resin and a chain transfer agent. The wire harness is constituted by using the covered wire with the terminal.

Description

  The present invention relates to an anticorrosive, a coated electric wire with a terminal, and a wire harness, and more specifically, an anticorrosive suitable for anticorrosion of an electrical connection portion between an electric wire conductor and a terminal fitting, The present invention relates to a wire harness using the covered electric wire with terminal.

  In recent years, the movement to improve fuel efficiency has been accelerated by reducing the weight of vehicles such as automobiles, and there is a demand for reducing the weight of the wire material constituting the wire harness. Therefore, the use of aluminum for the wire conductor has been studied.

  However, copper or a copper alloy having excellent electrical characteristics is generally used for the terminal fitting. Therefore, it is often used in a combination of an aluminum electric wire and a copper terminal fitting. If the material of the wire conductor and the terminal fitting are different, corrosion due to contact with different metals occurs at the electrical connection portion. This type of corrosion is more likely to occur than when the wire conductor and the terminal fitting are the same material.

  As a countermeasure, a method of preventing corrosion of the electrical connection portion by applying an anticorrosive agent for preventing corrosion to the electrical connection portion between the electric wire conductor and the terminal fitting has been used. The said anticorrosive uses a liquid thing from the point of the ease of application | coating, and a handleability, it is made to apply | coat to an electrical connection part, it is made to infiltrate, and a shape is maintained by hardening.

  Such an anticorrosive can be classified into a thermosetting type, a two-component mixed reaction curable type, a moisture curable type, a photocurable type, and the like, when classified by the resin curing mechanism. Among these, as the anticorrosive agent for the electrical connection portion, a photo-curing type, particularly an ultraviolet curable resin is often used because of its fast curing time and simple process (for example, see Patent Document 1).

JP 2011-256429 A

  However, when an ultraviolet curable resin is used as an anticorrosive agent for electrical connection parts, the gap between the wires of the electric wire or the portion covered by the terminal does not reach the ultraviolet ray, and the resin is in an uncured state, so the corrosion cannot be prevented. was there.

  The problem to be solved by the present invention is to provide an anticorrosive agent that can be cured even at a location where irradiated light does not reach in the photocurable anticorrosive agent. Moreover, it is providing the covered electric wire with a terminal using this, and a wire harness.

  In order to solve the above-described problems, the anticorrosive agent of the present invention is used for anticorrosion of a coated electric wire with a terminal having an electrical connection portion to which an electric wire conductor of a covered electric wire and a terminal fitting are electrically connected, and is cured by light irradiation. The gist of the photocurable anticorrosive agent is that the anticorrosive agent can cure a portion where light does not reach and contains a photocurable resin and a chain transfer agent.

  In the anticorrosive agent, the chain transfer agent has a compound containing at least one selected from urethane bond, urea bond and isocyanate group as component (a) and a metal-containing compound as component (b). It is preferable.

  In the anticorrosive 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 coated electric wire with a terminal of the present invention is a coated electric wire with a terminal in which an electric connecting portion where the electric wire conductor of the covered electric wire and the terminal fitting are electrically connected is coated with an anticorrosive agent, and the electric connecting portion is described above. The gist is that it is coated with an anticorrosive agent.

  In the electric wire with a terminal, the terminal fitting preferably has tin plating on the surface.

  The said electric wire with a terminal WHEREIN: It is preferable that the said electric wire conductor contains the strand which consists of aluminum or aluminum alloy.

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

  The anticorrosive agent of the present invention is used for anticorrosion of a coated electric wire with a terminal having an electrical connection portion where an electric wire conductor of a covered electric wire and a terminal fitting are electrically connected, and in the photocurable anticorrosive agent cured by light irradiation, Since the anticorrosive agent can be cured at a place where light does not reach and contains a photocurable resin and a chain transfer agent, it can be cured at a place where light does not reach.

  The coated electric wire with a terminal according to the present invention is such that the electric connection portion where the electric wire conductor of the coated electric wire and the terminal fitting are electrically connected is covered with the anticorrosive agent, so that it is cured at a place where the irradiation light does not reach. It is possible to improve the anticorrosion performance by increasing the shape maintainability of the waterproof portion.

  Since the wire harness of the present invention has the above-described coated electric wire with a terminal, a highly reliable wire harness excellent in the anticorrosion performance of the electric connection portion between the electric wire conductor and the terminal fitting can be obtained.

FIG. 1 is an external perspective view showing an example of a covered covered electric wire according to the present invention. 2 is a longitudinal sectional view taken along line AA in FIG. FIG. 3 is an explanatory diagram for explaining the corrosion test methods of Examples and Comparative Examples.

  Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings. FIG. 1 is an external perspective view showing an example of a coated electric wire with a terminal according to the present invention, and FIG. 2 is a longitudinal sectional view taken along line AA in FIG. As shown in FIG. 1 and FIG. 2, the terminal-equipped covered electric wire 1 is electrically connected to the electric wire conductor 3 of the covered electric wire 2 in which the electric wire conductor 3 is covered with the insulator 4 and the terminal fitting 5 through the electric connection portion 6. Has been. The electrical connection 6 is covered with an anticorrosive 7. The anticorrosive 7 is obtained by curing a photocurable anticorrosive composition that is cured by light irradiation. The composition of the anticorrosive agent 7 can be cured at a place where light does not reach and contains a photocurable resin and a chain transfer agent.

  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. However, the UV curable material is uncured in the area where UV rays are shielded by normal UV curing, but 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 alone or in combination of two or more.

  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 photo-curing resin is not particularly limited, and a stirring device such as a mixing mixer is used 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 composition of the anticorrosive agent can contain various additives as required 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. Can be mentioned.

  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 composition of the anticorrosive agent 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.

  In the electric wire with terminal 1 shown in FIG. 1, the terminal fitting 5 has a tab-like connection portion 51 formed of an elongated flat plate connected to the mating terminal, and a wire barrel 52 formed to extend at the end of the connection portion 51. And an electric wire fixing portion 54 including an insulation barrel 53.

  In the electrical connection portion 6, the insulator 4 at the end of the covered electric wire 2 is peeled off to expose the electric wire conductor 3, and the exposed electric wire conductor 3 is crimped to one side of the terminal metal fitting 5. And the terminal fitting 5 are connected. The wire barrel 52 of the terminal fitting 5 is crimped from above the wire conductor 3 of the covered electric wire 2 so that the wire conductor 3 and the terminal fitting 5 are electrically connected. Further, the insulation barrel 53 of the terminal fitting 5 is crimped from above the insulator 4 of the covered electric wire 2.

  Further, the range indicated by the alternate long and short dash line in FIG. 1 is formed as an anticorrosion part in which the surface of the electrical connection part 6 is covered with the anticorrosive 7. In addition, the anticorrosion part of FIG. 1 is shown in a state where the anticorrosive agent 7 is seen through. The anticorrosion part is in a state in which the anticorrosive 7 is filled in the inside of the electric wire conductor 3 or the contact portion between the electric wire conductor 3 and the terminal fitting 5, and moisture etc. enters from the outside and the terminal fitting or electric wire conductor. This prevents the metal parts from corroding.

  The part which the anticorrosive 7 of the anticorrosion part has coat | covered is the following parts. The front end side of the covered electric wire 2 is covered so as to slightly protrude from the front end of the electric wire conductor 3 to the connecting portion 51 side of the terminal fitting 5. The distal end side of the terminal fitting 5 is covered so as to protrude slightly from the end of the insulation barrel 53 to the insulator 4 side of the covered electric wire 2. The portion where the end of the covered wire 2 is peeled off and the wire conductor 3 is exposed is completely covered with the anticorrosive 7 and is not exposed to the outside.

  As shown in FIG. 2, the side surface of the terminal fitting 5 is also covered with the anticorrosive agent 7. The anticorrosive 7 is coated with a predetermined thickness along the outer peripheral shape of the terminal fitting 5 and the covered electric wire 2. 2 is not coated with the anticorrosive 7 on the back surface side of the terminal metal fitting 5 which is the lower side in FIG. 2 (for convenience, the wire crimping surface of the terminal metal fitting is the front surface and the opposite surface is the back surface).

  If the electrical connection is not affected, the back side of the wire fixing portion 54 of the terminal fitting 5 (including the back side of the wire barrel 52 and the insulation barrel 53) may be covered with the anticorrosive 7. .

  It is preferable to apply the composition so that the anticorrosive agent 7 has a thickness of 0.01 to 0.1 mm after application. If the thickness of the anticorrosive 7 becomes too thick, it may be difficult to insert the terminal fitting into the connector. Moreover, when the thickness of the anticorrosive 7 becomes too thin, there exists a possibility that anticorrosion performance may become inadequate.

  Application | coating of the composition of the anticorrosive 7 can use well-known means, such as a dripping method, the apply | coating method, and an extrusion method. In applying the anticorrosive composition, the temperature of the composition may be adjusted by heating, cooling, or the like. The composition of the anticorrosive 7 is preferably applied by a coating method in which shear stress is applied. When a shear stress is applied to the composition of the anticorrosive agent 7 at the time of application, the viscosity is lowered and it becomes easy to penetrate into the gaps and the like.

  Hereinafter, the other structure of the covered electric wire 1 with a terminal is demonstrated. The electric wire conductor 3 of the covered electric wire 2 is made of a stranded wire formed by twisting a plurality of strands 3a. 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 wire conductor 3 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 insulator 4 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 insulator 4. Examples of the additive include a flame retardant, a filler, a colorant and the like.

  Examples of the material (material for the base material) of the terminal fitting 5 include various copper alloys and copper in addition to brass that is generally used. A part (for example, a contact) or the entire surface of the terminal fitting 5 may be plated with various metals such as tin, nickel, and gold. The anticorrosive agent of the present invention is particularly excellent in adhesion to tin plating.

  In order to manufacture the coated electric wire 1 with a terminal, the electric wire fixing part 54 of the terminal metal fitting 5 is first crimped to the terminal of the covered electric wire 2 which peeled off the tip and exposed the electric wire conductor 3 by a predetermined length, The wire conductor 3 and the terminal fitting 5 are connected. Next, the composition of the anticorrosive 7 is applied to the surface of the connection portion between the wire conductor 3 and the terminal fitting 5. Next, the anticorrosive agent 7 is irradiated with light such as ultraviolet rays under predetermined conditions to cure the composition, whereby the terminal-coated electric wire 1 is obtained.

  Conditions for ultraviolet irradiation can be appropriately selected according to the composition of the anticorrosive and the like. As an irradiation apparatus used for ultraviolet irradiation, a known apparatus can be used. As the irradiation apparatus, for example, a light source such as a bulb-type UV lamp or LED-UV lamp in which Hg, Hg / Xe, a metal halide compound, or the like is sealed 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.

  Hereinafter, the wire harness of the present invention will be described. The wire harness of this invention consists of what bundled the several covered electric wire 2 containing the said covered electric wire 1 with a terminal. In the wire harness, a part of the covered electric wire may be the covered electric wire 1 with a terminal of the present invention, or all may be the covered electric wire 1 with a terminal of the present invention.

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

  The wire harness of the present invention is suitable for being routed in a vehicle such as an automobile, and is particularly suitable for being routed in an engine room or a vehicle in a wet area. In such a place, since it is easy to receive the influence of a heat | fever and water, if a wire harness is routed in such a place, it will become easy to generate | occur | produce rust in the electrical connection part of the electric wire conductor 3 and the terminal metal fitting 5. FIG. According to the wire harness of this invention, generation | occurrence | production of the rust in the electrical connection part 6 of the electric wire conductor 3 and the terminal metal fitting 5 in the covered electric wire 1 with a terminal can be suppressed effectively.

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

(1) Preparation of anticorrosive agents 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 Indicates the material. 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 lysyltetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] 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)
Hereinafter, the Example of an anticorrosive agent and a comparative example are shown. In the examples and comparative examples of the anticorrosive agent, ultraviolet curable resins (A-1 to A-4) shown in Table 2 were used. 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 -19 anticorrosive 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 covered electric wire For 100 parts by mass of polyvinyl chloride (degree of polymerization 1300), 40 parts by mass of diisononyl phthalate as a plasticizer, 20 parts by mass of calcium bicarbonate as a filler, and calcium zinc-based stabilizer 5 as a stabilizer A polyvinyl chloride composition was prepared by mixing parts by mass at 180 ° C. with an open roll and forming the pellets with a pelletizer. Next, using a 50 mm extruder, the polyvinyl chloride composition is 0.28 mm thick around a wire conductor (cross-sectional area 0.75 mm) made of an aluminum alloy twisted wire in which seven aluminum alloy wires are twisted together. Extrusion coated. This produced the covered electric wire (PVC electric wire).

(3) Production of covered electric wire with terminal After stripping the end of the above covered electric wire and exposing the electric wire conductor, a male crimp terminal fitting made of brass (tab width 0.64 mm) widely used for automobiles Was crimped and crimped to the end of the covered electric wire. Next, an anticorrosive agent having the composition shown in Tables 3 and 4 was applied to the electrical connection portion between the electric wire conductor and the terminal fitting, and the exposed electric wire conductor and the barrel of the terminal fitting were covered with various anticorrosive agents. Then, the hardening process for predetermined time was performed on each hardening conditions, the anticorrosion agent was hardened, and the covered electric wire with a terminal was produced. Each anticorrosive was applied at a thickness of 0.05 mm, and cured by UV irradiation with a UV lamp (100 mW / cm ² manufactured by SEN Special Light Company) for 20 seconds.

[Anti-corrosion performance evaluation method]
As shown in FIG. 3, the coated electric wire with terminal 1 is connected to the positive electrode of the 12V power source 10, and the pure copper plate 20 (width 1 cm × length 2 cm × thickness 1 mm) is connected to the negative electrode of the 12V power source 2, The electrical connection part of the electric wire conductor of the electric wire 1 and a terminal metal fitting and the pure copper plate 20 were immersed in 300cc NaCl5% aqueous solution 30, and it supplied with electricity at 12V for 2 minutes. After energization, ICP emission analysis of NaCl 5% aqueous solution 4 was performed, and the amount of aluminum ions eluted from the wire conductor of the covered wire 1 with terminals was measured. The case where the elution amount was less than 0.1 ppm was judged as good (◯), and the case where the elution amount was 0.1 ppm or more was judged as poor (x). The anticorrosion performance test was evaluated both at the initial stage after curing the anticorrosive and after the thermal shock. The thermal shock was a thermal shock in which one cycle of holding at minus 40 ° C. for 30 minutes and then holding at plus 85 ° C. for 30 minutes was repeated for 500 cycles.

  As shown in Table 3, as for the covered electric wire with a terminal using the anticorrosive agent of Examples 2-1 to 2-19, the anticorrosion performance was good at the initial stage and after the thermal shock (◯). On the other hand, the coated electric wires with terminals using the materials of Comparative Examples 2-1 to 2-6, as shown in Table 4, the internal ultraviolet curable resin that does not reach the ultraviolet irradiation light does not cure, so that it is anticorrosive from the beginning. Was bad.

  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.

  For example, although the covered electric wire 1 with a terminal of the said Example uses the male terminal which has a tab-shaped connection part as the terminal metal fitting 5, it is not limited to this. For example, the terminal fitting may be a female terminal that can be fitted with a male terminal, or a tuning fork terminal. Further, the terminal fitting 5 may not be provided with the insulation barrel 53 but may be crimped only by the wire barrel 52. Further, the connection method between the electric wire conductor 3 and the terminal fitting 5 is not limited to crimping by a barrel, and may be a method such as pressure resistance welding, ultrasonic welding, or soldering. Moreover, in the said Example, although the electric wire conductor 3 which consists of a twisted wire was used, the electric wire conductor 3 may use a single core wire.

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

Claims (7)

In the photo-curing type anticorrosive used for the corrosion protection of the coated electric wire with a terminal having an electrical connection portion where the electric wire conductor of the coated electric wire and the terminal fitting are electrically connected, and cured by light irradiation,
The anticorrosive 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 anticorrosive agent according to claim 1.   The anticorrosive 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.   4. The covered electric wire with a terminal in which the electric connection portion where the electric wire conductor of the covered electric wire and the terminal fitting are electrically connected is covered with an anticorrosive agent, and the electric connection portion is any one of claims 1 to 3. A coated electric wire with a terminal, which is coated with an anticorrosive agent.   The said terminal metal fitting has tin plating on the surface, The covered electric wire with a terminal of Claim 4 characterized by the above-mentioned.   The said electric wire conductor contains the strand which consists of aluminum or aluminum alloys, The covered electric wire with a terminal of Claim 4 or Claim 5 characterized by the above-mentioned.   A wire harness comprising the covered electric wire with a terminal according to any one of claims 4 to 6.

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