JP7704556B2 - Conductor sealing composition, electric wire with terminal, wire harness, and method for manufacturing electric wire with terminal and wire harness - Google Patents

Description

The present invention relates to a composition for sealing conductor wires, a terminal-attached electric wire, a wire harness, and a method for manufacturing the terminal-attached electric wire and the wire harness.

2. Description of the Related Art Wire harnesses, each of which is made up of a plurality of insulated wires, are used as electrical wiring in automobiles, home appliances, and the like.
The wire harness has an exposed bundle portion including a splice portion (joint portion) formed by stripping the insulation layer of each insulated electric wire and welding or crimping a part of the exposed conductor wire to each other, and a part (coated bundle portion) in which the parts of the insulated electric wires covered with the insulation layer are bundled together. The exposed bundle portion is usually covered with resin to prevent corrosion due to water, electric leakage, etc.
For example, Patent Document 1 describes a composition liquid containing at least a photopolymerization initiator, a thermal radical polymerization initiator, a redox catalyst, and a polymerizable compound, and a method for manufacturing a wire harness using the composition liquid. According to the technology described in Patent Document 1, the exposed bundle portion and the ends of the exposed bundle portion and the covered bundle portion adjacent to the exposed bundle portion are sealed with the composition liquid, thereby increasing the airtightness of the sealed portion and increasing the waterproofness (water stoppage) of the wire harness.
Patent Document 2 also describes a liquid composition containing at least a photopolymerization initiator, a thermal radical polymerization initiator, and a polymerizable compound, and a method for manufacturing a wire harness using the liquid composition. The technology described in Patent Document 2 also claims that the waterproofness (water-stopping property) of the obtained wire harness can be improved by sealing the exposed bundle portion and the ends of the exposed bundle portion and the covered bundle portion adjacent to the exposed bundle portion with the liquid composition.

Patent No. 5526731 Patent No. 5526732

However, the inventors' investigations have revealed that the curing properties of the liquid compositions described in the above-mentioned patent documents are easily impaired by the effects of oxygen, etc., and as a result, the exposed bundle parts cannot be adequately sealed deep inside, and there are limitations to improving the water-stopping properties. In addition, it has been found that the thermal radical polymerization initiators contained in the liquid compositions described in the above-mentioned patent documents are easily decomposed, and the liquid compositions have poor storage stability.

In view of the above circumstances, the present invention aims to provide a conductor sealing composition that has excellent storage stability and exhibits excellent curing properties, and is capable of imparting a sufficiently high level of water-stopping properties to the joints of multiple conductors while suppressing corrosion of the conductors due to the curing reaction. The present invention also aims to provide an insulated electric wire with terminals and a wire harness that use the conductor sealing composition, as well as methods for producing the same.

That is, the above problems were solved by the following means.
＜1＞
A composition for sealing a conductor wire, comprising the following components (A), (B), (D) and (E), or the following components (C), (D) and (E):
(A) radically polymerizable compound (B) cationic polymerizable compound (C) radically polymerizable and cationic polymerizable compound (D) photoradical polymerization initiator (E) cationic polymerization initiator <2>
The conductor sealing composition according to <1>, wherein the component (E) contains a thermal latent cationic polymerization initiator.
＜3＞
The composition for sealing a conductor wire according to <1> or <2>, wherein, in a total content of 100 parts by mass of the components (A) and (B), a content of the component (A) is 50 to 90 parts by mass, and a content of the component (B) is 10 to 50 parts by mass.
＜4＞
A terminal-attached electric wire in which a coated conductor wire and a terminal are connected,
The coated conductor wire includes a coating portion and a conductor wire exposed from a tip of the coating portion,
The terminal has a terminal body and a crimping portion, and the crimping portion includes a conductor crimping portion to which the conductor wire is crimped, a coating crimping portion to which the coating portion is crimped, and an inter-barrel portion between the conductor crimping portion and the coating crimping portion, and at least a portion between the coating crimping portion and an end of the exposed conductor wire and other than the crimping portion is sealed with a cured product of the conductor sealing composition according to any one of <1> to <3>.
＜5＞
A plurality of electric wires each having an exposed conductor portion and a coated conductor portion are bundled together,
The exposed conductor portion is welded to form a joint,
A wire harness, wherein the conductor joint portion is sealed with a cured product of the conductor sealing composition according to any one of <1> to <3>.
＜6＞
A method for manufacturing an electric wire with a terminal in which a coated conductor wire and a terminal are connected, comprising the steps of:
The coated conductor wire includes a coating portion and a conductor wire exposed from a tip of the coating portion,
The terminal has a terminal body and a crimping portion, and the crimping portion includes a conductor crimping portion to which the conductor wire is crimped, a coating crimping portion to which the coating portion is crimped, and an inter-barrel portion between the conductor crimping portion and the coating crimping portion. The method for manufacturing an electric wire with a terminal includes: a step (1) of applying the conductor sealing composition according to any one of <1> to <3> to at least a portion between the coating crimping portion and an end of the exposed conductor wire and other than the crimping portion; and a step (2) of curing the conductor sealing composition.
＜７＞
A method for producing a wire harness, comprising: a step (1) of applying the conductor sealing composition according to any one of <1> to <3> to a joint portion of conductors exposed from a plurality of electric wires; and a step (2) of curing the conductor sealing composition.
＜8＞
The method for manufacturing a wire harness according to <7>, further comprising ultrasonically welding exposed conductors from a plurality of electric wires to form joints of the exposed conductors.
＜9＞
The method for producing a wire harness according to <7> or <8>, wherein the steps (1) and (2) are the following steps (1a) and (2a):
Step (1a): A step of immersing the joint in the conductor sealing composition in an insulating container having an ultraviolet transmittance of 50% or more and at least a part of which is flat. Step (2a): A step of irradiating the insulating container with ultraviolet light in a ring shape from the outside.

The conductor sealing composition of the present invention has excellent storage stability. In addition, the conductor sealing composition of the present invention exhibits excellent curability, and is capable of imparting a sufficiently high level of water-stopping property to a joint between a plurality of conductors while suppressing corrosion of the conductors due to a curing reaction.
The wire harness and the electric wire with terminal of the present invention are excellent in electrical conductivity and watertightness because corrosion of the conductor is suppressed.
According to the manufacturing method of the electric wire with terminal of the present invention, the electric wire with terminal of the present invention can be obtained. Also, according to the manufacturing method of the wire harness of the present invention, the wire harness of the present invention can be obtained.

FIG. 1 is a perspective view showing one embodiment of an electric wire with a terminal of the present invention. FIG. 2 is a cross-sectional view showing one embodiment of an electric wire with a terminal of the present invention. FIG. 3 is a diagram including a joint portion of an embodiment of the wire harness of the present invention. FIG. 4 is a diagram showing a method for testing the waterproofing property of an electric wire with a terminal. FIG. 5 is a diagram showing a method for testing the waterproofness of a wire harness.

[Conductor sealing composition]
The conductor sealing composition of the present invention contains the following components (A), (B), (D), and (E), or the following components (C), (D), and (E). Hereinafter, the "conductor sealing composition" may be simply referred to as the "composition".
(A) Radically Polymerizable Compound (Component (A))
(B) Cationic polymerizable compound (component (B))
(C) Radically Polymerizable and Cationic Polymerizable Compound (Component (C))
(D) Photoradical polymerization initiator (component (D))
(E) Cationic Polymerization Initiator (Component (E))
Components (A) to (E) and the optional components described below may each be used alone or in combination of two or more.
Hereinafter, a form in which the conductor sealing composition of the present invention contains the above components (A), (B), (D), and (E), i.e., a form in which the above components (A), (B), (D), and (E) are essential components, will be referred to as "Form 1." On the other hand, a form in which the conductor sealing composition of the present invention contains the above components (C), (D), and (E), i.e., a form in which the above components (C), (D), and (E) are essential components, will be referred to as "Form 2."
The components contained in the conductor sealing composition of the present invention will be described below.

<(A) Radically Polymerizable Compound>
The component (A) used in the present invention is a compound capable of undergoing radical polymerization by the action of a photoradical polymerization initiator, that is, a compound having a radical polymerizable group. The component (A) does not have a cationic polymerizable group.
The component (A) used in the present invention may be a monofunctional radically polymerizable compound (a compound having one radically polymerizable group) or a polyfunctional radically polymerizable compound (a compound having two or more (preferably 2 to 4) radically polymerizable groups). As the component (A) used in the present invention, a monofunctional radically polymerizable compound is preferable.

The radical polymerizable group is not particularly limited as long as it is a functional group capable of undergoing a radical polymerization reaction, and examples thereof include groups containing a carbon-carbon double bond, and specific examples thereof include a vinyl group and a (meth)acryloyl group. When component (A) has two or more radical polymerizable groups, these radical polymerizable groups may be the same or different.
Component (A) may be an oligomer or a polymer. In the present invention, the term "(meth)acryloyl group" refers to both an acryloyl group and a methacryloyl group in one term.
The molecular weight of the component (A) is not particularly limited and is, for example, 20 to 1,000, preferably 50 to 500, and more preferably 80 to 300.
When component (A) is an oligomer or polymer, the weight average molecular weight of component (A) is not particularly limited and is, for example, 40 to 10,000, preferably 100 to 5,000, and more preferably 200 to 3,000.

In the present invention, the weight average molecular weight of an oligomer or polymer is a value measured as a polystyrene-equivalent molecular weight by gel permeation chromatography (GPC) under the following measurement conditions.
Measurement device: Nexera XR GPC (product name, manufactured by Shimadzu Corporation)
Column: Shodex KF806L (trade name, manufactured by Showa Denko K.K.), 3 columns connected together Eluent: Tetrahydrofuran Flow rate: 0.8 mL/min
Measurement temperature: 40
Detection means: RID (Differential Refraction Detector)

As the component (A), a radically polymerizable compound having a (meth)acryloyl group is preferred, and specifically, a (meth)acrylic acid ester is preferred.
Specific examples of component (A) include the compounds used in the examples described below and the compounds shown below, but the present invention is not limited to these compounds.
Specifically, isobornyl (meth)acrylate, bornyl (meth)acrylate, tricyclodecanyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, 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, 5-hydroxypropyl ... 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, ) 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 acrylate, diacetone (meth)acrylamide, isobutoxymethyl (meth)acrylamide, N,N-dimethyl (meth)acrylamide, t-octyl (meth)acrylamide, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, 7-amino-3,7-dimethyloctyl (meth)acrylate, N,N-diethyl (meth)acrylamide and N,N-dimethylaminopropyl (meth)acrylamide mono(meth)acrylates, as well as 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 Licor 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)isocyanurate tri(meth)acrylate, tris(2-hydroxyethyl)isocyanurate di(meth)acrylate, tricyclodecane dimethylol di(meth)acrylate, EO (ethylene oxide) adduct of bisphenol A Di(meth)acrylate, di(meth)acrylate of polyol of EO adduct or PO (propylene oxide) adduct of hydrogenated bisphenol A, epoxy (meth)acrylate of diglycidyl ether of bisphenol A to which (meth)acrylate is added, triethylene glycol divinyl ether, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, trimethylolpropane EO adduct tri(meth)acrylate, trisacryloyloxyethyl phosphate, pentaerythritol tri(meth)acrylate, Examples of the poly(meth)acrylate include 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 oligo(meth)acrylate, pentaerythritol oligo(meth)acrylate, (poly)urethane (meth)acrylate, and poly(meth)acrylate such as (poly)butadiene (meth)acrylate.

<(B) Cationic Polymerizable Compound>
The component (B) used in the present invention is a compound capable of undergoing cationic polymerization by the action of a cationic polymerization initiator, that is, a compound having a cationic polymerizable group. The component (B) does not have a radically polymerizable group.
Component (B) used in the present invention may be a monofunctional cationically polymerizable compound (a compound having one cationically polymerizable group) or a polyfunctional cationically polymerizable compound (a compound having two or more (preferably 2 to 4, more preferably 2 or 3, particularly preferably 2) cationically polymerizable groups). As component (B) used in the present invention, a polyfunctional cationically polymerizable compound is preferred.

The cationic polymerizable group is not particularly limited as long as it is a functional group capable of generating a cationic polymerization reaction, and examples thereof include an epoxy group, an oxetanyl group, and a vinyl ether group, with an epoxy group being preferred. When component (B) has two or more cationic polymerizable groups, these cationic polymerizable groups may be the same or different.
Component (B) may be oligomeric or polymeric.
The molecular weight of the component (B) is not particularly limited and is, for example, 20 to 1,000, preferably 50 to 500, and more preferably 80 to 300.
When component (B) is an oligomer or a polymer, the weight average molecular weight of component (B) is not particularly limited and is, for example, 40 to 10,000, preferably 100 to 5,000, and more preferably 200 to 3,000.
Specific examples of component (B) include the compounds used in the examples described below and the compounds shown below, but the present invention is not limited to these compounds.
Specific examples include epoxy compounds, oxetane compounds, oxolane compounds, cyclic acetal compounds, cyclic lactone compounds, thiirane compounds, thietane compounds, vinyl ether compounds, spiroorthoester compounds (reaction products of epoxy compounds and lactones), ethylenically unsaturated compounds, cyclic ether compounds, cyclic thioether compounds, and vinyl compounds.
Examples of the epoxy compound include bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, brominated bisphenol A diglycidyl ether, brominated bisphenol F diglycidyl ether, brominated bisphenol S diglycidyl ether, epoxy novolac resin, hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, hydrogenated bisphenol S diglycidyl ether, and 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexane carboxylate. , 2-(3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy)cyclohexane-meta-dioxane, bis(3,4-epoxycyclohexylmethyl)adipate, vinylcyclohexene oxide, 4-vinylepoxycyclohexane, bis(3,4-epoxy-6-methylcyclohexylmethyl)adipate, 3,4-epoxy-6-methylcyclohexyl-3',4'-epoxy-6'-methylcyclohexanecarboxylate, methylenebis(3,4-epoxycyclohexane), dicyclopentadiene diepoxide, di(3) of ethylene glycol ,4-epoxycyclohexylmethyl) ether, ethylene bis(3,4-epoxycyclohexane carboxylate), dioctyl epoxyhexahydrophthalate, di-2-ethylhexyl epoxyhexahydrophthalate, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane triglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ethers; aliphatic polyhydric alcohols such as ethylene glycol, propylene glycol, and glycerin. Examples of such glycidyl ethers include polyglycidyl ethers of polyether polyols obtained by adding one or more alkylene oxides to phenol; diglycidyl esters of aliphatic long-chain dibasic acids; monoglycidyl ethers of aliphatic higher alcohols; monoglycidyl ethers of polyether alcohols obtained by adding alkylene oxides to phenol, cresol, butylphenol, or these; glycidyl esters of higher fatty acids; epoxidized soybean oil, epoxy butyl stearate, epoxy octyl stearate, epoxidized linseed oil, and epoxidized polybutadiene.
Other specific examples include oxetanes such as trimethylene oxide, 3,3-dimethyloxetane, 3,3-dichloromethyloxetane, 3-ethyl-3-phenoxymethyloxetane, and bis(3-ethyl-3-methyloxy)butane; oxolanes such as tetrahydrofuran and 2,3-dimethyltetrahydrofuran; cyclic acetals such as trioxane, 1,3-dioxolane, and 1,3,6-trioxanecyclooctane; cyclic lactones such as β-propiolactone and ε-caprolactone; thiiranes such as ethylene sulfide, 1,2-propylene sulfide, and thioepichlorohydrin; thietanes such as 3,3-dimethylthietane; vinyl ethers such as ethylene glycol divinyl ether, triethylene glycol divinyl ether, and trimethylolpropane trivinyl ether; Examples include spiro orthoesters obtained by reacting an epoxy compound with a lactone; ethylenically unsaturated compounds such as vinylcyclohexane, isobutylene, and polybutadiene; and derivatives of the above-mentioned compounds.

In the embodiment 1, the combination of component (A) and component (B) is preferably a combination of a monofunctional radical polymerizable compound and a polyfunctional cationic polymerizable compound. By using a combination of a monofunctional radical polymerizable compound and a polyfunctional cationic polymerizable compound, the difference in crosslink density due to curing between the surface and the inside of the electric wire can be reduced. That is, the joint portion can be sealed with a cured product having a crosslink density that is nearly uniform throughout. In this way, the curability of the conductor sealing composition of the present invention can be further increased, and corrosion of the conductor can be suppressed. Note that the conductor sealing composition of the present invention may be used to seal the conductor and also to cover parts other than the conductor (for example, parts where the conductor is covered) depending on the form of use.
In the conductor sealing composition of the present invention, the ratio (mass ratio) of the contents of component (A) and component (B) is not particularly limited. From the viewpoint of effectively suppressing the inhibition of curing of the composition due to oxygen or moisture and the corrosion of the conductor due to acid, for example, in 100 parts by mass of the total content of components (A) and (B), the content of component (A) is preferably 10 to 90 parts by mass and the content of component (B) is preferably 10 to 90 parts by mass, the content of component (A) is more preferably 50 to 90 parts by mass and the content of component (B) is 10 to 50 parts by mass, and the content of component (A) is particularly preferably 55 to 75 parts by mass and the content of component (B) is 25 to 45 parts by mass.

<(C) Radically Polymerizable and Cationic Polymerizable Compound>
The component (C) used in the present invention is a compound which is radically polymerizable by the action of a radical polymerization initiator and cationic polymerizable by the action of a cationic polymerization initiator, that is, a compound which has both a radically polymerizable group and a cationic polymerizable group.
The radical polymerizable group and cationically polymerizable group contained in the component (C) used in the present invention include the radical polymerizable group contained in the above component (A) and the cationically polymerizable group contained in the above component (B), respectively.
The number of radically polymerizable groups and cationically polymerizable groups contained in component (C) is not particularly limited, and a total of 2 to 10 groups is preferable, 2 to 6 groups is more preferable, and 2 or 3 groups is even more preferable.

When component (C) has two or more radically polymerizable groups, these radically polymerizable groups may be the same or different. The same applies when component (C) has two or more cationically polymerizable groups.

Component (C) may be an oligomer or a polymer.
The molecular weight of the component (C) is not particularly limited and is, for example, 20 to 1,000, preferably 50 to 500, and more preferably 80 to 300.
When component (C) is an oligomer or a polymer, the weight average molecular weight of component (C) is not particularly limited and is, for example, 40 to 10,000, preferably 100 to 5,000, and more preferably 200 to 3,000.
Specific examples of component (C) include the compounds used in the Examples described below, but the present invention is not limited to these compounds.

<(D) Photoradical polymerization initiator>
Component (D) is not particularly limited as long as it is a substance that releases a substance (radical) that initiates radical polymerization upon irradiation with light. As component (D) of the present invention, a normal photoradical polymerization initiator can be used, and examples thereof include an acylphosphine oxide photoradical polymerization initiator, an acetophenone photoradical polymerization initiator, and an o-acyloxime photoradical polymerization initiator.
Specific examples of component (D) include the compounds used in the Examples described below, but the present invention is not limited to these compounds.

<(E) Cationic Polymerization Initiator>
In the present invention, as component (E), either a substance that releases a substance (cation) that initiates cationic polymerization upon irradiation with light (a photocationic polymerization initiator) or a substance that releases a cation upon heating (a thermal latent cationic polymerization initiator) can be used.
The cationic photopolymerization initiators that can be used in the present invention can be roughly divided into onium salt-based cationic photopolymerization initiators and nonionic cationic photopolymerization initiators. Note that, in the present invention, cationic photopolymerization initiators other than these may also be used.

The onium salt-based photocationic polymerization initiator is not particularly limited, and examples thereof include organic sulfonium salt compounds, organic oxonium salt compounds, organic ammonium salt compounds, organic phosphonium salt compounds, and organic iodonium salt compounds.Specific examples thereof include those having a counter anion such as B(C ₆ F ₅ ) ^{4 −} , SbF ₆ ⁻ , SbCl ₆ ⁻ , SbF ₄ ⁻ , FSO ₃ ⁻ , AsF ₆ ⁻ , PF ₆ ⁻ , BF ₄ ⁻ , or CF ₃ SO ₃ ⁻ .
Commercially available onium salt-based cationic photopolymerization initiators include, for example, IRGACURE (registered trademark, omitted hereinafter) 250, IRGACURE 270, IRGACURE 290 (all trade names, manufactured by BASF Corporation), WPI-113, WPI-116, WPI-169, WPI-170, WPI-124, WPAG-638, WPAG-469, WPAG-370, WPAG-367, WPAG-336 (all trade names, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), B2380, B2381, C1390, D2238, D2248, D2253, I0591, T1608, T1609, T2041, T2042 (all trade names, manufactured by Tokyo Chemical Industry Co., Ltd.), and Examples of such products include ADEKA CORPORATION, AT-6992, At-6976 (all trade names, manufactured by ACETO Corporation), CPI-100, CPI-100P, CPI-101A, CPI-200K, CPI-210S, CPI-310B, CPI-310FG, IK-1, IK-2 (all trade names, manufactured by San-Apro Ltd.), SP-056, SP-066, SP-130, SP-140, SP-150, SP-170, SP-171, SP-172 (all trade names, manufactured by ADEKA CORPORATION), CD-1010, CD-1011, CD-1012 (all trade names, manufactured by Sartomer Corporation), and PI2074 (manufactured by Rhodia Japan, trade name).

The nonionic photocationic polymerization initiator that can be used in the present invention is not particularly limited, and examples thereof include a phenacylsulfone-type photocationic polymerization initiator, an o-nitrobenzyl ester-type photocationic polymerization initiator, an iminosulfonate-type photocationic polymerization initiator, and a sulfonate ester-type photocationic polymerization initiator of N-hydroxyimide.
Specific examples of the nonionic photocationic polymerization initiator include sulfonyl diazomethane, oxime sulfonate, imide sulfonate, 2-nitrobenzyl sulfonate, disulfone, pyrogallol sulfonate, p-nitrobenzyl-9,10-dimethoxyanthracene-2-sulfonate, N-sulfonyl-phenylsulfonamide, trifluoromethanesulfonic acid-1,8-naphthalimide, nonafluorobutanesulfonic acid-1,8-naphthalimide, perfluorooctane sulfonic acid-1,8-naphthalimide, pentafluorobenzenesulfonic acid-1,8-naphthalimide, nonafluorobutanesulfonic acid-1,3,6-trioxo-3,6-dihydro-1H-11-thia-azacyclopentaanthracen-2-yl ester, nonafluorobutanesulfonic acid-8-isopropyl-1,3,6-trioxo-3,6-di Hydro-1H-11-thia-2-azacyclopentaanthracen-2-yl ester, 1,2-naphthoquinone-2-diazide-5-sulfonic acid chloride, 1,2-naphthoquinone-2-diazide-4-sulfonic acid chloride, 1,2-benzoquinone-2-diazide-4-sulfonic acid chloride, 1,2-naphthoquinone-2-diazide-5-sulfonic acid sodium salt, 1,2-naphthoquinone-2-diazide-4-sulfonic acid sodium salt 1,2-benzoquinone-2-diazide-4-sulfonate, sodium 1,2-naphthoquinone-2-diazide-5-sulfonate, potassium 1,2-naphthoquinone-2-diazide-4-sulfonate, potassium 1,2-benzoquinone-2-diazide-4-sulfonate, methyl 1,2-benzoquinone-2-diazide-5-sulfonate, and methyl 1,2-benzoquinone-2-diazide-4-sulfonate.
Examples of commercially available nonionic photocationic polymerization initiators include WPAG-145, WPAG-149, WPAG-170, and WPAG-199 (all trade names, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), D2963, F0362, M1209, and M1245 (all trade names, manufactured by Tokyo Chemical Industry Co., Ltd.), SP-082, SP-103, SP-601, and SP-606 (all trade names, manufactured by ADEKA Corporation), SIN-11 (trade name, manufactured by Sanbo Chemical Research Institute), and NT-1TF (trade name, manufactured by San-Apro Ltd.).

The thermal latent cationic polymerization initiator that can be used in the present invention is not particularly limited, and for example, an onium salt-based thermal cation generator such as an organic onium salt compound in which a cationic component and an anionic component are paired can be used. Examples of the cationic component include cations such as various onium salt-based compounds such as organic sulfonium salt compounds, organic oxonium salt compounds, organic ammonium salt compounds, organic phosphonium salt compounds, and organic iodonium salt compounds. On the other hand, examples of the anionic component include B(C ₆ F ₅ ) ₄ ^- , SbF ₆ ^- , SbF ₄ ^- , AsF ₆ ^- , PF ₆ ^- , BF ₄ ^- , and CF ₃ SO ₃ ^- .
Further, for example, organometallic complexes such as aluminum chelate complexes, iron-allene complexes, titanocene complexes, and arylsilanol-aluminum complexes, oxime sulfonate-based acid generators, diazomethane-based acid generators such as bisalkyl or bisarylsulfonyl diazomethanes and poly(bissulfonyl)diazomethanes, nitrobenzylsulfonate-based acid generators, iminosulfonate-based acid generators, disulfone-based acid generators, etc. also function as thermal acid generators. These may be used alone or in combination of two or more.
Commercially available thermal latent cationic polymerization initiators include, for example, K-PURE (registered trademark) CXC-1612, K-PURE CXC-1613, K-PURE CXC-1614, K-PURE CXC-1738, K-PURE CXC-2700, K-PURE TAG-2689, K-PURE TAG-2681, K-PURE TAG-2685, K-PURE TAG-2690, K-PURE TAG-2712, and K-PURE TAG-2713 (all of which are KING San-Aid SI-100L, San-Aid SI-110L, San-Aid SI-150L (all of which are product names manufactured by Sanshin Chemical Industry Co., Ltd.) and the like.

In the embodiment 1, the contents of components (D) and (E) in the composition of the present invention are not particularly limited. For example, 0.1 to 10 parts by mass, and preferably 0.2 to 8 parts by mass, of component (D) may be used relative to 100 parts by mass of component (A). On the other hand, 0.1 to 10 parts by mass, and preferably 1 to 10 parts by mass of component (E) may be used relative to 100 parts by mass of component (B).
In the embodiment 2, the content of components (D) and (E) in the composition of the present invention is not particularly limited. For example, 1 to 10 parts by mass of components (D) and (E) in total can be used relative to 100 parts by mass of component (C), and it is preferable to use 2 to 8 parts by mass. In the embodiment 2, for example, 0.1 to 10 parts by mass of component (D) can be used relative to 100 parts by mass of component (C), and it is preferable to use 0.2 to 8 parts by mass. In the embodiment 2, for example, 0.1 to 10 parts by mass of component (E) can be used, and it is preferable to use 1 to 10 parts by mass.

From the viewpoint of more efficiently curing the composition by the heat of the radical reaction, the component (E) of the present invention preferably contains a thermal latent cationic polymerization initiator.
In addition, from the viewpoint of more efficiently curing the composition by the combined effect of ultraviolet irradiation and the polymerization heat by ultraviolet irradiation, the component (E) of the present invention preferably contains a combination of a photocationic polymerization initiator and a thermal latent cationic polymerization initiator. In this case, the ratio (mass ratio) of the content of the photocationic polymerization initiator to the content of the thermal latent cationic polymerization initiator in the composition is not particularly limited, and can be, for example, the content of the photocationic polymerization initiator: the content of the thermal latent cationic polymerization initiator = 1:10 to 10:1, preferably 1:6 to 6:1, and more preferably 1:3 to 3:1.

<Other ingredients>
In addition to the above-mentioned components, the conductor sealing composition of the present invention may contain other components, such as a polymerization inhibitor, an antioxidant, a copper inhibitor, a flame retardant, a filler, a pigment, a dye, a defoamer, a leveling agent, a viscosity adjuster, etc., within the range that does not impair the effects of the present invention.
The conductor sealing composition of the present invention may contain component (C) within a range that does not impair the effects of the present invention in form 1. In form 1, the content of component (C) in the composition is preferably 10 parts by mass or less, and more preferably 5 parts by mass or less, per 100 parts by mass of the total content of components (A) and (B).
Furthermore, the conductor sealing composition of the present invention may contain components (A) and (B) within a range that does not impair the effects of the present invention in form 2. In form 2, the total content of components (A) and (B) per 100 parts by mass of component (C) in the composition is preferably 70 parts by mass or less, and more preferably 50 parts by mass or less.

[Method of manufacturing the conductor sealing composition]
The conductor sealing composition of the present invention can be obtained in form 1 by mixing the above-mentioned components (A), (B), (D), and (E) and, if necessary, the above-mentioned optional components, and kneading them with a commonly used kneading device such as a batch-type kneader such as a roll, kneader, or Banbury mixer, or a twin-screw extruder. Similarly, the conductor sealing composition of the present invention can be obtained in form 2 by mixing the above-mentioned components (C), (D), and (E) and, if necessary, the above-mentioned optional components, and kneading them with a commonly used kneading device such as a batch-type kneader such as a roll, kneader, or Banbury mixer, or a twin-screw extruder.

[Terminal wire]
The electric wire with terminal of the present invention is, for example, a coating material for an electric wire with terminal of JP 2020-164669 A, in which a cured product of the conductor sealing composition of the present invention is applied.
The electric wire with terminal of the present invention is an electric wire with terminal in which a covered conductor wire and a terminal are connected.
In the present invention, the coated conductor wire includes a coating portion and a conductor wire exposed from a tip of the coating portion,
The terminal has a terminal body and a crimping portion. The crimping portion comprises a conductor crimping portion to which the conductor wire is crimped, a coating crimping portion to which the coating portion is crimped, and a barrel-interface portion between the conductor crimping portion and the coating crimping portion, and at least the area between the coating crimping portion and the exposed end of the conductor wire and other than the crimping portion is sealed with a cured product of the conductor sealing composition of the present invention.
In the electric wire with terminal of the present invention, in the above-mentioned embodiment, it is preferable that the entire area from the coating crimp portion to the exposed end of the conductor is sealed with a cured product of the conductor sealing composition of the present invention.

Hereinafter, a preferred embodiment of the electric wire with terminal of the present invention will be described with reference to the drawings. Fig. 1 is a perspective view of an electric wire with terminal 10, and Fig. 2 is a cross-sectional view. Fig. 1 is a perspective view of a cured product (cured product of a conductor sealing composition) 17a. The electric wire with terminal 10 is configured by connecting a terminal 1 and a coated conductor wire 11.

The coated conductor 11 is composed of a conductor 13a made of aluminum or an aluminum alloy and a coating 15 that coats the conductor 13a. That is, the coated conductor 11 has the coating 15 and the conductor 13a exposed from its tip. The conductor 13a is, for example, a twisted wire in which multiple strands are twisted together.

The terminal 1 is an open barrel type and is made of, for example, copper or a copper alloy. A coated conductor wire 11 is connected to the terminal 1. The terminal 1 is configured by connecting a terminal body 3 and a crimping portion 5 via a transition portion 4. The transition portion 4, located between the crimping portion 5 and the terminal body 3, is open at the top.

The terminal body 3 is a plate material of a predetermined shape formed into a cylindrical body with a rectangular cross section. The terminal body 3 has an elastic contact piece inside, which is formed by folding the plate material into the rectangular cylindrical body. The terminal body 3 is connected by inserting a male terminal or the like into the front end. In the following explanation, an example is shown in which the terminal body 3 is a female terminal that allows the insertion of an insertion tab (not shown) of a male terminal or the like, but in the present invention, the detailed shape of the terminal body 3 is not particularly limited. For example, an insertion tab of a male terminal may be provided instead of the female terminal body 3.

The crimping portion 5 is the portion that is crimped to the coated conductor wire 11, and before crimping, the cross section perpendicular to the longitudinal direction of the terminal 1 has a generally U-shaped barrel shape. The crimping portion 5 of the terminal 1 is made up of a conductor crimping portion 7 that crimps the conductor wire 13 exposed from the coating portion 15 at the tip side of the coated conductor wire 11, a coating crimping portion 9 that crimps the coating portion 15 of the coated conductor wire 11, and a barrel portion 8 between the conductor crimping portion 7 and the coating crimping portion 9.

A portion of the inner surface of the conductor crimping portion 7 has serrations (not shown) in the width direction (perpendicular to the longitudinal direction). By forming the serrations in this manner, the oxide film on the surface of the conductor 13a is easily destroyed when the conductor 13 is crimped, and the contact area with the conductor 13a can be increased.

At the tip of the coated conductor wire 11, the coating 15 is stripped off to expose the internal conductor wire 13a. The coating 15 of the coated conductor wire 11 is crimped by the coating crimping part 9 of the terminal 1. The conductor wire 13a exposed when the coating 15 is stripped off is crimped by the conductor crimping part 7. The conductor wire 13a and the terminal 1 are electrically connected at the conductor crimping part 7. The end face of the coating 15 is located in the inter-barrel part 8 between the coating crimping part 9 and the conductor crimping part 7.

In the present invention, at least the portion between the coating crimping portion 9 and the exposed end of the conductor 13a and other than the crimping portion 5 is covered with the cured product 17a. That is, at least the portion between the coating crimping portion 9 and the exposed end of the conductor 13a and other than the crimping portion 5 is covered with the cured product 17a, and the conductor 13a is not exposed to the outside due to the cured product 17a. That is, the gap inside the conductor 13a is filled with the cured product of the conductor sealing composition of the present invention, and the surface of the conductor 13a has a layer (resin coating layer) made of a resin coating material obtained by curing the conductor sealing composition of the present invention.
In the electric wire with terminal of the present invention in the above-mentioned embodiment, it is preferable that the entire conductor 13a from the coating crimp portion 9 to the exposed end of the conductor 13a is sealed with a cured product 17a of the conductor sealing composition of the present invention.

[Method of manufacturing electric wire with terminal]
The manufacturing method of an electric wire with terminal of the present invention is a manufacturing method of an electric wire with terminal in which a coated conductor wire and a terminal are connected,
The coated conductor wire includes a coating portion and a conductor wire exposed from a tip of the coating portion,
The terminal has a terminal body and a crimping portion. The crimping portion includes a conductor crimping portion to which the conductor wire is crimped, a coating crimping portion to which the coating portion is crimped, and a barrel-interval portion between the conductor crimping portion and the coating crimping portion. The method includes a step (1) of applying the conductor sealing composition of the present invention to at least a portion between the coating crimping portion and the exposed end of the conductor wire other than the crimping portion, and a step (2) of curing the conductor sealing composition.
For the production of the electric wire with terminal of the present invention, for example, JP 2020-164669 A can be referred to. However, it is preferable that the curing of the conductor sealing composition of the present invention is performed in the same manner as the manufacturing method of the wire harness described later.

[Wire harness]
The wire harness of the present invention is formed by bundling a plurality of electric wires each having an exposed conductor portion and a conductor coating portion, and the exposed conductor portions are welded to form a joint portion (including a conductor bundle and a fiber core), and the conductor joint portion is sealed with a cured product of the conductor sealing composition of the present invention. That is, the gap inside the joint portion is filled with the cured product of the conductor sealing composition of the present invention, and the surface of the joint portion has a layer (resin coating layer) made of a resin coating material obtained by curing the conductor sealing composition of the present invention. The wire harness of the present invention may have an intermediate layer or a shielding layer between the joint portion and the resin coating layer.

[Manufacturing method of wire harness]
The wire harness of the present invention can be obtained by applying the conductor sealing composition of the present invention to the inside and surface of a joint formed by welding an exposed conductor portion, and curing the conductor sealing composition by irradiating the applied conductor sealing composition with ultraviolet light for 1 to 300 seconds. A photoradical polymerization initiator absorbs light to generate radicals, which initiates, for example, ring-opening polymerization. On the other hand, a photocationic polymerization initiator absorbs light and abstracts hydrogen to generate cations, which initiates, for example, ring-opening polymerization.
When a thermal latent cationic polymerization initiator is used, it is preferable to heat the composition at 60 to 150° C. (preferably 80 to 120° C.) for 1 to 120 minutes after the ultraviolet irradiation.
The joint is preferably formed by ultrasonically welding the exposed conductor portion. As long as the exposed conductor portion can be welded, the conditions of the ultrasonic welding are not particularly limited. For example, JP-A-2019-18226, JP-A-2019-181525, and JP-A-2019-186070 can be referenced.

The method of applying the conductor sealing composition to the joint is not particularly limited, and examples thereof include dip coating, dispenser coating, and cast coating, and dip coating is preferred. The dip coating can be performed by immersing the joint in an ultraviolet-transmitting insulating container containing the conductor sealing composition.
The ultraviolet transmittance of the insulating container is, for example, 30% or more, and preferably 50% or more.
The material of the insulating container is not particularly limited as long as it is insulating. For example, a container made of polyvinyl chloride, polyethylene, polypropylene, acrylic resin or polyethylene terephthalate can be used.
The shape of the insulating container is not particularly limited, and examples thereof include a flat shape, a cylindrical shape, and a shape that combines a flat shape and a cylindrical shape (all in cross section), and an insulating container that is at least partially flat is preferred.
The ultraviolet irradiation can be carried out by a normal method. In the present invention, it is preferable to use a ring-shaped ultraviolet irradiation device (ring light), place the container in the ring of the device, and irradiate the joint with ultraviolet rays while immersing the joint in the conductor sealing composition.

The conductor wire may be a single wire or a stranded wire, and may be a bare wire or a tin-plated or enamel-coated wire. Metal materials for forming the conductor wire include soft copper, copper alloys, aluminum, and the like.
The diameter and material of the conductor wire, the thickness of the resin coating layer, etc. are not particularly limited and may be appropriately determined depending on the purpose and application. The thickness of the resin coating layer is not particularly limited and is, for example, about 0.2 to 0.5 mm.

The shape and material of the conductor can be any conductor that is generally used in wire harnesses (copper, aluminum, etc.).

The present invention will be described in more detail with reference to examples. Note that the present invention should not be construed as being limited by these examples except as provided for in the present invention.

<Preparation of Conductor Sealing Composition>
According to the compositions (composition components (components (A) to (E), thermal radical polymerization initiator, and redox catalyst) and their contents) shown in Tables 1-1 and 1-2 described later (hereinafter, Tables 1-1 and 1-2 are collectively referred to as Table 1), the components were uniformly mixed and stirred in a light-shielded glass container for 10 minutes at 2,500 rpm using a Homo Disper manufactured by Primix Corporation, to obtain compositions for sealing conductor wires of Examples 1 to 18 and Comparative Examples 1 to 4.

[Test Example 1] Storage stability The conductor sealing compositions of Examples 1 to 18 and Comparative Examples 1 to 4 were allowed to stand at 25° C. for 30 days in the dark. The viscosity before and after storage was measured, and the viscosity after storage was evaluated according to the following evaluation criteria, with the viscosity before storage being taken as 100%. "3" to "5" are pass marks for this test.

- Viscosity evaluation criteria -
5: Less than 105% 4: 105% or more but less than 110% 3: 110% or more but less than 120% 2: 120% or more but less than 130% 1: 130% or more

The viscosity was measured in accordance with JIS Z 8803 (2011) using a No. 3 rotor at a rotation speed of 30 rpm.

<Making a Wire Harness>
Description will be given with reference to FIG.
The insulating coating layer was removed from three aluminum alloy electric wires 18 (alloy composition AL-Mg-Si, length 0.2 m, conductor cross-sectional area 0.75 mm ² (≒0.75 sq) ⁾ and two copper electric wires 18 (length 0.2 m, conductor cross-sectional area 0.75 mm 2 (≒0.75 sq)) up to 2 cm from one end to expose a part of the conductor 13b (conductor). The exposed conductor part was ultrasonically welded. A conductor sealing composition was poured into a flat or cylindrical container made of soft polyvinyl chloride, and the welded conductor part (joint 19) was immersed in the composition. The composition was cured by irradiating it with a 365 nm ultraviolet ring light from outside the container for 90 seconds, and the welded conductor part was sealed with the cured product 17b to obtain a wire harness 20.
The aluminum alloy electric wire used was ALVUS (product name) manufactured by Furukawa Electric Co., Ltd., and the copper electric wire used was CIVUS (product name) manufactured by Furukawa Electric Co., Ltd.
Ultrasonic welding was performed using an ultrasonic metal welding machine GMX-20DP (trade name) manufactured by Branson Co. A bundle of exposed conductor parts (4 mm wide on the horn side, 4.5 mm wide on the anvil side) was placed on an anvil and ultrasonic vibration was applied in the direction of gravity with a pressure of 2 kN for 2 seconds to weld them.
The output was 2400 W, the oscillation frequency was 15 kHz, and the amplitude at the tip of the horn under no load was about 53 μm (peak to peak).

<Preparation of wire with terminal>
The following description will be given with reference to FIG.
The insulating coating layer of three aluminum alloy electric wires (coated electric wires 11 in FIG. 1) (alloy composition AL-Mg-Si, length 0.2 m, conductor cross-sectional area 0.75 mm ² (≒0.75 sq)) was removed up to 2 cm from one end to expose part of the conductor 13a (conductor).
The three conducting wires 13a were fastened and fixed with the front leg portion, or the wire barrel portion, of the terminal fitting, and the covering portion 15 was fastened and fixed with the rear leg portion, or the insulation barrel, of the fitting of the terminal 1 (2.3II terminal (product name) manufactured by Furukawa AS), thereby electrically and mechanically connecting the conductor of the covered electric wire 11 and the fitting of the terminal 1.

[Performance evaluation]
Using each of the wire harnesses and electric wires with terminals produced as described above, performance evaluation was carried out by the following tests.

Test Example 2: Water Stoppage (1) Wire Harness (Examples 1 to 16 and Comparative Examples 1 to 4) The following will be described with reference to FIG.
A joint 19 of the wire harness was placed in a water tank 21 filled with water, and pressurized air was sent from the end of one of the five electric wires, 18, by a regulator 22 at an air pressure of 49 kPa. The pressurized air passed through the electric wire 18, and the presence or absence of air leakage from the other four electric wires was evaluated according to the following evaluation criteria. "3" to "5" indicate passing the test. Note that although FIG. 5 shows three electric wires other than the electric wire 18, the total number of electric wires in the wire harness used in the actual test was five (four electric wires were confirmed to have air leakage).

-Evaluation criteria-
5: There was no air leakage at all.
4: There was a small air leak from one electrical wire.
3: There was a slight air leak from 2 to 4 electrical wires.
2: There was a large air leak from 1 to 3 electrical wires.
1: There was a large air leak from four electrical wires.

(2) Regarding the wire with terminal (Examples 17 and 18)
Description will be given with reference to FIG.
One end of the electric wire with terminal 10 was placed in a water tank 21 filled with water, and pressurized air was sent from the end of one of the three covered electric wires 11 toward the terminal 1 by a regulator 22 at an air pressure of 49 kPa. The pressurized air passed through the covered electric wire 11, and the presence or absence of air leakage from the terminal was evaluated according to the following evaluation criteria. "3" to "5" are pass marks for this test.

-Evaluation criteria-
5: No air leakage whatsoever occurred for 10 seconds after the start of supplying pressurized air.
4: One or two air bubbles leaked within 10 seconds of starting to supply pressurized air.
3: Three to five air bubbles leaked within 10 seconds of starting to supply pressurized air.
2: Six to ten air bubbles leaked within 10 seconds of starting to supply pressurized air.
1: 11 or more air bubbles leaked within 10 seconds after the start of pressurized air supply.

Test Example 3 Curability The cured product covering the conductor of a wire harness was peeled off, and the curing reaction rate (%) of the side of the cured product that had been in contact with the conductor and the curing reaction rate (%) of the side of the cured product that had not been in contact with the conductor were measured, and the difference (%) in the curing reaction rate was evaluated according to the following evaluation criteria.
The cured product covering the conductor of the terminal-attached electric wire was peeled off, and the curing reaction rate (%) of the side of the cured product that had been in contact with the conductor and the curing reaction rate (%) of the side of the cured product that had not been in contact with the conductor were measured, and the difference (%) in the curing reaction rate was evaluated according to the following evaluation criteria.
The following evaluation criteria are common to Examples 1 to 18 and Comparative Examples 1 to 4. "3" to "5" are pass marks for this test.

-Evaluation criteria-
5: The difference in the curing reaction rate is less than 3%. 4: The difference in the curing reaction rate is 3% or more but less than 5%. 3: The difference in the curing reaction rate is 5% or more but less than 7%. 2: The difference in the curing reaction rate is 7% or more but less than 10%. 1: The difference in the curing reaction rate is 10% or more.

The curing reaction rate was measured by measuring the infrared absorption peak at a wave number of 1407 cm ^-1 with a peak appearing at a wavelength of 1506 to 1570 cm ^-1 as a reference peak.
Specifically, the curing reaction rate of the cured product was calculated by microscopic ATR (Attenuated Total Reflection) measurement using the FT-IR method. This measurement was performed by bringing the cured product into contact with germanium crystals, irradiating the cured product with infrared light, and measuring the spectrum of light absorbed by the cured product and reflected by the germanium crystals.

Curing reaction rate difference (%)
=(1-(SAbs./SRef.)/(DAbs./DRef.))×100
"SAbs." indicates the absorption peak of the side of the cured material that was in contact with the conductor, "SRef." indicates the reference peak of the side of the cured material that was in contact with the conductor, "DAbs." is the absorption peak of the side of the cured material that was in contact with the conductor, and "DRef." is the reference peak of the side of the cured material that was in contact with the conductor.

[Test Example 4] Corrosion resistance After peeling off the cured product in [Test Example 3], the surface area of the corroded part of the conductor was measured and evaluated according to the following evaluation criteria. The following evaluation criteria are common to Examples 1 to 18 and Comparative Examples 1 to 4. "3" to "5" are pass marks for this test.

-Evaluation criteria-
5: The surface area of the corroded part is 0 ^mm2
4: The surface area of the corroded part is greater than 0 ^mm2 and less than 3.0 ^mm2. 3: The surface area of the corroded part is 3.0 ^mm2 or more and less than 10.0 ^mm2. 2: The surface area of the corroded part is 10.0 ^mm2 or more and less than 50.0 ^mm2. 1: The surface area of the corroded part is 50.0 ^mm2 or more.

The surface area of the corroded portion was determined by measuring the 3D shape of the target object by 3D scanning the conductor after peeling off the cured material using a 3D shape measuring device (VR-5200 (product name) manufactured by Keyence Corporation) to find the surface area of the corroded portion.

The results are summarized in Table 1 below.

The content of each component in the table is in parts by mass. Blank spaces and "-" mean that the corresponding component is not included.

Notes for the table:
AL: Aluminum alloy wire (alloy composition Al-Mg-Si, length 0.2 m, conductor cross-sectional area 0.75 mm ² (≒0.75 sq))
Cu: Copper electric wire (length 0.2 m, conductor cross-sectional area 0.75 mm ² (≒ 0.75 sq))
Example 1
(Component (A): Radically Polymerizable Compound)
Isobornyl acrylate (monofunctional) (manufactured by Nippon Shokubai Co., Ltd.)
(Component (B): Cationic Polymerizable Compound)
3',4'-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate ("Celloxide 2021P" (product name) manufactured by Daicel Corporation)
(Component (D): Photoradical polymerization initiator)
1-Hydroxy-cyclohexyl-phenyl-ketone ("omnirad184" (product name) manufactured by IGM Resins B.V.)
(Component (E) (light): cationic polymerization initiator)
Triarylsulfonium salt ("CPI-300" (product name) manufactured by San-Apro Co., Ltd. (photocationic polymerization initiator))

Example 2
(Component (A): Radically Polymerizable Compound)
Isobornyl acrylate (monofunctional) (manufactured by Nippon Shokubai Co., Ltd.)
(Component (B): Cationic Polymerizable Compound)
3',4'-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate ("Celloxide 2021P" (product name) manufactured by Daicel Corporation)
(Component (D): Photoradical polymerization initiator)
1-Hydroxy-cyclohexyl-phenyl-ketone ("omnirad184" (product name) manufactured by IGM Resins B.V.)
(Component (E) (Heat): Cationic Polymerization Initiator)
4-Hydroxyphenylbenzylmethylsulfonium (manufactured by Sanshin Chemical Industry Co., Ltd.) (thermal latent cationic polymerization initiator)

Example 3
(Component (A): Radically Polymerizable Compound)
Isobutyl acrylate (monofunctional) (manufactured by Nippon Shokubai Co., Ltd.)
(Component (B): Cationic Polymerizable Compound)
ε-Caprolactone modified 3',4'-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate (difunctional epoxy) ("Celloxide 2081" (product name) manufactured by Daicel Corporation)
(Component (D): Photoradical polymerization initiator)
2,4,6-trimethylbenzoyl-diphenylphosphine oxide ("omnirad TPO H" (product name) manufactured by IGM Resins B.V.)
(Component (E) (Heat): Cationic Polymerization Initiator)
San-Apro Co., Ltd. "TA-100" (product name) (onium salt type thermal latent cationic polymerization initiator)

Example 4
(Component (A): Radically Polymerizable Compound)
(2-Methyl-2-ethyl-1,3-dioxolan-4-yl)methyl acrylate (monofunctional) ("MEDOL-10" (product name) manufactured by Osaka Organic Chemical Industry Co., Ltd.)
(Component (B): Cationic Polymerizable Compound)
ε-Caprolactone modified 3',4'-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate (difunctional epoxy) ("Celloxide 2081" (product name) manufactured by Daicel Corporation)
(Component (D): Photoradical polymerization initiator)
2,4,6-trimethylbenzoyl-diphenylphosphine oxide ("omnirad TPO H" (product name) manufactured by IGM Resins B.V.)
(Component (E) (Heat): Cationic Polymerization Initiator)
Trialkylsulfonium salt ("CP-66" (trade name) manufactured by ADEKA Corporation) (thermal latent cationic polymerization initiator)

Example 5
(Component (A): Radically Polymerizable Compound)
Isobornyl acrylate (monofunctional) (manufactured by Nippon Shokubai Co., Ltd.)
(Component (B): Cationic Polymerizable Compound)
3',4'-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate (difunctional epoxy) ("Celloxide 2021P" (product name) manufactured by Daicel Corporation)
(Component (D): Photoradical polymerization initiator)
1-Hydroxy-cyclohexyl-phenyl-ketone ("omnirad184" (product name) manufactured by IGM Resins B.V.)
(Component (E) (light): cationic polymerization initiator)
Triarylsulfonium salt ("CPI-300" (product name) manufactured by San-Apro Co., Ltd. (photocationic polymerization initiator))
(Component (E) (Heat): Cationic Polymerization Initiator)
Aromatic sulfonium salt (anion component: SbF ₆ ⁻ ) (Sanshin Chemical Industry Co., Ltd., “Sanaid SI-60L” (product name)) (thermal latent cationic polymerization initiator)

Example 6
(Component (A): Radically Polymerizable Compound)
Isobutyl acrylate (monofunctional) (manufactured by Nippon Shokubai Co., Ltd.)
(Component (B): Cationic Polymerizable Compound)
ε-Caprolactone modified 3',4'-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate (difunctional epoxy) ("Celloxide 2081" (product name) manufactured by Daicel Corporation)
(Component (D): Photoradical polymerization initiator)
2,4,6-trimethylbenzoyl-diphenylphosphine oxide ("omnirad TPO H" (product name) manufactured by IGM Resins B.V.)
(Component (E) (light): cationic polymerization initiator)
Triarylsulfonium salt ("CPI-300" (product name) manufactured by San-Apro Co., Ltd.) (photocationic polymerization initiator)
(Component (E) (Heat): Cationic Polymerization Initiator)
"TA-100" (product name) manufactured by San-Apro Co., Ltd. (onium salt type thermal latent cationic polymerization initiator)

(Example 7)
(Component (A): Radically Polymerizable Compound)
(2-Methyl-2-ethyl-1,3-dioxolan-4-yl)methyl acrylate (monofunctional) ("MEDOL-10" (product name) manufactured by Osaka Organic Chemical Industry Co., Ltd.)
(Component (B): Cationic Polymerizable Compound)
3',4'-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate (difunctional epoxy) ("Celloxide 2021P" (product name) manufactured by Daicel Corporation)
"Aron Oxetane OXT-211 (POX)" (product name) (monofunctional oxetane) manufactured by Toagosei Co., Ltd.
20 parts by weight of a difunctional epoxy and 20 parts by weight of a monofunctional oxetane were used.
(Component (D): Photoradical polymerization initiator)
2,4,6-trimethylbenzoyl-diphenylphosphine oxide ("omnirad TPO H" (product name) manufactured by IGM Resins B.V.)
(Component (E) (light): cationic polymerization initiator)
Triarylsulfonium salt ("SP-152" (product name) manufactured by ADEKA Corporation) (photocationic polymerization initiator)
(Component (E) (Heat): Cationic Polymerization Initiator)
Trialkylsulfonium salt ("CP-66" (product name) manufactured by ADEKA Corporation) (thermal cationic polymerization initiator)

(Example 8)
(Component (A): Radically Polymerizable Compound)
Isobornyl acrylate (monofunctional) (manufactured by Nippon Shokubai Co., Ltd.)
(Component (B): Cationic Polymerizable Compound)
3',4'-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate (difunctional epoxy) ("Celloxide 2021P" (product name) manufactured by Daicel Corporation)
(Component (D): Photoradical polymerization initiator)
1-Hydroxy-cyclohexyl-phenyl-ketone ("omnirad184" (product name) manufactured by IGM Resins B.V.)
(Component (E) (light): cationic polymerization initiator)
Triarylsulfonium salt ("CPI-300" (product name) manufactured by San-Apro Co., Ltd.) (photocationic polymerization initiator)

(Example 9)
(Component (A): Radically Polymerizable Compound)
Isobornyl acrylate (monofunctional) (manufactured by Nippon Shokubai Co., Ltd.)
(Component (B): Cationic Polymerizable Compound)
3',4'-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate (difunctional epoxy) ("Celloxide 2021P" (product name) manufactured by Daicel Corporation)
(Component (D): Photoradical polymerization initiator)
1-Hydroxy-cyclohexyl-phenyl-ketone ("omnirad184" (product name) manufactured by IGM Resins B.V.)
(Component (E) (light): cationic polymerization initiator)
Triarylsulfonium salt ("CPI-300" (product name) manufactured by San-Apro Co., Ltd.) (photocationic polymerization initiator)

Example 10
(Component (A): Radically Polymerizable Compound)
Isobornyl acrylate (monofunctional) (manufactured by Nippon Shokubai Co., Ltd.)
(Component (B): Cationic Polymerizable Compound)
3',4'-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate (difunctional epoxy) ("Celloxide 2021P" (product name) manufactured by Daicel Corporation)
(Component (D): Photoradical polymerization initiator)
1-Hydroxy-cyclohexyl-phenyl-ketone ("omnirad184" (product name) manufactured by IGM Resins B.V.)
(Component (E) (light): cationic polymerization initiator)
Triarylsulfonium salt ("CPI-300" (product name) manufactured by San-Apro Co., Ltd.) (photocationic polymerization initiator)

(Example 11)
(Component (A): Radically Polymerizable Compound)
Isobornyl acrylate (monofunctional) (manufactured by Nippon Shokubai Co., Ltd.)
(Component (B): Cationic Polymerizable Compound)
3',4'-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate (difunctional epoxy) ("Celloxide 2021P" (product name) manufactured by Daicel Corporation)
(Component (D): Photoradical polymerization initiator)
1-Hydroxy-cyclohexyl-phenyl-ketone ("omnirad184" (product name) manufactured by IGM Resins B.V.)
(Component (E) (light): cationic polymerization initiator)
Triarylsulfonium salt ("CPI-300" (product name) manufactured by San-Apro Co., Ltd.) (photocationic polymerization initiator)

Example 12
(Component (A): Radically Polymerizable Compound)
Isobornyl acrylate (monofunctional) (manufactured by Nippon Shokubai Co., Ltd.)
(Component (B): Cationic Polymerizable Compound)
3',4'-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate (difunctional epoxy) ("Celloxide 2021P" (product name) manufactured by Daicel Corporation)
(Component (C): Radically Polymerizable and Cationic Polymerizable Compound)
Glycidyl methacrylate (having one methacryloyl group and one epoxy group) (manufactured by Mitsubishi Gas Chemical Company, Inc.)
(Component (D): Photoradical polymerization initiator)
1-Hydroxy-cyclohexyl-phenyl-ketone ("omnirad184" (product name) manufactured by IGM Resins B.V.)
(Component (E) (light): cationic polymerization initiator)
Triarylsulfonium salt ("CPI-300" (product name) manufactured by San-Apro Co., Ltd.) (photocationic polymerization initiator)

Example 13
(Component (A): Radically Polymerizable Compound)
Isobornyl acrylate (monofunctional) (manufactured by Nippon Shokubai Co., Ltd.)
(Component (C): Radically Polymerizable and Cationic Polymerizable Compound)
Glycidyl methacrylate (having one methacryloyl group and one epoxy group) (manufactured by Mitsubishi Gas Chemical Company, Inc.)
(Component (D): Photoradical polymerization initiator)
1-Hydroxy-cyclohexyl-phenyl-ketone ("omnirad184" (product name) manufactured by IGM Resins B.V.)
(Component (E) (light): cationic polymerization initiator)
Triarylsulfonium salt ("CPI-300" (product name) manufactured by San-Apro Co., Ltd.) (photocationic polymerization initiator)

(Example 14)
(Component (A): Radically Polymerizable Compound)
Isobornyl acrylate (monofunctional) (manufactured by Nippon Shokubai Co., Ltd.)
(Component (B): Cationic Polymerizable Compound)
"VNBB-SE" (product name) manufactured by ENEOS Corporation (monofunctional alicyclic epoxy)
(Component (D): Photoradical polymerization initiator)
1-Hydroxy-cyclohexyl-phenyl-ketone ("omnirad184" (product name) manufactured by IGM Resins B.V.)
(Component (E) (light): cationic polymerization initiator)
Triarylsulfonium salt ("CPI-300" (product name) manufactured by San-Apro Co., Ltd.) (photocationic polymerization initiator)

(Example 15)
(Component (A): Radically Polymerizable Compound)
Trimethylolpropane triacrylate (multifunctional) ("Viscoat #295" (product name) manufactured by Osaka Organic Chemical Industry Co., Ltd.)
(Component (B): Cationic Polymerizable Compound)
3',4'-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate (difunctional epoxy) ("Celloxide 2021P" (product name) manufactured by Daicel Corporation)
(Component (D): Photoradical polymerization initiator)
1-Hydroxy-cyclohexyl-phenyl-ketone ("omnirad184" (product name) manufactured by IGM Resins B.V.)
(Component (E) (light): cationic polymerization initiator)
Triarylsulfonium salt ("CPI-300" (product name) manufactured by San-Apro Co., Ltd.) (photocationic polymerization initiator)

(Example 16)
(Component (C): Radically Polymerizable and Cationic Polymerizable Compound)
Glycidyl methacrylate (having one methacryloyl group and one epoxy group) (manufactured by Mitsubishi Gas Chemical Company, Inc.)
(Component (D): Photoradical polymerization initiator)
1-Hydroxy-cyclohexyl-phenyl-ketone ("omnirad184" (product name) manufactured by IGM Resins B.V.)
(Component (E) (light): cationic polymerization initiator)
Triarylsulfonium salt ("CPI-300" (product name) manufactured by San-Apro Co., Ltd.) (photocationic polymerization initiator)

(Example 17)
(Component (A): Radically Polymerizable Compound)
Isobornyl acrylate (monofunctional) (manufactured by Nippon Shokubai Co., Ltd.)
(Component (B): Cationic Polymerizable Compound)
3',4'-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate ("Celloxide 2021P" (product name) manufactured by Daicel Corporation)
(Component (D): Photoradical polymerization initiator)
1-Hydroxy-cyclohexyl-phenyl-ketone ("omnirad184" (product name) manufactured by IGM Resins B.V.)
(Component (E) (light): cationic polymerization initiator)
Triarylsulfonium salt ("CPI-300" (product name) manufactured by San-Apro Co., Ltd. (photocationic polymerization initiator))

(Example 18)
(Component (A): Radically Polymerizable Compound)
Isobornyl acrylate (monofunctional) (manufactured by Nippon Shokubai Co., Ltd.)
(Component (B): Cationic Polymerizable Compound)
3',4'-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate ("Celloxide 2021P" (product name) manufactured by Daicel Corporation)
(Component (D): Photoradical polymerization initiator)
1-Hydroxy-cyclohexyl-phenyl-ketone ("omnirad184" (product name) manufactured by IGM Resins B.V.)
(Component (E) (Heat): Cationic Polymerization Initiator)
Aromatic sulfonium salt (anion component: SbF ₆ ⁻ ) (Sanshin Chemical Industry Co., Ltd., “Sanaid SI-60L” (product name)) (thermal latent cationic polymerization initiator)

(Comparative Example 1)
(Component (A): Radically Polymerizable Compound)
Isobornyl acrylate (monofunctional) (manufactured by Nippon Shokubai Co., Ltd.)
(Component (D): Photoradical polymerization initiator)
1-Hydroxy-cyclohexyl-phenyl-ketone ("omnirad184" (product name) manufactured by IGM Resins B.V.)

(Comparative Example 2)
(Component (A): Radically Polymerizable Compound)
Isobornyl acrylate (monofunctional) (manufactured by Nippon Shokubai Co., Ltd.)
(Component (D): Photoradical polymerization initiator)
1-Hydroxy-cyclohexyl-phenyl-ketone ("omnirad184" (product name) manufactured by IGM Resins B.V.)
(Thermal radical polymerization initiator)
Cumene hydroperoxide ("Percumyl H" (product name) manufactured by Nippon Oil & Fats Co., Ltd.)

(Comparative Example 3)
(Component (A): Radically Polymerizable Compound)
Isobornyl acrylate (monofunctional) (manufactured by Nippon Shokubai Co., Ltd.)
(Component (D): Photoradical polymerization initiator)
1-Hydroxy-cyclohexyl-phenyl-ketone ("omnirad184" (product name) manufactured by IGM Resins B.V.)
(Thermal radical polymerization initiator)
Cumene hydroperoxide ("Percumyl H" (product name) manufactured by Nippon Oil & Fats Co., Ltd.)
(Redox catalyst)
Copper ethylhexanoate II (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)

(Comparative Example 4)
(Component (A): Radically Polymerizable Compound)
Isobornyl acrylate (monofunctional) (manufactured by Nippon Shokubai Co., Ltd.)
(Component (B): Cationic Polymerizable Compound)
3',4'-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate (difunctional epoxy) ("Celloxide 2021P" (product name) manufactured by Daicel Corporation)
(Thermal radical polymerization initiator)
Cumene hydroperoxide ("Percumyl H" (product name) manufactured by Nippon Oil & Fats Co., Ltd.)
(Component (E) (light): cationic polymerization initiator)
Triarylsulfonium salt ("CPI-300" (product name) manufactured by San-Apro Co., Ltd.) (photocationic polymerization initiator)
(Component (E) (Heat): Cationic Polymerization Initiator)
Aromatic sulfonium salt (anion component: SbF ₆ ⁻ ) (Sanshin Chemical Industry Co., Ltd., “Sanaid SI-60L” (product name)) (thermal latent cationic polymerization initiator)

The following can be seen from Table 1.
The composition of Comparative Example 1 contains a radical polymerizable compound (component (A)) and a photoradical polymerization initiator (component (D)) as defined in the present invention. However, the composition of Comparative Example 1 does not contain a cationic polymerizable compound (component (B)) and a cationic polymerization initiator (component (E)) as defined in the present invention. Furthermore, the composition of Comparative Example 1 does not contain a radically polymerizable and cationic polymerizable compound (component (C)). The wire harness produced using the composition of Comparative Example 1 has poor interwire watertightness and internal curing properties.
The composition of Comparative Example 2 contains component (A), component (D) and a thermal radical polymerization initiator. However, the composition of Comparative Example 2 does not contain component (B) and component (E). The composition of Comparative Example 2 also does not contain component (C). The composition of Comparative Example 2 has poor storage stability. In addition, the wire harness produced using the composition of Comparative Example 2 has poor interwire watertightness and internal curing properties.
The composition of Comparative Example 3 contains component (A), component (D), a thermal radical polymerization initiator, and a redox catalyst. However, the composition of Comparative Example 3 does not contain component (B) and component (E). The composition of Comparative Example 3 also does not contain component (C). The composition of Comparative Example 3 has poor storage stability. In addition, the wire harness produced using the composition of Comparative Example 3 has poor interwire watertightness and internal curing properties.
The composition of Comparative Example 4 contains components (A), (B), (E) and a thermal radical polymerization initiator. However, the composition of Comparative Example 4 does not contain component (D). The composition of Comparative Example 4 also does not contain component (C). The composition of Comparative Example 4 has poor storage stability. In addition, the wire harness produced using the composition of Comparative Example 4 has poor interwire watertightness and internal curing properties.
In contrast, the composition of the present invention has excellent storage stability, and the wire harnesses and electric wires with terminals produced using the composition of the present invention all have excellent inter-wire watertightness, internal curing properties, and corrosion resistance (Examples 1 to 18).

Reference Signs List 1 Terminal 3 Terminal body 4 Transition section 5 Crimping section 7 Conductor crimping section 8 Inter-barrel section 9 Covering crimping section 10 Electric wire with terminal 11 Covered conductor wire 13a, 13b Conductor wire 15 Covering section 17a, 17b Cured product (cured product of conductor sealing composition)
18 Electric wire 19 Joint (joint sealed with a cured product of the conductor sealing composition)
20 Wire harness 21 Water tank 22 Regulator F, G Air flow is shown.

Claims (8)

A composition for sealing a conductor wire, comprising the following components (A), (B), (D), and (E), or the following components (C), (D), and (E):
(A) a radically polymerizable compound, (B) a cationic polymerizable compound, (C) a radically polymerizable and cationic polymerizable compound, (D) a photoradical polymerization initiator, and (E) a cationic polymerization initiator.
When the composition for sealing a conductor wire contains components (A), (B), (D), and (E), the content of the component (A) is 50 to 90 parts by mass, and the content of the component (B) is 10 to 50 parts by mass, relative to 100 parts by mass of the total content of the components (A) and (B).
(However, this does not include a conductor sealing composition that contains an imide compound as a component other than the components (A) to (E) .) The conductor sealing composition according to claim 1, wherein the component (E) contains a thermally latent cationic polymerization initiator. A terminal-attached electric wire in which a coated conductor wire and a terminal are connected,
The coated conductor wire includes a coating portion and a conductor wire exposed from a tip of the coating portion,
3. An electric wire with a terminal, the electric wire having a terminal body and a crimping portion, the crimping portion including a conductor crimping portion to which the conductor wire is crimped, a coating crimping portion to which the coating portion is crimped, and an inter-barrel portion between the conductor crimping portion and the coating crimping portion, and at least a portion between the coating crimping portion and an end of the exposed conductor wire and other than the crimping portion is sealed with a cured product of the conductor sealing composition according to claim 1 or 2. A plurality of electric wires each having an exposed conductor portion and a coated conductor portion are bundled together,
The exposed conductor portion is welded to form a joint,
A wire harness, wherein the conductor joint portion is sealed with a cured product of the conductor sealing composition according to claim 1 or 2. A method for manufacturing an electric wire with a terminal in which a coated conductor wire and a terminal are connected, comprising the steps of:
The coated conductor wire includes a coating portion and a conductor wire exposed from a tip of the coating portion,
the terminal has a terminal body and a crimping portion, the crimping portion including a conductor crimping portion to which the conductor wire is crimped, a coating crimping portion to which the coating portion is crimped, and a barrel-interface portion between the conductor crimping portion and the coating crimping portion, the method comprising: a step (1) of applying the conductor sealing composition according to claim 1 or 2 to at least a portion between the coating crimping portion and an end of the exposed conductor wire and other than the crimping portion; and a step (2) of curing the conductor sealing composition. A method for manufacturing a wire harness, comprising the steps of: applying the conductor sealing composition according to claim 1 or 2 to a joint portion of conductors exposed from a plurality of electric wires; and curing the conductor sealing composition. The method for manufacturing a wire harness according to claim 6, further comprising ultrasonically welding exposed conductors from a plurality of electric wires to form joints of the exposed conductors. The method for producing a wire harness according to claim 6 or 7, wherein the steps (1) and (2) are the following steps (1a) and (2a):
Step (1a): A step of immersing the joint in the conductor sealing composition in an insulating container having an ultraviolet transmittance of 50% or more and at least a part of which is flat. Step (2a): A step of irradiating the insulating container with ultraviolet light in a ring shape from the outside.

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