CN1914771A - Method for waterproofing connection part of covered wire - Google Patents
Method for waterproofing connection part of covered wire Download PDFInfo
- Publication number
- CN1914771A CN1914771A CNA2005800032730A CN200580003273A CN1914771A CN 1914771 A CN1914771 A CN 1914771A CN A2005800032730 A CNA2005800032730 A CN A2005800032730A CN 200580003273 A CN200580003273 A CN 200580003273A CN 1914771 A CN1914771 A CN 1914771A
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- electric wire
- connecting portion
- curable
- cyanoacrylate
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01R—ELECTRICALLY-CONDUCTIVE CONNECTIONS; STRUCTURAL ASSOCIATIONS OF A PLURALITY OF MUTUALLY-INSULATED ELECTRICAL CONNECTING ELEMENTS; COUPLING DEVICES; CURRENT COLLECTORS
- H01R4/00—Electrically-conductive connections between two or more conductive members in direct contact, i.e. touching one another; Means for effecting or maintaining such contact; Electrically-conductive connections having two or more spaced connecting locations for conductors and using contact members penetrating insulation
- H01R4/22—End caps, i.e. of insulating or conductive material for covering or maintaining connections between wires entering the cap from the same end
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01R—ELECTRICALLY-CONDUCTIVE CONNECTIONS; STRUCTURAL ASSOCIATIONS OF A PLURALITY OF MUTUALLY-INSULATED ELECTRICAL CONNECTING ELEMENTS; COUPLING DEVICES; CURRENT COLLECTORS
- H01R13/00—Details of coupling devices of the kinds covered by groups H01R12/70 or H01R24/00 - H01R33/00
- H01R13/46—Bases; Cases
- H01R13/52—Dustproof, splashproof, drip-proof, waterproof, or flameproof cases
- H01R13/5216—Dustproof, splashproof, drip-proof, waterproof, or flameproof cases characterised by the sealing material, e.g. gels or resins
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- Connections Effected By Soldering, Adhesion, Or Permanent Deformation (AREA)
- Sealing Material Composition (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Abstract
The present invention provides a method for waterproofing connection parts of covered wires which enables to surely make an electrically connected connection part of a covered wire waterproof by a simple and quick process at low cost. A method for waterproofing connection parts of covered wires is that a curing sealing material is injected into a protective cap for protecting a connection part of a covered wire, then the connection part and a covered portion near the connection part of the covered wire are put in the sealing material, and then the sealing material is cured. The sealing material is a photocuring cyanoacrylate resin composition which has a viscosity of not more than 200 mPa.s at 25 DEG in the uncured state and a tensile elongation at break of not less than 20% after curing. The sealing material is cured by irradiation of an electromagnetic wave having a wavelength capable of curing the sealing material.
Description
Technical field
The present invention relates to the connecting portion method for waterproofing of coated electric wire, relate in particular to the connecting portion method for waterproofing of the coated electric wire of suitable Wiring harness for vehicle (wire harness).
Background technology
In the bunch in spreading all over the car body of automobile, be provided with manyly with the coated electric wire wire connecting connecting portion that diverges mutually, but the connection processing portion of the wire ends of such electrical connection need insulate reliably to the outside, and waterproof.Therefore, various electric wire connection methods has been proposed up to now.
For example, if according to opening the mutual method of attachment of disclosed electric wire in the clear 63-157163 communique in fact, as shown in Figure 4, the heart yearn of the electric wire A2 of bunch A1 and electric wire A3 interconnected and after forming connecting portion A4, make a pair of heat insulating lamella A5 of the lining of electric wire A2, A3 and same material superimposed, and above-mentioned connecting portion A4 is wrapped, then, use this heat insulating lamella of ultrasonic wave coating A5, implement lining by adhering to.But in the occasion of the mutual jockey of this electric wire, though above-mentioned connecting portion A4 is insulated, water often enters in the heat insulating lamella A5 from the gap or the gap between electric wire of electric wire and thin slice, can not make this connecting portion A4 waterproof reliably.In addition, need the ultrasonic wave coating machine, therefore increase such problem with regard to the expense that manufacturing equipment is arranged.
In addition, if use special method of attachment of opening disclosed coated electric wire in the flat 1-189881 communique, shown in Fig. 5 (a), the mutual twisted of the heart yearn of a pair of electric wire B6 after forming connecting portion B7, is sandwiched dividing plate B8 between above-mentioned a pair of electric wire B6.Then in the large-diameter portion B9a of heat-shrinkable tube B9, insert electric wire B6, in the minor diameter B9b that keeps metal sleeve B10, insert above-mentioned connecting portion B7.Then, shown in Fig. 5 (b), when assembling is over, above-mentioned metal sleeve B10 riveting is lived, above-mentioned connecting portion B7 is firmly fixed after, heat hot collapsible tube B9 shrinks it, seals by the surface that sticks to electric wire B6.But the method for attachment of this coated electric wire need many materials such as heat-shrinkable tube, metal sleeve, dividing plate, thereby cost uprises.In addition, not only flow chart is many, and needs manufacturing equipment in each operation, is caused by cost of equipment that therefore manufacturing cost increases.Have, the contact resistance of lining and pipe inner face is big, because metal sleeve B10 end is run at the tip sometimes, so connecting portion B7 is not easy to insert in the metal sleeve B10 again.
In addition, opening disclosed technology in clear 63-157163 communique and the flat 1-189881 communique of Te Kai in fact, in case, will all have the such problem of electric current electric leakage that flows in the electric wire that makes further because capillarity water is invaded in the lining from the gap between heart yearn if water has entered the heart yearn part.
If use special method of attachment of opening disclosed coated electric wire in the flat 9-55278 communique, as shown in Figure 6, the heart yearn 21b that exposes from the lining 21a of several electric wires 21 is mutually after connecting portion 25 is electrically connected, it is in the binding agent that near connecting portion 25 and heart yearn 21b, the heart yearn 21b lining 21a is immersed in cyano group, making above-mentioned cyano group is that binding agent is impregnated in the gap between heart yearn, then seals by near the lining 21a that covers with insulating component connecting portion 25 and heart yearn 21b, the heart yearn 21b.Under the situation of the method for attachment of this coated electric wire, making cyano group is that binding agent is impregnated in the gap between heart yearn, be cured, anti-whereby sealing is invaded in the lining from the gap of heart yearn, but it is thin that the cyano group that covers heart yearn 21b is the adhesive cures thing, and have the acceptant such problem of hydrolysis that is caused by moisture.
In addition, if use the special encapsulating method of opening disclosed electric wire connecting portion in the flat 11-178142 communique, as shown in Figure 7, interconnect and when the heat-shrinkable tube 82 that seals with hot-melt adhesive 83 with an inwall coating hot-melt adhesive 83 and an end in the outside of the electric wire connecting portion 81 that forms coats in each conductor ends that makes several electric wire W, to these heat-shrinkable tube 82 enforcement heat treatments and seal.The encapsulating method of this electric wire connecting portion is with making the hot-melt adhesive of electric wire connecting portion fusion be full of the gap, solidify then, the electric wire connecting portion is sealed, but though molten condition takes place, but hot-melt adhesive is mobile low, thereby is difficult for being full of gap inboard between electric wire, the part that lining portion has come off, allow the intrusion of water easily, and still exist worried this problem of water proofing property.
Patent documentation 1: open clear 63-157163 communique in fact
Patent documentation 2: the spy opens flat 01-189881 communique
Patent documentation 3: the spy opens flat 09-055278 communique
Patent documentation 4: the spy opens flat 11-178142 communique
Summary of the invention
The object of the present invention is to provide improve above-mentioned problem in the past, promptly can implement the connecting portion of the coated electric wire that is electrically connected simple, rapid, low-cost, the connecting portion method for waterproofing of the coated electric wire of water-proofing treatment reliably.
The connecting portion method for waterproofing of coated electric wire of the present invention is finished in order to solve above-mentioned problem; after in the protective cap of the connecting portion of protective covering electric wire, injecting the curable encapsulant; near in the sealing material connecting portion of the connecting portion of insertion coated electric wire and this coated electric wire covered part; then make in the connecting portion method for waterproofing of the coated electric wire that this curable encapsulant solidifies; it is characterized in that; viscosity when this curable encapsulant is under its uncured state 25 ℃ is less than or equal to 200mPas; and the tension fracture elongation rate after solidifying is for more than or equal to 20% the cyanoacrylate resin combination with photo-curable, and above-mentioned cured carries out the electromagnetic wave of the wavelength that this curable encapsulant can solidify by irradiation on above-mentioned curable encapsulant.
In addition, the connecting portion method for waterproofing of coated electric wire of the present invention, in the connecting portion method for waterproofing of above-mentioned coated electric wire, cyanoacrylate resin combination with above-mentioned photo-curable contains following (A), (B) and (C), and this tension fracture elongation rate of solidfied material with cyanoacrylate resin combination of photo-curable is more than or equal to 20%.
(A) 2-cyanoacrylate
(B) in molecule, has at least one side's of 2 acryloyl groups and methacryl optical polymerism resinous principle
(C) optical free radical polymerization initiator
In addition; the connecting portion method for waterproofing of coated electric wire of the present invention; in the connecting portion method for waterproofing of above-mentioned coated electric wire; above-mentioned protective cap constitutes by seeing through above-mentioned electromagnetic material; and the electromagnetic wave that makes above-mentioned wavelength sees through this protective cap from the outside of this protective cap, is radiated on the above-mentioned curable encapsulant.
Use the connecting portion method for waterproofing of coated electric wire of the present invention, concerning the connecting portion of the coated electric wire that is electrically connected, since simple, rapidly, so productivity ratio is good, because cost is low, the ratio of performance to price is also good, and, can implement reliable water-proofing treatment.
Description of drawings
Fig. 1 is the figure that expression utilizes the connecting portion of the wire terminations that method of the present invention handles.
Fig. 2 is the oblique view of expression electric wire assembly.
Fig. 3 is illustrated in the figure that inserts the situation of electric wire assembly in the insulator cap that binding agent enters.
Fig. 4 is illustrated in the real figure of the method for attachment of disclosed electric wire in the clear 63-157163 communique that opens.
Fig. 5 is illustrated in the figure that the spy opens the method for attachment of disclosed coated electric wire in the flat 1-189881 communique.
Fig. 6 is illustrated in the figure that the spy opens the method for attachment of disclosed coated electric wire in the flat 9-55278 communique.
Fig. 7 is illustrated in the figure that the spy opens the method for attachment of disclosed coated electric wire in the flat 11-178142 communique.
Symbol description
60 protective caps
The major diameter part of 61 protective caps
The small diameter portion of 62 protective caps
70 electric wire assemblies
71 electric wires (coated electric wire)
The 71a covered part
The 71b heart yearn
75 connecting portions
65 curable encapsulants
The connection processing portion of 200 wire terminations
Embodiment
In the present invention, as the curable encapsulant, need to use cyanoacrylate resin combination with photo-curable.Promptly, the curable encapsulant that has photo-curable by use, can be with rapid, low installation cost, implement reliably to solidify, because this curable encapsulant is the cyanoacrylate resin combination, so after curing, become the bulkhead (first bulkhead) of the crosslinked not facile hydrolysis of 3 dimensions.
Have again, the micro-moisture that is present in coated electric wire surface or connecting portion surface is brought into play function as initator, make the cyanoacrylate resin combination generation anionic polymerization on every side of this moisture, and become the cationic polymerization resins solidfied material layer of the 2nd bulkhead, even invade near the heart yearn if therefore break through the water of the trace of the 1st bulkhead, also can prevent the immersion of sealing fully to the heart yearn gap by the 2nd bulkhead.
In addition, in the present invention, the resin combination of so-called photo-curable is by irradiates light, and the resin combination of the chemical reaction type of radical polymerization can take place.
Cyanoacrylate resin combination with the photo-curable that uses among the present invention, the tension fracture elongation rate of solidfied material must be more than or equal to 20%.The tension fracture elongation rate of solidfied material is to be No. 3 coupons of dumb-bell shape of making of standard under 23 ℃, the environment of relative humidity (RH) 50% with JIS K6251, uses the value of stretching test machine determination of the condition of draw speed 10mm/min.
In general, the solidfied material of cyanoacrylate resin combination is hard and crisp, and the tension fracture elongation rate of solidfied material is less than 5%.If the solidfied material to so general cyanoacrylate resin combination gives thermal shock, just produced be full of cracks.Therefore when using so general cyanoacrylate resin combination, generation can not be kept the possibility of sufficient water resistance, but it is cyanoacrylate resin combination more than or equal to 20% photo-curable that the present invention is to use the tension fracture elongation rate that has after the curing, improve cold-resistant thermal shock by leaps and bounds, therefore such a be full of cracks is prevented from, as a result of, the connecting portion to electric wire can positively carry out water-proofing treatment.Specifically, the durability such as the desired thermal endurance of bunch, cold resistance, humidity resistance, cold-resistant thermal shock, resistance to water and resistance to salt water of automobile can be satisfied, the high water-proofing treatment of reliability can be carried out.
Has tension fracture elongation rate after such curing and is cyanoacrylate resin combination more than or equal to 20% photo-curable; by in common cyanoacrylate resin combination, cooperating at least one side's who for example in molecule, has 2 acryloyl groups and methacryl optical polymerism resinous principle, just can finish.
At this,, except following (A), (C), wish to contain following (B) as the cyanoacrylate resin combination that uses among the present invention with photo-curable.
(A) 2-cyanoacrylate
(B) in molecule, has the optical polymerism resinous principle of at least one side in 2 acryloyl groups and the methacryl
(C) optical free radical polymerization initiator
At this, illustrate in greater detail these each compositions.
(A) the 2-cyanoacrylate is to have anionic polymerization and free-radical polymerised monomer, becomes the principal component of the cyanoacrylate resin combination with photo-curable.For such 2-cyanoacrylate, all be suitable for as the widely used 2-cyanoacrylate of principal component of cyanoacrylate moment binding agent.Preferred 2-cyanoacrylate is the compound of representing with following formula I.
Formula I
(in following formula, R is alkyl, cycloalkyl, haloalkyl, alkoxyalkyl, alkenyl, cycloalkenyl, alkynyl or aryl.)
Preferred 2-cyanoacrylate, R among the above-mentioned formula I is the alkyl of carbon number 1～8, cycloalkyl, haloalkyl, alkoxyalkyl, alkenyl, cycloalkenyl, alkynyl or aryl, as preferred object lesson, can enumerate R is the 2-Methyl 2-cyanoacrylate of alkyl, the 2-cyanacrylate, 2-alpha-cyanoacrylate n-propyl, 2-alpha-cyanoacrylate isopropyl ester, the positive butyl ester of 2-alpha-cyanoacrylate, the 2-isobutylcyanoacrylate, 2-alkyl cyanoacrylate classes such as 2-alpha-cyanoacrylate n-octyl, R is the 2-alpha-cyanoacrylate allyl ester of unsaturated group, 2-alpha-cyanoacrylate alkene ester or 2-alpha-cyanoacrylate alkynes ester classes such as 2-alpha-cyanoacrylate alkynes propyl ester, 2-alpha-cyanoacrylate 2,2, the 2-trifluoro ethyl ester, 2-alpha-cyanoacrylate 2,2,3,2-alpha-cyanoacrylate fluoroalkyl ester classes such as 3-tetrafluoro propyl ester, 2-alpha-cyanoacrylate methoxyl group ethyl ester, 2-alpha-cyanoacrylate alkoxy alkyl classes such as 2-alpha-cyanoacrylate ethoxy ethyl ester, but be not limited to these.These 2-cyanoacrylates can be a kind, and can mix several uses.
The preferred 2-cyanoacrylate that uses among the present invention is 2-cyanacrylate, 2-alpha-cyanoacrylate n-propyl, 2-alpha-cyanoacrylate isopropyl ester, the positive butyl ester of 2-alpha-cyanoacrylate, 2-isobutylcyanoacrylate, 2-alpha-cyanoacrylate methoxyl group ethyl ester, 2-alpha-cyanoacrylate ethoxy ethyl ester.
The optical polymerism resinous principle that has at least one side of 2 acryloyl groups and methacryl in the present invention in (B) molecule of Shi Yonging is so long as the optical polymerism resinous principle that can give percentage elongation to the solidfied material of cyanoacrylate resin combination with photo-curable just.Can enumerate the following optical polymerism resinous principle of picture particularly.
Polyethylene glycol two (methyl) acrylate (has ア ロ ニ Star Network ス M-260 as commercially available product: Toagosei Co., Ltd's system, NK ester A-600,23G: Xin Zhong village chemical industry Co., Ltd. system etc., below identical), polypropylene glycol two (methyl) acrylate (ア ロ ニ Star Network ス M-270: Toagosei Co., Ltd's system, NK ester APG-700: Xin Zhong village chemical industry Co., Ltd. system etc.), urethanes (methyl) acrylate (ア ロ ニ Star Network ス M-1310: Toagosei Co., Ltd's system, UV3000B: The Nippon Synthetic Chemical Industry Co., Ltd's system etc.), polyester (methyl) acrylate (ア ロ ニ Star Network ス M-6100: Toagosei Co., Ltd's system, KAYARAD HX-620: Nippon Kayaku K. K's system etc.), EO modification two (methyl) acrylate of bisphenol-A (ア ロ ニ Star Network ス M-210: Toagosei Co., Ltd's system etc.), but be not limited to these.These light-cured resins can be a kind, and can mix several uses.Moreover so-called above-mentioned " (methyl) acrylate " expression can be that " methacrylate " also can be " acrylate " (following identical).
Even among these light-cured resins, preferentially use polyethylene glycol two (methyl) acrylate, polypropylene glycol two (methyl) acrylate, carbamate (methyl) acrylate, polyester (methyl) acrylate.
In addition, good for the cold-resistant thermal shock of the solidfied material that makes the curable encapsulant, the glass transition temperature of light-cured resin solidfied material (Tg) preferably is less than or equal to 0 ℃.Though lower limit is restriction especially not, if consider adhesiveness, it is real being greater than or equal to-50 ℃.
These light-cured resin compositions are to the use level in the 2-cyanoacrylate, with both total amount as benchmark, the light-cured resin composition preferably more than or equal to 1 weight %, be less than or equal to 50 weight %, be more preferably more than or equal to 10 weight %, be less than or equal to 40 weight %.If the use level of light-cured resin composition is littler than 1 weight %, often can not give sufficient percentage elongation to the solidfied material after solidifying, on the other hand, if surpass 50 weight %, the viscosity of resin combination rises, resin combination does not often soak between heart yearn in the gap of waiting, and moment adhesiveness problem such as slack-off is arranged.
(C) optical free radical polymerization initiator that uses among so-called the present invention be utilize by rayed cause take hydrogen by force or cracking makes (A) 2-cyanoacrylate and (B) has the optical free radical polymerization initiator that at least one side's of 2 acryloyl groups and methacryl the radical polymerization of optical polymerism resinous principle begins, can use known optical free radical polymerization initiator.Can enumerate the following optical free radical polymerization initiator of picture particularly.
(1) as taking the hydrogen type by force, benzophenone, 2 is arranged, benzophenones such as 4-benzophenone of dichloro, methyl o-benzoylbenzoate, benzil, 4,4 '-benzil classes such as benzil of dimethoxy, ketones such as camphorquinone etc.
(2) as the light fracture mode; benzoin is arranged; benzoin methylether; benzoin classes such as benzoin ethyl ether; acetophenone; 4-phenoxy group ww-dichloroacetophenone; acetophenone classes such as the 4-tert-butyl group-ww-dichloroacetophenone; 2-hydroxy-2-methyl-1-phenyl-propane-1-ketone; 1-hydroxyl-cyclohexyl-Alpha-hydroxy ketones such as phenyl-ketone; methyl isobutyryl-phosphinic acids methyl esters; methyl isobutyryl-phosphinic acids phenyl ester; 2; 4; 6-trimethylbenzene formyl diphenyl phosphine oxide; two (2; 4; 6-trimethylbenzene formyl)-phenyl phosphine oxide; two (2,6-dimethoxy benzoyl)-2,4; acylphosphine oxide classes such as 4-tri-methyl-amyl phosphine oxide etc., but be not limited to these.These optical free radical polymerization initiators can be a kind, but also several are also used.
Even among these optical free radical polymerization initiators, consider from the photo-curable aspect, preferentially select Alpha-hydroxy ketone and acylphosphine oxide class.These optical free radical polymerization initiators; (A) 2-cyanoacrylate and (B) in molecule, have a total amount of the optical polymerism resinous principle of 2 (methyl) acryloyl groups relatively; contain more than or equal to 0.01 weight %, be less than or equal to 10 weight %, preferably contain more than or equal to 0.1 weight %, be less than or equal to 5 weight %.
Zero other composition
In the cyanoacrylate resin combination of the photo-curable that in having the present invention, uses, as desired composition, can in normally used scope, cooperate stabilizer, polymerization accelerant, polymerization initiator, thickener and other the additive shown in following aptly.
[stabilizer]
It is additive for the storage-stable that improves the curable encapsulant, can enumerate anionic polymerization stabilizers such as sulfur dioxide, nitric oxide, hydrogen fluoride, sultone compound, BF3 complex compound, methanesulfonic acid, p-methyl benzenesulfonic acid, or quinhydrones, quinhydrones monomethyl ether, catechol, 1,2, radical polymerization stabilizers such as 3-benzenetriol.
[polymerization accelerant]
Be the additive for the anionic polymerization that improves the curable encapsulant, the additive that binding speed is accelerated, can enumerate crown ether-like, sila crown ether-like, カ リ Network ス ア レ Application class etc.
[polymerization initiator]
Be in order to improve the free-radical polymerised additive of curable encapsulant, to add organic peroxides such as di-tert-butyl hydrogen peroxide, cumene hydroperoxide.
[thickener]
Cyanoacrylate resin combination with photo-curable of the present invention, viscosity in the time of 25 ℃ is to be less than or equal to 200mPas, in order to adjust impregnability in this scope to electric wire, thickener can be used, polymethyl methacrylate, methyl methacrylate/(methyl) acrylate copolymer, cellulose derivative etc. can be enumerated.
Except that above-mentioned, add adaptation imparting agent, dyestuff, spices, filler, crosslinking agent, flexibilizer ( Off Na one) etc. according to purpose.About these, technique known also all can be used in the past.
Cyanoacrylate resin combination with the photo-curable that uses among the present invention, the viscosity under 25 ℃ must be to be less than or equal to 200mPas with E type viscometer determining, preferred viscosity is to be less than or equal to 100mPas.When the viscosity of curable encapsulant is higher than 200mPas, the curable encapsulant utilizes soaking into of the gap of capillarity between heart yearn to become insufficient, in addition, thickness attenuation as the cationic polymerization resins layer in the lining of the 2nd bulkhead, or almost forfeiture, can not embody sufficient waterproof effect.
About connecting portion method for waterproofing, below explain with reference to the accompanying drawings according to coated electric wire of the present invention.
In the connection processing portion 200 of wire terminations shown in Figure 1; the heart yearn 71b that exposes from the covered part 71a of several coated electric wires 71 is each other when connecting portion 75 is electrically connected; near the connecting portion 75 of coated electric wire and the connecting portion 75 of this coated electric wire 71 covered part 71a is made of the electromagnetic insulating properties synthetic resin that sees through 200～500nm, utilizes the protective cap 60 connecting portion, that the round-ended cylinder shape is arranged of protective covering electric wire to cover.Be full of above-mentioned protective cap 60 and heart yearn 71b then and form curable encapsulant (cyanoacrylate resin combination) 65 between near the heart yearn 71b of connecting portion 75 the 71a of lining portion with photo-curable; by rayed generation radical polymerization, and form thick, firm layer.
[method of attachment of electric wire]
Method of attachment to the electric wire in the connection processing portion 200 of such wire terminations is illustrated.At first, remove the covered part 71a of the end of several electric wires 71, every heart yearn 71b is exposed after, roughly consistent for the tip, make every wire 71 mutually along.The state that adheres to mutually at the heart yearn 71b that makes every wire 71 forms the connecting portion 75 that heart yearn 71b is electrically connected mutually by deposited or crimping then, makes electric wire assembly 70 as shown in Figure 2.
[encapsulating method between the dipping method of curable encapsulant, gap between heart yearn and electric wire]
Then; as shown in Figure 3; curable encapsulant 65 in inside has been injected the protective cap that bottom tube-like is arranged 60 of curable encapsulant 65 in advance inserts the end portion of said wires assemblies 70; not only connecting portion 75 and heart yearn 71b then, and near the 71a of lining portion the heart yearn 71b is immersed in the above-mentioned curable encapsulant 65.Here, near the 71a of lining portion of so-called heart yearn 71b, mean usually lining portion more than or equal to 3mm, be less than or equal to 20mm.If covered part is too short, the danger of waterproof reliability step-down is just arranged, if long, it is excessive that handling part just becomes, for example in the occasion of bunch, the operability variation, meanwhile, it is many that the waste of material becomes.The layer of above-mentioned curable encapsulant 65 is thicker, the short time of not taking place to be produced by anionic polymerization solidifies, therefore can insert the end portion of said wires assembly 70 easily, and the viscosity during owing to 25 ℃ under the use its uncured state is the curable encapsulant 65 that is less than or equal to 200mPas, therefore utilize the wetting-out rate in the gap of capillarity between heart yearn fast, after the end portion of said wires assembly 70 was inserted the several seconds, curable encapsulant 65 was just finished soaking into of between heart yearn gap fully.The part on the curable encapsulant that soaked into 65 contact heart yearn surfaces with the moisture on the surface that is present in heart yearn as initator generation anionic polymerization and driving fit on heart yearn, as waterproof and sealing material (sealant) performance function.In addition; be soaked between electric wire, spread; the curable encapsulant 65 that does not contact from the part of the light of protective cap 60 outsides also solidifies as initator generation anionic polymerization with the moisture that is present in covered part 71a surface, as the waterproof and sealing material between electric wire (sealant) performance function.
[process for photocuring of curable encapsulant and encapsulating method]
Be filled in the uncured portion of the terminal insertion portion and the curable encapsulant 65 between the protective cap 60 of said wires assembly 70; electromagnetic wave as the wavelength that the curable encapsulant is solidified; for example by the irradiation visible light or the ultraviolet ray or both; just radical polymerization can easily take place, the short time can finish connecting portion 75, heart yearn 71b and heart yearn 71b (connecting portion 75) but near the photocuring of rayed part of covered part 71a.
[necessary amount in electromagnetic wave irradiation source and the curing]
As the electromagnetic wave irradiation source of using among the present invention, can enumerate Cooper-Hewitt lamp, high-pressure mercury-vapor lamp, xenon lamp, metal halide lamp etc.Electromagnetic wave must be the electromagnetic wave that makes the curable wavelength of curable encapsulant, but the normally ultraviolet ray of 200～500nm and visible light.Light quantity necessary, that see through protective cap 60 is engaged in the kind of the Photoepolymerizationinitiater initiater in the used curable encapsulant and the influence of amount, thereby can not be limited in the photocuring of curable encapsulant, is defined as more than or equal to 100mJ/cm usually
2, especially preferably be defined as more than or equal to 200mJ/cm
2, be less than or equal to 10000mJ/cm
2
[protective cap]
The material of protective cap is so long as insulating properties; and through the electromagnetic wave that makes the curable wavelength of used curable encapsulant; normally more than or equal to 200nm, be less than or equal to 500nm electromagnetic material just; specifically; can enumerate resins such as flexible vinyl chloride resin, polypropylene, polyethylene, polysiloxanes, acrylic compounds, Merlon, polyester, polyamide, polytetrafluoroethylene, but be not limited to these.
The shape of protective cap; if connecting portion that can the protective covering electric wire is not subjected to the impact from electricity, machinery or chemistry; just without limits; bottom tube-like, taper, bucket-shaped etc. are for example arranged; shape about peristome and recess; in order to insert the connecting portion of coated electric wire easily, may be prescribed as shape arbitrarily.
Moreover; not to see through protective cap to supply with electromagnetic wave; but when utilizing in addition method that the curable encapsulant is supplied with electromagnetic wave; for example the lining portion with coated electric wire imports optical fiber together in the curable encapsulant; this optical fiber is as the means of lead-in light; when supplying with electromagnetic wave etc. in the curable encapsulant, protective cap can use the electromagnetic material that can not see through curable used curable encapsulant wavelength.Moreover at this moment, after the curing of curable encapsulant, optical fiber also can cut off in position.
As mentioned above; the present invention has the connection processing portion that inserts coated electric wire in the protective cap of cyanoacrylate resin combination of photo-curable holding low viscosity, extensibility than higher certain; after flooding; shine electromagnetic simple process, can implement extremely simple, rapid, low-cost and reliable water-proofing treatment at the connecting portion of the coated electric wire that is electrically connected.
Embodiment
Below, enumerate embodiment, illustrate in greater detail the present invention.Moreover the performance evaluation in each embodiment and the Comparative Examples is carried out according to following method.
＜protective cap 〉
Flexible vinyl chloride resin system, thickness: 1mm
＜electric wire assembly 〉
The end that covers a side of electric wire at 10 velamens connects the heart yearn crimping and the electric wire assembly of formation
＜have a cyanoacrylate resin combination of photo-curable 〉
The curable encapsulant of forming shown in preparation table 1 and the table 2 is estimated each characteristic as following.Moreover, in order to contrast, study similarly for the curable encapsulant of forming shown in the table 3.
[viscosity]
Use E type viscosimeter, the viscosity when measuring 25 ℃.
[setting time (set time)]
According to JIS K6861, use the test piece (test piece) of copper, the time when reaching the adhesion strength of regulation is as setting time.
[photo-curable]
Use ア イ グ ラ Off イ Star Network ス Co., Ltd. system コ Application ベ ア type light illuminator (metal halide lamp 1500w), measure the accumulative total light quantity of necessity when thick 2mm is solidified.In addition, the mensuration of light quantity is used at the center that has at wavelength 365nm place of ゥ シ オ Electric Co., Ltd system and carried out by the light-receiving device UVD-C365 of light and accumulative total quantometer UIT-150.
[tension fracture elongation rate]
The tension fracture elongation rate of solidfied material for No. 3 coupons of the dumb-bell shape of making according to JIS K6251 (thickness 2mm), under 23 ℃, the environment of relative humidity 50%, under the condition of draw speed: 10mm/min, uses cupping machine to measure.
[curable encapsulant suction lift]
In protective cap, inject 1g curable encapsulant with glass pipette; insert the electric wire assembly therein; use ア イ グ ラ Off イ Star Network ス system light illuminator (high-pressure mercury-vapor lamp 600W), carry out rayed (accumulative total light quantity: 6000mJ/cm from the both sides of clamping protective cap
2).After 24 hours, divide incision with the insulative body portion of implementing the electric wire of water-proofing treatment like this, measure the suction lift of curable encapsulant.
[cold-resistant thermal shock]
To carrying out cold shock testing, measure until the cycle-index that be full of cracks takes place in the curable encapsulant with the above-mentioned electric wire that has similarly carried out water-proofing treatment.
Experimental condition: warm condition: 100 ℃, 60 minutes.Cool condition :-40 ℃, 60 minutes.
Moreover the ellipsis in the table 1 is represented following compound (but the Tg in the parantheses represents the glass transition temperature about the solidfied material of compound).
M-1310: polyalcohol type urethanes diacrylate (Tg:-25 ℃), HX-620: polyester diacrylate (Tg:-8 ℃), M-225 (Tg:-8 ℃) and M-270 (Tg:-32 ℃): polypropyleneglycol diacrylate, M-260: polyethyleneglycol diacrylate (Tg:-34 ℃), M-220: tripropylene glycol diacrylate (Tg:90 ℃), DPHA: dipentaerythritol five acrylate and dipentaerythritol acrylate (Tg:＞250 ℃).Irg819: two (2,4,6-trimethylbenzene formyl)-phenyl phosphine oxide, Irg1800:1-hydroxyl-cyclohexyl-phenyl-ketone and two (2,6-dimethoxy benzoyl)-2,4,4-tri-methyl-amyl phosphine oxide with 75: 25 mixture of weight ratio, DC1173:2-hydroxy-2-methyl-1-phenyl-propane-1-ketone, Irg184:1-hydroxyl-cyclohexyl-phenyl-ketone.PMMA: polymethyl methacrylate.
Table 1
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | |||
| Composition (use level (weight %) | (A) 2-cyanoacrylate | Isobutyl ester (50) | Isobutyl ester (70) | Isobutyl ester (90) | Isobutyl ester (70) | Isobutyl ester (70) | |
| (B) photopolymerization resin | M-1310(50) | M-1310(30) | M-1310(10) | HX-620(30) | HX-620(30) | ||
| (C) optical free radical polymerization initiator | Irg819(3) | Irg819(3) | Irg819(3) | Irg819(3) | Irg819(3) | ||
| Thickener | PMMA(3) | ||||||
| Estimate | Viscosity | mPa· | 30 | 13 | 10 | 10 | 140 |
| Setting time | Second | 90 | 10 | 5 | 10 | 20 | |
| Photo-curable | mJ/cm 2 | 4000 | 4000 | 6000 | 4000 | 4000 | |
| Tension fracture elongation rate | ％ | 120 | 105 | 35 | 40 | 20 | |
| The electric wire suction lift | mm | 15 | 30 | 30 | 30 | 5 | |
| Cold-resistant thermal shock | Cycle-index | ＞1000 | ＞1000 | 600 | 600 | 300 | |
Table 2
| Embodiment 6 | Embodiment 7 | Embodiment 8 | Embodiment 9 | |||
| Composition (use level (weight %) | (A) 2-cyanoacrylate | Isobutyl ester (70) | Isobutyl ester (70) | Isobutyl ester (70) | Ethoxy ethyl ester (70) | |
| (B) photopolymerization resin | M-225(30) | M-260(30) | M-270(30) | HX-620(30) | ||
| (C) optical free radical polymerization initiator | Irg819(3) | Irg1800(3) | Irg819(2) | Irg819(2) | ||
| Thickener | DC1173(2) | Irg184(2) | ||||
| Estimate | Viscosity | mPa·s | 6 | 10 | 8 | 18 |
| Setting time | Second | 10 | 20 | 10 | 5 | |
| Photo-curable | mJ/cm 2 | 4000 | 4000 | 6000 | 6000 | |
| Tension fracture elongation rate | ％ | 28 | 80 | 78 | 58 | |
| The electric wire suction lift | mm | 35 | 30 | 30 | 30 | |
| Cold-resistant thermal shock | Cycle-index | 100 | ＞1000 | ＞1000 | ＞1000 | |
Table 3
| Comparative Examples 1 | Comparative Examples 2 | Comparative Examples 3 | Comparative Examples 4 | |||
| Composition (use level (weight %) | (A) 2-cyanoacrylate | Isobutyl ester (70) | Isobutyl ester (70) | Isobutyl ester (70) | Ethyl ester (100) | |
| (B) photopolymerization resin | M-220(30) | DPHA(30) | HX-620(30) | |||
| (C) optical free radical polymerization initiator | Irg819(3) | Irg819(3) | Irg819(3) | |||
| Thickener | PMMA(5) | |||||
| Ethyl dicyclopentadienyl iron (5) | ||||||
| Estimate | Viscosity | mpa·s | 5 | 10 | 550 | 2 |
| Setting time | Second | 10 | 10 | 30 | 3 | |
| Photo-curable | mJ/cm 2 | 4000 | 2000 | - | 2000 | |
| Tension fracture elongation rate | ％ | 5 | 0 | - | 3 | |
| The electric wire suction lift | mm | 35 | 30 | 0 | 35 | |
| Cold-resistant thermal shock | Cycle-index | 0 | 0 | - | 0 | |
"-" expression is estimated in the table.
Can judge from last tabulation 1～3, the cyanoacrylate resin combination that uses among the present invention with photo-curable, viscosity is less than or equal to 200mPas, tension fracture elongation rate is the scope more than or equal to 20%, cyanoacrylate resin combination with such photo-curable, the setting time relevant with productivity ratio all is to be less than or equal to 180 seconds, therefore can guarantee good productivity ratio, even and if the lower cost device, photo-curable also is to guarantee the needed 10000mJ/cm of being less than or equal to of good productivity ratio
2, in addition we know, satisfy the 5mm of the electric wire suction lift obtain sufficient water proofing property or higher, have again, have necessary patience more than or equal to 100 times in the cold-resistant thermal shock of target of anti-environmental change when long-term use the or resistance to impact.
In addition, be applied to Wiring harness for vehicle, during test under the environment that automobile produced of the reality of carrying out to consider, confirm that the connecting portion of relevant embodiments of the invention is kept sufficient water proofing property at the connecting portion of the embodiment of relevant above-mentioned the present application.
Industrial applicibility
The present invention can implement simple, rapid, low-cost to the connecting portion of the coated electric wire that can use in Wiring harness for vehicle etc., be electrically connected, reliably water-proofing treatment.
According to the present invention, moisture is suppressed to the intrusion of insulating component inside, therefore do not have the corrosion of heart yearn or the electric wire that caused to the intrusion of coating inside by moisture in the current leakage that flows, to water-fast, resistant to saline solution Reliability Enhancement.
Claims (3)
1. the connecting portion method for waterproofing of coated electric wire; be after in the protective cap of the connecting portion of protective covering electric wire, injecting the curable encapsulant; near in the sealing material connecting portion of the connecting portion of insertion coated electric wire and this coated electric wire covered part; then make the connecting portion method for waterproofing of the coated electric wire of this curable encapsulant curing; it is characterized in that; this curable encapsulant is that the viscosity 25 ℃ the time is less than or equal to 200mPas under its uncured state; and the tension fracture elongation rate after solidifying is more than or equal to 20% the cyanoacrylate resin combination with photo-curable, and above-mentioned cured is undertaken by the electromagnetic wave of the wavelength that above-mentioned curable encapsulant irradiation made this curable encapsulant and can solidify.
2. the connecting portion method for waterproofing of coated electric wire according to claim 1, it is characterized in that, above-mentioned cyanoacrylate resin combination with photo-curable contains following (A), (B) and (C), and the tension fracture elongation rate of solidfied material of cyanoacrylate resin combination with this photo-curable is more than or equal to 20%
(A) 2-cyanoacrylate,
(B) in molecule, have at least one side's of 2 acryloyl groups and methacryl optical polymerism resinous principle,
(C) optical free radical polymerization initiator.
3. the connecting portion method for waterproofing of coated electric wire according to claim 1 and 2; it is characterized in that; above-mentioned protective cap is made by seeing through above-mentioned electromagnetic material; and the electromagnetic wave that makes above-mentioned wavelength sees through this protective cap from the outside of this protective cap, is radiated on the above-mentioned curable encapsulant.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2004019039 | 2004-01-27 | ||
| JP019039/2004 | 2004-01-27 |
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| CN1914771A true CN1914771A (en) | 2007-02-14 |
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| Application Number | Title | Priority Date | Filing Date |
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| CNA2005800032730A Pending CN1914771A (en) | 2004-01-27 | 2005-01-27 | Method for waterproofing connection part of covered wire |
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| JP (1) | JPWO2005071792A1 (en) |
| CN (1) | CN1914771A (en) |
| WO (1) | WO2005071792A1 (en) |
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| Publication number | Publication date |
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| JPWO2005071792A1 (en) | 2007-07-26 |
| WO2005071792A1 (en) | 2005-08-04 |
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