Composition for wire sealing, wire with terminal, wire harness, and method for manufacturing wire with terminal and wire harness

Abstract

To provide a conductive wire sealing composition, a wire with a terminal, and a wire harness, which are excellent in storage stability, and, while showing excellent curability and suppressing corrosion of a conductive wire (conductor) due to a curing reaction, capable of imparting sufficiently high level of water stopping performance to junctions of a plurality of conductive wires, and a manufacturing method of a wire with a terminal and a wire harness.SOLUTION: There are provided a conductive wire sealing composition containing the following components (A), (B), (D) and (E), or the following components (C), (D) and (E), a wire with a terminal, and a wire harness, as well as a manufacturing method a wire with a terminal and a wire harness. (A) Radically polymerizable compound (B) Cationic polymerizable compound (C) Radically polymerizable and cationic polymerizable compound (D) Radical photopolymerization initiator (E) Cationic polymerization initiator.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a composition for sealing a conductive wire, a wire with a terminal, a wire harness, and a method for manufacturing a wire with a terminal and a wire harness.

Background Art

[0002] In automobiles, home appliances, etc., a wire harness in which a plurality of insulated wires are bundled is used as electrical wiring. A wire harness includes an exposed bundle portion including a splice portion (joint portion) formed by welding or crimping a part of the conductive wires exposed by stripping the insulating layers of the respective insulated wires to each other, and a portion (coated bundle portion) in which portions covered with the insulating layers of the respective insulated wires are bundled. The exposed bundle portion is usually coated with a resin for the purpose of preventing corrosion by water, leakage of electricity, 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 technique described in Patent Document 1, by sealing the exposed bundle portion and the end portion of the coated bundle portion adjacent to the exposed bundle portion with the composition liquid, the airtightness of the sealed portion can be enhanced, and it is said that the waterproof property (water stoppage property) of the wire harness can be enhanced. Further, Patent Document 2 describes a composition liquid 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 composition liquid. The technique described in Patent Document 2 also states that by sealing the exposed bundle portion and the end portion of the coated bundle portion adjacent to the exposed bundle portion with the composition liquid, the waterproof property (water stoppage property) of the obtained wire harness can be enhanced.

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Patent Document 2

[0004] However, according to the studies by the present inventors, the composition liquids described in the above patent documents are likely to have their curability impaired by the influence of oxygen or the like. As a result, it has been found that the exposed bundle portions cannot be sufficiently sealed to a deep part and there are limitations in improving the water stoppage property. Further, it has also been found that the thermal radical polymerization initiator contained in the composition liquids described in the above patent documents is easily decomposed and the composition liquids are inferior in storage stability.

[0005] In view of the above situation, an object of the present invention is to provide a composition for sealing a conductor that is excellent in storage stability, exhibits excellent curability, suppresses corrosion of a conductor by a curing reaction, and can impart a sufficiently high level of water stoppage property to joints of a plurality of conductors. Another object of the present invention is to provide an insulated electric wire with terminals and a wire harness using the composition for sealing a conductor, and each manufacturing method thereof. MEANS FOR SOLVING THE PROBLEMS

[0006] That is, the above problems have been solved by the following means. <1> A composition for sealing a conductor containing the following components (A), (B), (D) and (E), or the following components (C), (D) and (E). (A) Radical polymerizable compound (B) Cationic polymerizable compound (C) Radical polymerizable and cationic polymerizable compound (D) Photo radical polymerization initiator (E) Cationic polymerization initiator <2> The composition for sealing a conductor according to <1>, wherein the component (E) contains a thermal latent cationic polymerization initiator. <3> In 100 parts by mass of the total content of the components (A) and (B), 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. The wire sealing composition according to <1> or <2>. <4> An electric wire with a terminal in which a coated wire and a terminal are connected, The coated wire includes a coated portion and a wire exposed from the tip of the coated portion, The terminal has a terminal body and a crimping portion. The crimping portion includes a wire crimping portion where the wire is crimped, a coating crimping portion where the coated portion is crimped, and a barrel portion between the wire crimping portion and the coating crimping portion. At least the portion from the coating crimping portion to the end of the exposed wire and other than the crimping portion is sealed with a cured product of the wire sealing composition according to any one of <1> to <3>. An electric wire with a terminal. <5> A plurality of electric wires having a wire exposed portion and a wire coated portion are bundled together, A joint portion is formed by welding the wire exposed portions, The wire joint portion is sealed with a cured product of the wire sealing composition according to any one of <1> to <3>. A wire harness. <6> A method for manufacturing an electric wire with a terminal in which a coated wire and a terminal are connected, The coated wire includes a coated portion and a wire exposed from the tip of the coated portion, The terminal has a terminal body and a crimping portion. The crimping portion includes a wire crimping portion where the wire is crimped, a coating crimping portion where the coated portion is crimped, and a barrel portion between the wire crimping portion and the coating crimping portion. The method for manufacturing an electric wire with a terminal includes a step (1) of applying the wire sealing composition according to any one of <1> to <3> to at least the portion from the coating crimping portion to the end of the exposed wire and other than the crimping portion, and a step (2) of curing the wire sealing composition. <7> A method for manufacturing a wire harness, comprising: a step (1) of applying the composition for sealing a conductor 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 composition for sealing a conductor. <8> The method for manufacturing a wire harness according to <7>, comprising ultrasonic welding of conductors exposed from a plurality of electric wires to form a joint portion of the exposed conductors. <9> The method for manufacturing 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 portion in the composition for sealing a conductor 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 ultraviolet rays in a ring shape from the outside of the insulating container.

Advantages of the Invention

[0007] The composition for sealing a conductor of the present invention has excellent storage stability. Further, the composition for sealing a conductor of the present invention exhibits excellent curability and can impart a sufficiently high level of water stoppage to the joint portion of a plurality of conductors while suppressing corrosion of the conductors due to the curing reaction. The wire harness and the electric wire with a terminal of the present invention are excellent in conductivity and water stoppage because corrosion of the conductors is suppressed. According to the method for manufacturing an electric wire with a terminal of the present invention, the electric wire with a terminal of the present invention can be obtained. Further, according to the method for manufacturing a wire harness of the present invention, the wire harness of the present invention can be obtained.

Brief Description of the Drawings

[0008]

Figure 1

Figure 2

Figure 3

Figure 4

Figure 5

Embodiments for Carrying Out the Invention

[0009] [Composition for Sealing Conductive Wires] The composition for sealing conductive wires of the present invention contains the following components (A), (B), (D), and (E), or the following components (C), (D), and (E). Hereinafter, the "composition for sealing conductive wires" may also be simply referred to as the "composition". (A) Radical polymerizable compound (Component (A)) (B) Cationic polymerizable compound (Component (B)) (C) Radical polymerizable and cationic polymerizable compound (Component (C)) (D) Photo radical polymerization initiator (Component (D)) (E) Cationic polymerization initiator (Component (E)) Each of the components (A) to (E) and the optional components described later may be used alone as one kind of each component, or two or more kinds may be used in combination. Hereinafter, the form in which the composition for sealing conductive wires of the present invention contains the above components (A), (B), (D), and (E), that is, the form in which the above components (A), (B), (D), and (E) are essential components, is referred to as "Form 1". On the other hand, the form in which the composition for sealing conductive wires of the present invention contains the above components (C), (D), and (E), that is, the form in which the above (C), (D), and (E) are essential components, is referred to as "Form 2". Hereinafter, the components contained in the composition for sealing conductive wires of the present invention will be described.

[0010] <(A) Radical polymerizable compound> Component (A) used in the present invention is a compound that can be radically polymerized by the action of a photo radical polymerization initiator, that is, a compound having a radical polymerizable group. Component (A) does not have a cationic polymerizable group. Component (A) used in the present invention may be a monofunctional radically polymerizable compound (a compound having one radically polymerizable group), or may be a polyfunctional radically polymerizable compound (a compound having two or more (preferably 2 to 4) radically polymerizable groups). As component (A) used in the present invention, a monofunctional radically polymerizable compound is preferred.

[0011] The above-mentioned radically polymerizable group is not particularly limited as long as it is a functional group capable of causing a radical polymerization reaction. For example, a group containing a carbon-carbon double bond can be mentioned. Specific examples include a vinyl group and a (meth)acryloyl group. When component (A) has two or more radically polymerizable groups, these radically 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" represents both an acryloyl group and a methacryloyl group in one term. The molecular weight of component (A) is not particularly limited. For example, it is 20 to 1000, preferably 50 to 500, and more preferably 80 to 300. When component (A) is an oligomer or a polymer, the weight average molecular weight of component (A) is not particularly limited. For example, it is 40 to 10000, preferably 100 to 5000, and more preferably 200 to 3000.

[0012] In the present invention, the polymerization average molecular weight of an oligomer or a polymer is a value measured as the molecular weight in terms of polystyrene under the following measurement conditions by gel permeation chromatography (GPC). Measuring device: Nexera XR GPC (trade name, manufactured by Shimadzu Corporation) Column: Three Shodex KF806L (trade name, manufactured by Showa Denko KK) columns connected in series Eluent: Tetrahydrofuran Flow rate: 0.8 mL / min Measurement temperature: 40 Detection means: RID (differential refractive index detector)

[0013] As the component (A), a radically polymerizable compound having a (meth)acryloyl group is preferable, and specifically, a (meth)acrylate is preferable. Specific examples of the component (A) include the compounds used in the following examples and the following compounds, but the present invention is not limited to these compounds. Specifically, mono (meth) acrylates such as 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, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, isostearyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, methoxyethylene glycol (meth) acrylate, ethoxyethyl (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, methoxypolypropylene glycol (meth) acrylate, polyoxyethylene nonyl phenyl 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, and 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-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, 9,9-bis[4-(2-acryloyloxyethoxy)phenyl]fluorene, polyester di(meth)acrylate, tris(2-hydroxyethyl)isocyanurate tri(meth)acrylate, tris(2-hydroxyethyl)isocyanurate di(meth)acrylate, tricyclodecane dimethylol di(meth)acrylate, bisphenol A EO (ethylene oxide) adduct di(meth)acrylate, hydrogenated bisphenol A EO adduct or PO (propylene oxide) adduct of polyol di(meth)acrylate, epoxy(meth)acrylate obtained by adding (meth)acrylate to diglycidyl ether of bisphenol A, triethylene glycol divinyl ether compound, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, trimethylolpropane EO adduct tri(meth)acrylate, trisacryloyloxyethyl phosphate, pentaerythritol tetra(meth)acrylate, tetrafurfuryl alcohol oligo(meth)acrylate, ethyl carbitol oligo(meth)acrylate, 1,4-butanediol oligo(meth)acrylate, 1,6-hexanediol oligo(meth)acrylate, trimethylolpropane oligo(meth)acrylate, pentaerythritol oligo(meth)acrylate, (poly)urethane(meth)acrylate and (poly)butadiene(meth)acrylate and other poly(meth)acrylates can be mentioned.,

[0014] <(B) Cationically polymerizable compound> Component (B) used in the present invention is a compound capable of cationic polymerization by the action of a cationic polymerization initiator, that is, a compound having a cationic polymerizable group. Component (B) does not have a radical polymerizable group. Component (B) used in the present invention may be a monofunctional cationic polymerizable compound (a compound having one cationic polymerizable group), or a polyfunctional cationic polymerizable compound (a compound having two or more (preferably 2 to 4, more preferably 2 or 3, particularly preferably 2) cationic polymerizable groups). As component (B) used in the present invention, a polyfunctional cationic polymerizable compound is preferred.

[0015] The above cationic polymerizable group is not particularly limited as long as it is a functional group capable of causing a cationic polymerization reaction. Examples include an epoxy group, an oxetanyl group, and a vinyl ether group, and an epoxy group is 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 an oligomer or a polymer. The molecular weight of component (B) is not particularly limited. For example, it is 20 to 1000, 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. For example, it is 40 to 10000, preferably 100 to 5000, and more preferably 200 to 3000. Specific examples of component (B) include the compounds used in the following examples and the following compounds, but the present invention is not limited to these compounds. Specifically, for example, epoxy compounds, oxetane compounds, oxolane compounds, cyclic acetal compounds, cyclic lactone compounds, thiyrane compounds, thietane compounds, vinyl ether compounds, spiro orthoester compounds (reaction products of epoxy compounds and lactones), ethylenically unsaturated compounds, cyclic ether compounds, cyclic thioether compounds, and vinyl compounds can be mentioned. 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, 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexanecarboxylate, 2-(3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy)cyclohexane-meta-dioxane, bis(3,4-epoxycyclohexylmethyl) adipate, vinyl cyclohexene oxide, 4-vinyl epoxy cyclohexane, bis(3,4-epoxy-6-methylcyclohexylmethyl) adipate, 3,4-epoxy-6-methylcyclohexyl-3',4'-epoxy-6'-methylcyclohexanecarboxylate, methylene bis(3,4-epoxycyclohexane), dicyclopentadiene diepoxide, di(3,4-epoxycyclohexylmethyl) ether of ethylene glycol, ethylene bis(3,4-epoxycyclohexanecarboxylate), dioctyl epoxy hexahydrophthalate, di-2-ethylhexyl epoxy hexahydrophthalate, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane triglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ethers; polyglycidyl ethers of polyether polyols obtained by adding one or more alkylene oxides to aliphatic polyhydric alcohols such as ethylene glycol, propylene glycol, and glycerin; 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;Examples thereof include epoxidized soybean oil, butyl epoxystearate, octyl epoxystearate, epoxidized linseed oil, epoxidized polybutadiene, etc.; Other specific examples include oxetanes such as trimethylene oxide, 3,3 - dimethyloxetane, 3,3 - dichloromethyloxetane, 3 - ethyl - 3 - phenoxymethyloxetane, bis(3 - ethyl - 3 - methyloxy)butane; oxolanes such as tetrahydrofuran, 2,3 - dimethyltetrahydrofuran; cyclic acetals such as trioxane, 1,3 - dioxolane, 1,3,6 - trioxane cyclooctane; cyclic lactones such as β - propiolactone, ε - caprolactone; thiiranes such as ethylene sulfide, 1,2 - propylene sulfide, thioepichlorohydrin; thietanes such as 3,3 - dimethylthietane; vinyl ethers such as ethylene glycol divinyl ether, triethylene glycol divinyl ether, trimethylolpropane trivinyl ether; spiro orthoesters obtained by the reaction of an epoxy compound and a lactone; ethylenically unsaturated compounds such as vinylcyclohexane, isobutylene, polybutadiene; derivatives of each of the above compounds, etc. can be exemplified.

[0016] In Form 1, as the combination of component (A) and component (B), a combination of a monofunctional radical polymerizable compound and a polyfunctional cationic polymerizable compound is preferable. By using a combination of a monofunctional radical polymerizable compound and a polyfunctional cationic polymerizable compound, the difference in crosslinking density due to curing near the surface and inside the electric wire can be reduced. That is, the joint part can be sealed with a cured product having a crosslinking density that is uniformly close overall. In this way, the curability of the composition for sealing electric wires of the present invention can be further enhanced, and corrosion of the electric wires can be suppressed. In addition, depending on the usage form of the composition for sealing electric wires of the present invention, in addition to sealing the electric wires, it may be used to coat other parts (for example, the part where the electric wire is coated). In the composition for sealing a conductive wire 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 curing inhibition of the composition by oxygen and moisture and the corrosion of the conductor by an acid, for example, in 100 parts by mass of the total content of component (A) and component (B), the content of component (A) is 10 to 90 parts by mass, and the content of component (B) is preferably 10 to 90 parts by mass. More preferably, the content of component (A) is 50 to 90 parts by mass, and the content of component (B) is 10 to 50 parts by mass. Particularly preferably, the content of component (A) is 55 to 75 parts by mass, and the content of component (B) is 25 to 45 parts by mass.

[0017] <(C) Radical polymerizable and cationically polymerizable compound> Component (C) used in the present invention is a compound that can be radically polymerized by the action of a radical polymerization initiator and can be cationically polymerized by the action of a cationic polymerization initiator, that is, a compound having both a radically polymerizable group and a cationically polymerizable group. Examples of the radically polymerizable group and the cationically polymerizable group of component (C) used in the present invention include the radically polymerizable group of component (A) and the cationically polymerizable group of component (B). The number of the radically polymerizable group and the cationically polymerizable group of component (C) is not particularly limited, and the total is preferably 2 to 10, more preferably 2 to 6, and still more preferably 2 or 3.

[0018] 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.

[0019] Component (C) may be an oligomer or a polymer. The molecular weight of component (C) is not particularly limited. For example, it is 20 to 1000, preferably 50 to 500, and more preferably 80 to 300. When component (C) is an oligomer or polymer, the weight average molecular weight of component (C) is not particularly limited, and is, for example, from 40 to 10,000, preferably from 100 to 5,000, and more preferably from 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 such compounds.

[0020] <(D) Photo radical 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 light irradiation. As component (D) of the present invention, ordinary photo radical polymerization initiators can be used, and examples thereof include acylphosphine oxide photo radical polymerization initiators, acetophenone photo radical polymerization initiators, and o-acyl oxime photo radical polymerization initiators. Specific examples of component (D) include the compounds used in the examples described below, but the present invention is not limited to such compounds.

[0021] <(E) Cationic polymerization initiator> In the present invention, as component (E), either a substance that releases a substance (cation) that initiates cationic polymerization upon light irradiation (photo cationic polymerization initiator) or a substance that releases a cation upon heating (thermal latent cationic polymerization initiator) can be used. The photo cationic polymerization initiators that can be used in the present invention can be roughly classified into onium salt-based photo cationic polymerization initiators and non-ionic photo cationic polymerization initiators. In the present invention, photo cationic polymerization initiators of other types may also be used.

[0022] The onium salt-based photo cationic polymerization initiators are not particularly limited, and for example, organic sulfonium salt compounds, organic oxonium salt compounds, organic ammonium salt compounds, organic phosphonium salt compounds, and organic iodonium salt compounds can be used. Specifically, for example, B(C6F5) 4- , SbF6 - , SbCl6 - , SbF4 - , FSO3 - , AsF6- , PF6 - , BF4 - , or CF3SO3 - Those having a counter anion such as these can be mentioned. Examples of commercially available onium salt-based photo cationic polymerization initiators include, for example, IRGACURE (registered trademark, hereinafter omitted) 250, IRGACURE270, IRGACURE290 (all trade names, manufactured by BASF), 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 Corporation), B2380, B2381, C1390, D2238, D2248, D2253, I0591, T1608, T1609, T2041, T2042 (all trade names, manufactured by Tokyo Chemical Industry Co., Ltd.), AT-6992, At-6976 (all trade names, manufactured by ACETO), 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 (above, manufactured by ADEKA Corporation, trade name), CD-1010, CD-1011, CD-1012 (above, manufactured by Sartomer, trade name), PI2074 (manufactured by Rhodia Japan, trade name), etc.

[0023] The nonionic photo cationic polymerization initiator that can be used in the present invention is not particularly limited, and examples include a phenacyl sulfone type photo cationic polymerization initiator, an o-nitrobenzyl ester type photo cationic polymerization initiator, an iminosulfonate type photo cationic polymerization initiator, a sulfonic acid ester type photo cationic polymerization initiator of N-hydroxyimide, etc. Specific compounds of the nonionic photo cationic polymerization initiator include, for example, sulfonyldiazomethane, 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, perfluorooctanesulfonic 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-dihydro-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-sodium sulfonate, 1,2-naphthoquinone-2-diazide-4-sodium sulfonate, 1,2-benzoquinone-2-diazide-4-sodium sulfonate, 1,2-naphthoquinone-2-diazide-5-potassium sulfonate, 1,2-naphthoquinone-2-diazide-4-potassium sulfonate, 1,2-benzoquinone-2-diazide-4-potassium sulfonate, 1,2-naphthoquinone-2-diazide-5-methyl sulfonate, 1,2-benzoquinone-2-diazide-4-methyl sulfonate, and the like. Commercially available products of the nonionic photo cationic polymerization initiator include, for example, WPAG-145, WPAG-149, WPAG-170, WPAG-199 (all are trade names, manufactured by Fujifilm Wako Pure Chemical Corporation), D2963, F0362, M1209, M1245 (all are trade names, manufactured by Tokyo Chemical Industry Co., Ltd.), SP-082, SP-103, SP-601, SP-606 (all are trade names, manufactured by ADEKA Corporation), SIN-11 (trade name, manufactured by Sanpo Chemical Laboratory), NT-1TF (trade name, manufactured by San-Apro Ltd.), and the like.

[0024] The thermally latent cationic polymerization initiator that can be used in the present invention is not particularly limited. For example, an onium salt-based thermal cationic generator such as an organic onium salt compound in which a cation component and an anion component are paired is used. Examples of the cation 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 anion component include B(C6F5)4 - , SbF6 - , SbF4 - , AsF6 - , PF6 - , BF4 - , CF3SO3 - and the like. In addition, for example, organometallic complexes such as aluminum chelate complexes, iron-allyl complexes, titanocene complexes, arylsilanol-aluminum complexes, oxime sulfonate-based acid generators, diazomethane-based acid generators such as bisalkyl or bisaryl sulfonyldiazomethanes and poly(bissulfonyl)diazomethanes, nitrobenzyl sulfonate-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 products of the thermally latent cationic polymerization initiator 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, K-PURE TAG-2713 (manufactured by KING INDUSTRIES, trade names), Sun-Aid SI-45L, Sun-Aid SI-60L, Sun-Aid SI-80L, Sun-Aid SI-100L, Sun-Aid SI-110L, Sun-Aid SI-150L (manufactured by Sanshin Chemical Industry Co., Ltd., trade names), and the like.

[0025] In Form 1, in the composition of the present invention, the contents of components (D) and (E) are not particularly limited. For example, with respect to 100 parts by mass of component (A), 0.1 to 10 parts by mass of component (D) can be used, and preferably 0.2 to 8 parts by mass is used. On the other hand, with respect to 100 parts by mass of component (B), 0.1 to 10 parts by mass of component (E) can be used, and preferably 1 to 10 parts by mass is used. Also in Form 2, in the composition of the present invention, the contents of components (D) and (E) are not particularly limited. For example, with respect to 100 parts by mass of component (C), a total of 1 to 10 parts by mass of components (D) and (E) can be used, and preferably 2 to 8 parts by mass is used. Further, in Form 2, with respect to 100 parts by mass of component (C), for example, 0.1 to 10 parts by mass of component (D) can be used, and preferably 0.2 to 8 parts by mass is used. Also, for example, 0.1 to 10 parts by mass of component (E) can be used, and preferably 1 to 10 parts by mass is used.

[0026] Component (E) of the present invention preferably contains a thermally latent cationic polymerization initiator from the viewpoint of more efficiently curing the composition by the heat of the radical reaction. Also, component (E) of the present invention preferably contains a combination of a photo cationic polymerization initiator and a thermally latent cationic polymerization initiator from the viewpoint of more efficiently curing the composition by the combined effect of ultraviolet irradiation and the heat of polymerization by ultraviolet irradiation. In this case, the ratio (mass ratio) of the content of the photo cationic polymerization initiator to the content of the thermally latent cationic polymerization initiator in the composition is not particularly limited. For example, the content of the photo cationic polymerization initiator: the content of the thermally latent cationic polymerization initiator = 1:10 to 10:1 can be set, preferably 1:6 to 6:1, and more preferably 1:3 to 3:1.

[0027] <Other Components> In addition to the above components, the composition for wire encapsulation of the present invention may contain other components such as a polymerization inhibitor, an antioxidant, a copper poisoning inhibitor, a flame retardant, a filler, a pigment, a dye, an antifoaming agent, a leveling agent, a viscosity modifier, etc. within a range that does not impair the effects of the present invention. In addition, in Form 1, the wire-sealing composition of the present invention may contain component (C) as long as the effects of the present invention are not impaired. In Form 1, in the composition, the content of component (C) is preferably 10 parts by mass or less, more preferably 5 parts by mass or less, based on 100 parts by mass of the total content of components (A) and (B). In addition, in Form 2, the wire-sealing composition of the present invention may contain components (A) and (B) as long as the effects of the present invention are not impaired. In Form 2, in the composition, the total content of components (A) and (B) is preferably 70 parts by mass or less, more preferably 50 parts by mass or less, based on 100 parts by mass of component (C).

[0028] [Method for producing wire-sealing composition] In Form 1, the wire-sealing composition of the present invention can be obtained by formulating the above-described components (A), (B), (D), and (E), and optionally the above-described optional components, and kneading them with a batch kneader such as a roll, kneader, Banbury mixer, or a commonly used kneading device such as a twin-screw extruder. Similarly, in Form 2, the wire-sealing composition of the present invention can be obtained by formulating the above-described components (C), (D), and (E), and optionally the above-described optional components, and kneading them with a batch kneader such as a roll, kneader, Banbury mixer, or a commonly used kneading device such as a twin-screw extruder.

[0029] [Wire with terminal] The wire with terminal of the present invention is, for example, a wire with terminal in which a cured product of the wire-sealing composition of the present invention is applied as a coating material for the wire with terminal disclosed in JP-A-2020-164669. The wire with terminal of the present invention is a wire with terminal in which a covered conductor and a terminal are connected. In the present invention, the covered conductor includes a covered portion and a conductor exposed from the tip of the covered portion. The terminal has a terminal body and a crimping portion. The crimping portion includes a wire crimping portion to which the wire is crimped, a covering crimping portion to which the covering portion is crimped, and a barrel intermediate portion between the wire crimping portion and the covering crimping portion. At least the portion from the covering crimping portion to the end of the exposed wire and other than the crimping portion is sealed with a cured product of the composition for sealing a wire of the present invention. In the wire with a terminal of the present invention in the above form, it is preferable that the entire portion from the covering crimping portion to the end of the exposed wire is sealed with a cured product of the composition for sealing a wire of the present invention.

[0030] Hereinafter, with reference to the drawings, a preferred embodiment of the wire with a terminal of the present invention will be described. FIG. 1 is a perspective view showing a wire 10 with a terminal, and FIG. 2 is a cross-sectional view. Note that FIG. 1 is a view in which a cured product (cured product of the composition for sealing a wire) 17a is seen through. The wire 10 with a terminal is configured by connecting a terminal 1 and a covered wire 11.

[0031] The covered wire 11 includes a wire 13a made of aluminum or an aluminum alloy and a covering portion 15 that covers the wire 13a. That is, the covered wire 11 includes a covering portion 15 and a wire 13a exposed from its tip. The wire 13a is, for example, a stranded wire in which a plurality of strands are twisted together.

[0032] The terminal 1 is of an open barrel type and is made of, for example, copper or a copper alloy. The covered 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 has an opening at the upper side.

[0033] The terminal body 3 is formed by shaping a plate-like material of a predetermined shape into a cylindrical body with a rectangular cross-section. The terminal body 3 has, inside, an elastic contact piece formed by folding the plate-like material into the rectangular cylindrical body. The terminal body 3 has a male terminal or the like inserted and connected from the front end portion. In the following description, an example is shown in which the terminal body 3 is a female terminal that allows insertion of an insertion tab (not shown) such as a male terminal. However, in the present invention, the detailed shape of this 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.

[0034] The crimping portion 5 is a portion that is crimped to the covered conductor 11. Before crimping, it has a barrel shape with a substantially U-shaped cross-sectional shape perpendicular to the longitudinal direction of the terminal 1. The crimping portion 5 of the terminal 1 includes a conductor crimping portion 7 that crimps the conductor 13 exposed from the covering portion 15 to the tip side of the covered conductor 11, a covering crimping portion 9 that crimps the covering portion 15 of the covered conductor 11, and a barrel intermediate portion 8 between the conductor crimping portion 7 and the covering crimping portion 9.

[0035] On a part of the inner surface of the conductor crimping portion 7, serrations (not shown) are provided in the width direction (a direction perpendicular to the longitudinal direction). By forming such serrations, when the conductor 13 is crimped, it is easy to break the oxide film on the surface of the conductor 13a, and the contact area with the conductor 13a can be increased.

[0036] The tip of the covered conductor 11 has the covering portion 15 peeled off, and the internal conductor 13a is exposed. The covering portion 15 of the covered conductor 11 is crimped by the covering crimping portion 9 of the terminal 1. Also, the conductor 13a exposed by peeling off the covering portion 15 is crimped by the conductor crimping portion 7. In the conductor crimping portion 7, the conductor 13a and the terminal 1 are electrically connected. Note that the end face of the covering portion 15 is located in the barrel intermediate portion 8 between the covering crimping portion 9 and the conductor crimping portion 7.

[0037] In the present invention, at least the portion between the end of the conductive wire 13a exposed from the coated crimping portion 9 and outside the crimping portion 5 is covered with the cured product 17a. That is, at least the portion between the end of the conductive wire 13a exposed from the coated crimping portion 9 and outside the crimping portion 5 is covered with the cured product 17a, and the conductive wire 13a is not exposed to the outside by the cured product 17a. That is, the void inside the conductive wire 13a is filled with the cured product of the conductive wire sealing composition of the present invention, and a layer (resin coating layer) made of a resin coating material obtained by curing the conductive wire sealing composition of the present invention is provided on the surface of the conductive wire 13a. In the terminal-attached electric wire of the present invention in the above form, it is preferable that the entire portion from the end of the conductive wire 13a exposed from the coated crimping portion 9 is sealed with the cured product 17a of the conductive wire sealing composition of the present invention.

[0038] [Method for manufacturing a terminal-attached electric wire] The method for manufacturing a terminal-attached electric wire of the present invention is a method for manufacturing a terminal-attached electric wire in which a coated conductive wire and a terminal are connected, The coated conductive wire includes a coating portion and a conductive wire exposed from the tip of the coating portion, The terminal has a terminal body and a crimping portion, and the crimping portion includes a conductive wire crimping portion where the conductive wire is crimped, a coated crimping portion where the coating portion is crimped, and a barrel intermediate portion between the conductive wire crimping portion and the coated crimping portion, and includes at least a step (1) of applying the conductive wire sealing composition of the present invention to the portion between the coated crimping portion and the end of the exposed conductive wire and outside the crimping portion, and a step (2) of curing the conductive wire sealing composition. For the manufacture of the terminal-attached electric wire of the present invention, for example, reference can be made to Japanese Unexamined Patent Application Publication No. 2020-164669. However, the curing of the conductive wire sealing composition of the present invention is preferably performed in the same manner as the method for manufacturing a wire harness described later.

[0039] [Wire harness] The wire harness of the present invention is formed by bundling a plurality of electric wires each having a conductor exposed portion and a conductor coated portion, and the conductor exposed portions are welded to form a joint portion (including a conductor bundle and a fiber core wire), and the conductor joint portion is sealed with a cured product of the conductor sealing composition of the present invention. That is, the voids inside the joint portion are filled with the cured product of the conductor sealing composition of the present invention, and a layer (resin coating layer) made of a resin coating material obtained by curing the conductor sealing composition of the present invention is provided on the surface of the joint portion. Note that 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.

[0040] [Method for manufacturing 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 portion formed by welding the conductor exposed portions, and curing the applied conductor sealing composition by irradiating ultraviolet rays thereto for 1 to 300 seconds. A photo radical polymerization initiator absorbs light to generate radicals, and for example, initiates ring-opening polymerization. On the other hand, a photo cationic polymerization initiator absorbs light and generates cations by pulling out hydrogen, and for example, initiates ring-opening polymerization. In addition, when using a thermally latent cationic polymerization initiator, it is preferable to heat at 60 to 150°C (preferably 80 to 120°C) for 1 to 120 minutes after ultraviolet irradiation. The joint portion is preferably formed by ultrasonic welding of the conductor exposed portions. The conditions for ultrasonic welding are not particularly limited as long as the conductor exposed portions can be welded. For example, reference can be made to JP-A-2019-18226, JP-A-2019-181525, and JP-A-2019-186070.

[0041] The method for applying the conductor sealing composition to the joint portion is not particularly limited, and examples thereof include dip coating, dispenser coating, and casting coating, with dip coating being preferred. Dip coating can be performed by immersing the joint portion in an ultraviolet-transmissive insulating container containing the conductor sealing composition. The ultraviolet transmittance of the insulating container is, for example, 30% or more, preferably 50% or more. The material of the insulating container is not particularly limited as long as it is insulating. For example, containers made of polyvinyl chloride, polyethylene, polypropylene, acrylic resin, or polyethylene terephthalate can be used. The shape of the insulating container is not particularly limited. For example, flat shapes, cylindrical shapes, and shapes combining flat and cylindrical shapes (all in cross-section) can be mentioned. An insulating container with at least a part being flat is preferred. The ultraviolet irradiation can be carried out by ordinary methods. In the present invention, it is preferable to use a ring-shaped ultraviolet irradiation device (ring light), put the above container into the ring of the device, and irradiate ultraviolet rays in a state where the joint is immersed in the composition for sealing the conductor.

[0042] As the conductor, it can be a single wire or a stranded wire, and it can also be a bare wire or a wire coated with tin plating or enamel. Examples of the metal material forming the conductor include soft copper, copper alloy, aluminum, etc. There are no particular restrictions on the conductor diameter, the material of the conductor, the thickness of the resin coating layer, etc., and they can be appropriately determined according to 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.

[0043] The shape and material of the conductor may be any conductor as long as it has the shape and material (such as copper, aluminum, etc.) generally used in wire harnesses.

Examples

[0044] The present invention will be described in more detail based on the examples. It should be noted that the present invention is not construed as being limited by these examples except as defined in the present invention.

[0045] <Preparation of the composition for sealing the conductor> According to the compositions (components of the composition (components (A) to (E), thermal radical polymerization initiator, and redox catalyst) and their contents) shown in Table 1-1 and 1-2 below (hereinafter, Table 1-1 and Table 1-2 are collectively referred to as Table 1), in a light-shielded glass container, using a homodisper from Primix Corporation, each component was uniformly mixed and stirred at 23 °C and a rotational speed of 2500 rpm for 10 minutes to obtain the compositions for wire encapsulation of Examples 1 to 18 and Comparative Examples 1 to 4.

[0046] [Test Example 1] Storage Stability The compositions for wire encapsulation of Examples 1 to 18 and Comparative Examples 1 to 4 were allowed to stand in the dark at 25 °C for 30 days. The viscosity before storage and the viscosity after storage were measured, and when the viscosity before storage was taken as 100%, the viscosity after storage was evaluated according to the following evaluation criteria. "3" to "5" indicate passing this test. - Viscosity Evaluation Criteria - 5: Less than 105% 4: 105% or more and less than 110% 3: 110% or more and less than 120% 2: 120% or more and less than 130% 1: 130% or more The viscosity was measured using a No. 3 rotor at a rotational speed of 30 rpm in accordance with JIS Z 8803 (2011).

[0047] <Fabrication of Wire Harness> This will be described with reference to Figure 3. Three aluminum alloy electric wires 18 (alloy composition AL-Mg-Si, length 0.2 m, wire cross-sectional area 0.75 mm 2 (≈0.75 sq)) and three copper electric wires 18 (length 0.2 m, wire cross-sectional area 0.75 mm 2From one end of two (≈0.75 sq) wires, the insulating coating was removed up to 2 cm to expose a part of the conducting wire 13b (conductor). The exposed conductor part was ultrasonically welded. A composition for wire sealing was poured into a flat or cylindrical container made of soft vinyl chloride, and the welded conductor part (joint 19) was immersed. From outside the container, it was irradiated with a 365 nm ultraviolet ring light for 90 seconds to cure the composition for wire sealing, and the welded conductor part was sealed with the cured product 17b to obtain the wire harness 20. For the aluminum alloy electric wire, ALVUS (trade name) manufactured by Furukawa Electric Co., Ltd. was used, and for the copper electric wire, CIVUS (trade name) manufactured by Furukawa Electric Co., Ltd. was used. The ultrasonic welding was performed using an ultrasonic metal bonding machine GMX-20DP (trade name) manufactured by Branson. A bundle of the exposed conductor parts (width on the horn side: 4 mm, width on the anvil side: 4.5 mm) was placed on the anvil, and ultrasonic vibration was applied in the gravitational direction at a pressure of 2 kN for 2 seconds for joining. The output was 2400 W, the oscillation frequency was 15 kHz, and the amplitude at the tip of the horn at no load was about 53 μm (peak to peak).

[0048] <Manufacture of Electric Wire with Terminal> This will be described with reference to FIG. 1. For the aluminum alloy electric wire (coated electric wire 11 in FIG. 1) (alloy composition: Al-Mg-Si, length: 0.2 m, conductor cross-sectional area: 0.75 mm 2 (≈0.75 sq)) From one end of three wires, the insulating coating was removed up to 2 cm to expose a part of the conducting wire 13a (conductor). The three conducting wires 13a were clamped and fixed at the front foot part of the terminal fitting, so-called wire barrel part, and at the same time, the covering part 15 was clamped and fixed at the rear foot part of the fitting of the terminal 1 (2.3II terminal (trade name) manufactured by Furukawa AS), so-called insulation barrel, to electrically and mechanically connect the conductor of the coated electric wire 11 and the fitting of the terminal 1.

[0049] [Performance Evaluation] Using each wire harness and electric wire with terminal manufactured as described above, performance evaluation was performed by the following tests.

[0050] [Test Example 2] Waterstop Performance (1) For wire harnesses (Examples 1 to 16 and Comparative Examples 1 to 4) This will be described with reference to Fig. 5 The joint 19 of the wire harness was placed in a water tank 21 filled with water, and pressurized air was sent at an air pressure of 49 kPa from the end of one of the five electric wires 18 by a regulator 22. 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 this test. Although Fig. 5 shows that the number of electric wires other than the electric wire 18 is three, the total number of electric wires in the wire harness used in the actual test was five (four electric wires for which air leakage was confirmed). - Evaluation Criteria - 5: There was no air leakage at all 4: There was slight air leakage from one electric wire 3: There was slight air leakage from two to four electric wires 2: There was significant air leakage from one to three electric wires 1: There was significant air leakage from four electric wires (2) For electric wires with terminals (Examples 17 and 18) This will be described with reference to Fig. 4 One end of the electric wire 10 with a terminal was placed in a water tank 21 filled with water, and pressurized air was sent at an air pressure of 49 kPa from the end of one of the three coated conductors 11 towards the terminal 1 by a regulator 22. The pressurized air passed through the coated 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" indicate passing this test - Evaluation Criteria - 5: There was no air leakage at all for 10 seconds after starting to send the pressurized air 4: There was leakage of 1 to 2 air bubbles in 10 seconds after starting to send the pressurized air 3: There was leakage of 3 to 5 air bubbles in 10 seconds after starting to send the pressurized air 2: There was leakage of 6 to 10 air bubbles in 10 seconds after starting to send the pressurized air 1. There was leakage of 11 or more air bubbles within 10 seconds after starting to supply pressurized air.

[0051] [Test Example 3] Curing property The cured product covering the conducting wire of the wire harness was peeled off, and the curing reaction rate (%) on the side in contact with the conducting wire of the cured product and the curing reaction rate (%) on the side not in contact with the conducting wire of the cured product were measured, and the difference (%) in the curing reaction rate was applied to the following evaluation criteria for evaluation. The cured product covering the conducting wire of the electric wire with terminals was peeled off, and the curing reaction rate (%) on the side in contact with the conducting wire of the cured product and the curing reaction rate (%) on the side not in contact with the conducting wire of the cured product were measured, and the difference (%) in the curing reaction rate was applied to the following evaluation criteria for evaluation. The following evaluation criteria are common to Examples 1 to 18 and Comparative Examples 1 to 4. "3" to "5" indicate passing 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 and less than 5% 3: The difference in the curing reaction rate is 5% or more and less than 7% 2: The difference in the curing reaction rate is 7% or more and less than 10% 1: The difference in the curing reaction rate is 10% or more

[0052] The above curing reaction rate was measured by using the infrared light absorption peak at a wavenumber of 1407 cm -1 with the peak appearing at a wavelength of 1506 to 1570 cm -1 as the reference peak. Specifically, for the cured product, the curing reaction rate was calculated by microscopic ATR (Attenuated Total Reflection) measurement by the FT-IR method. This measurement was performed by bringing the cured product into contact with a germanium crystal, irradiating the cured product with infrared light, and measuring the spectrum absorbed by the cured product and reflected by the germanium crystal. Difference in curing reaction rate (%) =(1 - (SAbs. / SRef.) / (DAbs. / DRef.)) × 100 "SAbs." indicates the absorption peak on the side in contact with the conductive wire of the cured product, "SRef." indicates the reference peak on the side in contact with the conductive wire of the cured product, "DAbs." is the absorption peak on the side in contact with the conductive wire of the cured product, and "DRef." is the reference peak on the side in contact with the conductive wire of the cured product.

[0053] [Test Example 4] Corrosion Resistance After peeling off the cured product in [Test Example 3], the surface area of the corroded part of the conductive wire 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" indicate passing this test. -Evaluation Criteria- 5: The surface area of the corroded part is 0 mm 2 4: The surface area of the corroded part is 0 mm 2 exceeds 3.0 mm 2 and is less than 3: The surface area of the corroded part is 3.0 mm 2 or more and less than 10.0 mm 2 2: The surface area of the corroded part is 10.0 mm 2 or more and less than 50.0 mm 2 1: The surface area of the corroded part is 50.0 mm 2 or more The surface area of the corroded part was determined by measuring the 3D shape of the object by 3D scanning the conductive wire after peeling off the cured product using a 3D shape measuring machine (VR-5200 (trade name) manufactured by Keyence Corporation).

[0054] The results obtained are summarized in Table 1 below.

[0055]

Table 1-1

[0056]

Table 1-2

[0057] The content of each component in the table is in parts by mass. A blank and "-" mean that the corresponding component is not included.

[0058] AL: Aluminum alloy electric 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): Radical polymerizable compound) Isobornyl acrylate (monofunctional) (manufactured by Nippon Shokubai Co., Ltd.) (Component (B): Cationic polymerizable compound) 3’,4’-Epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate (DICEL "CELoxide 2021P" (trade name)) (Component (D): Photo radical polymerization initiator) 1-Hydroxy-cyclohexyl-phenyl-ketone (IGM Resins B.V. "omnirad184" (trade name)) (Component (E) (light): Cationic polymerization initiator) Triarylsulfonium salt (SAN-APRO "CPI-300" (trade name)) (photo cationic polymerization initiator))

[0059] (Example 2) (Component (A): Radical polymerizable compound) Isobornyl acrylate (monofunctional) (manufactured by Nippon Shokubai Co., Ltd.) (Component (B): Cationic polymerizable compound) 3’,4’-Epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate (DICEL "CELoxide 2021P" (trade name)) (Component (D): Photo radical polymerization initiator) 1-Hydroxy-cyclohexyl-phenyl-ketone ("omnirad184" (trade name) manufactured by IGM Resins B.V.) (Component (E) (heat): Cationic polymerization initiator) 4-Hydroxyphenylbenzylmethylsulfonium (manufactured by Sanshin Chemical Industry Co., Ltd.) (heat latent cationic polymerization initiator))

[0060] (Example 3) (Component (A): Radical 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 (bifunctional epoxy) ("Celoxide 2081" (trade name) manufactured by Daicel Corporation) (Component (D): Photo radical polymerization initiator) 2,4,6-Trimethylbenzoyl-diphenylphosphine oxide ("omnirad TPO H" (trade name) manufactured by IGM Resins B.V.) (Component (E) (heat): Cationic polymerization initiator) "TA-100" (trade name) manufactured by San-Apro Ltd. (onium salt type heat latent cationic polymerization initiator))

[0061] (Example 4) (Component (A): Radical polymerizable compound) (2-Methyl-2-ethyl-1,3-dioxolan-4-yl)methyl acrylate (monofunctional) ("MEDOL-10" (trade name) manufactured by Osaka Organic Chemical Industry Co., Ltd.) (Component (B): Cationic polymerizable compound) ε-Caprolactone-modified 3’,4’-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate (bifunctional epoxy) ("Celoxide 2081" (trade name) manufactured by Daicel Corporation) (Component (D): Photo radical polymerization initiator) 2,4,6-Trimethylbenzoyl-diphenylphosphine oxide (「omnirad TPO H」(trade name) manufactured by IGM Resins B.V.) (Component (E) (heat): Cationic polymerization initiator) Trialkylsulfonium salt (「CP-66」(trade name) manufactured by ADEKA) (Thermal latent cationic polymerization initiator))

[0062] (Example 5) (Component (A): Radical polymerizable compound) Isobornyl acrylate (monofunctional) (manufactured by Nippon Shokubai Co., Ltd.) (Component (B): Cationic polymerizable compound) 3’,4’-Epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate (bifunctional epoxy) (「Celoxide 2021P」(trade name) manufactured by Daicel Corporation) (Component (D): Photo radical polymerization initiator) 1-Hydroxy-cyclohexyl-phenyl-ketone (「omnirad184」(trade name) manufactured by IGM Resins B.V.) (Component (E) (light): Cationic polymerization initiator) Triarylsulfonium salt (「CPI-300」(trade name) manufactured by San-Apro) (Photo cationic polymerization initiator)) (Component (E) (heat): Cationic polymerization initiator) Aromatic sulfonium salt (anion component: SbF6 - )(「Sun-Aid SI-60L」(trade name) manufactured by Sanshin Chemical Industry Co., Ltd.) (Thermal latent cationic polymerization initiator))

[0063] (Example 6) (Component (A): Radical 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 (bifunctional epoxy) (「Celoxide 2081」(trade name) manufactured by Daicel Corporation) (Component (D): Photoinitiator for free radical polymerization) 2,4,6-Trimethylbenzoyl-diphenylphosphine oxide (manufactured by IGM Resins B.V., trade name "omnirad TPO H") (Component (E) (light): Cationic polymerization initiator) Triarylsulfonium salt (manufactured by San-Apro, trade name "CPI-300") (photo cationic polymerization initiator) (Component (E) (heat): Cationic polymerization initiator) "TA-100" (trade name) manufactured by San-Apro (onium salt type thermally latent cationic polymerization initiator)

[0064] (Example 7) (Component (A): Radical polymerizable compound) (2-Methyl-2-ethyl-1,3-dioxolan-4-yl)methyl acrylate (monofunctional) (manufactured by Osaka Organic Chemical Industry Co., Ltd., trade name "MEDOL-10") (Component (B): Cationic polymerizable compound) 3’,4’-Epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate (bifunctional epoxy) (manufactured by Daicel, trade name "Celoxide 2021P") "Aron Oxetane OXT-211(POX)" (trade name) manufactured by Toagosei Co., Ltd. (monofunctional oxetane) 20 parts by mass of bifunctional epoxy and 20 parts by mass of monofunctional oxetane were used. (Component (D): Photoinitiator for free radical polymerization) 2,4,6-Trimethylbenzoyl-diphenylphosphine oxide (manufactured by IGM Resins B.V., trade name "omnirad TPO H") (Component (E) (light): Cationic polymerization initiator) Triarylsulfonium salt (manufactured by ADEKA, trade name "SP-152") (photo cationic polymerization initiator) (Component (E) (heat): Cationic polymerization initiator) Trialkylsulfonium salt (manufactured by ADEKA, trade name "CP-66") (thermal cationic polymerization initiator)

[0065] (Example 8) (Component (A): Radical polymerizable compound) Isobornyl acrylate (monofunctional) (manufactured by Nippon Shokubai Co., Ltd.) (Component (B): Cationic polymerizable compound) 3’,4’-Epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate (bifunctional epoxy) (manufactured by Daicel Corporation, "Celoxide 2021P" (trade name)) (Component (D): Photoinitiator for radical polymerization) 1-Hydroxy-cyclohexyl-phenyl-ketone (manufactured by IGM Resins B.V., "omnirad184" (trade name)) (Component (E) (light): Cationic polymerization initiator) Triarylsulfonium salt (manufactured by San-Apro Ltd., "CPI-300" (trade name)) (photo cationic polymerization initiator)

[0066] (Example 9) (Component (A): Radical polymerizable compound) Isobornyl acrylate (monofunctional) (manufactured by Nippon Shokubai Co., Ltd.) (Component (B): Cationic polymerizable compound) 3’,4’-Epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate (bifunctional epoxy) (manufactured by Daicel Corporation, "Celoxide 2021P" (trade name)) (Component (D): Photoinitiator for radical polymerization) 1-Hydroxy-cyclohexyl-phenyl-ketone (manufactured by IGM Resins B.V., "omnirad184" (trade name)) (Component (E) (light): Cationic polymerization initiator) Triarylsulfonium salt (manufactured by San-Apro Ltd., "CPI-300" (trade name)) (photo cationic polymerization initiator)

[0067] (Example 10) (Component (A): Radical polymerizable compound) Isobornyl acrylate (monofunctional) (manufactured by Nippon Shokubai Co., Ltd.) (Component (B): Cationic polymerizable compound) 3’,4’-Epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate (bifunctional epoxy) (manufactured by Daicel Corporation, "Celloxide 2021P" (trade name)) (Component (D): Photoinitiator for free radical polymerization) 1-Hydroxy-cyclohexyl-phenyl-ketone (manufactured by IGM Resins B.V., "omnirad184" (trade name)) (Component (E) (light): Photoinitiator for cationic polymerization) Triarylsulfonium salt (manufactured by San-Apro Ltd., "CPI-300" (trade name)) (photoinitiator for cationic polymerization)

[0068] (Example 11) (Component (A): Radical polymerizable compound) Isobornyl acrylate (monofunctional) (manufactured by Nippon Shokubai Co., Ltd.) (Component (B): Cationic polymerizable compound) 3’,4’-Epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate (bifunctional epoxy) (manufactured by Daicel Corporation, "Celloxide 2021P" (trade name)) (Component (D): Photoinitiator for free radical polymerization) 1-Hydroxy-cyclohexyl-phenyl-ketone (manufactured by IGM Resins B.V., "omnirad184" (trade name)) (Component (E) (light): Photoinitiator for cationic polymerization) Triarylsulfonium salt (manufactured by San-Apro Ltd., "CPI-300" (trade name)) (photoinitiator for cationic polymerization)

[0069] (Example 12) (Component (A): Radical polymerizable compound) Isobornyl acrylate (monofunctional) (manufactured by Nippon Shokubai Co., Ltd.) (Component (B): Cationic polymerizable compound) 3’,4’-Epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate (bifunctional epoxy) (manufactured by Daicel Corporation, "Celloxide 2021P" (trade name)) (Component (C): Radical polymerizable and cationic polymerizable compound) Glycidyl methacrylate (having one methacryloyl group and one epoxy group) (manufactured by Mitsubishi Gas Chemical Company) (Component (D): Photo radical polymerization initiator) 1-Hydroxy-cyclohexyl-phenyl-ketone (trade name "omnirad184" manufactured by IGM Resins B.V.) (Component (E) (light): Cationic polymerization initiator) Triaryl sulfonium salt (trade name "CPI-300" manufactured by San-Apro) (photo cationic polymerization initiator)

[0070] (Example 13) (Component (A): Radical polymerizable compound) Isobornyl acrylate (monofunctional) (manufactured by Nippon Shokubai Co., Ltd.) (Component (C): Radical polymerizable and cationic polymerizable compound) Glycidyl methacrylate (having one methacryloyl group and one epoxy group) (manufactured by Mitsubishi Gas Chemical Company) (Component (D): Photo radical polymerization initiator) 1-Hydroxy-cyclohexyl-phenyl-ketone (trade name "omnirad184" manufactured by IGM Resins B.V.) (Component (E) (light): Cationic polymerization initiator) Triaryl sulfonium salt (trade name "CPI-300" manufactured by San-Apro) (photo cationic polymerization initiator)

[0071] (Example 14) (Component (A): Radical polymerizable compound) Isobornyl acrylate (monofunctional) (manufactured by Nippon Shokubai Co., Ltd.) (Component (B): Cationic polymerizable compound) "VNBB-SE" (trade name) (monofunctional alicyclic epoxy) manufactured by ENEOS (Component (D): Photo radical polymerization initiator) 1-Hydroxy-cyclohexyl-phenyl-ketone (trade name "omnirad184" manufactured by IGM Resins B.V.) (Component (E) (light): Cationic polymerization initiator) Triaryl sulfonium salt ("CPI-300" (trade name) manufactured by San-Apro, Ltd.) (photo cationic polymerization initiator)

[0072] (Example 15) (Component (A): Radical polymerizable compound) Trimethylolpropane triacrylate (polyfunctional) ("Biscoat #295" (trade name) manufactured by Osaka Organic Chemical Industry Co., Ltd.) (Component (B): Cationic polymerizable compound) 3’,4’-Epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate (bifunctional epoxy) ("Celloxide 2021P" (trade name) manufactured by Daicel Corporation) (Component (D): Photo radical polymerization initiator) 1-Hydroxy-cyclohexyl-phenyl-ketone ("omnirad184" (trade name) manufactured by IGM Resins B.V.) (Component (E) (light): Cationic polymerization initiator) Triaryl sulfonium salt ("CPI-300" (trade name) manufactured by San-Apro, Ltd.) (photo cationic polymerization initiator)

[0073] (Example 16) (Component (C): Radical polymerizable and cationic polymerizable compound) Glycidyl methacrylate (having one methacryloyl group and one epoxy group) (manufactured by Mitsubishi Gas Chemical Company) (Component (D): Photo radical polymerization initiator) 1-Hydroxy-cyclohexyl-phenyl-ketone ("omnirad184" (trade name) manufactured by IGM Resins B.V.) (Component (E) (light): Cationic polymerization initiator) Triaryl sulfonium salt ("CPI-300" (trade name) manufactured by San-Apro, Ltd.) (photo cationic polymerization initiator)

[0074] (Example 17) (Component (A): Radical polymerizable compound) Isobornyl acrylate (monofunctional) (manufactured by Nippon Shokubai Co., Ltd.) (Component (B): Cationic polymerizable compound) 3’,4’-Epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate (manufactured by Daicel Corporation, "Celloxide 2021P" (trade name)) (Component (D): Photoinitiator for free radical polymerization) 1-Hydroxy-cyclohexyl-phenyl-ketone (manufactured by IGM Resins B.V., "omnirad184" (trade name)) (Component (E) (light): Photoinitiator for cationic polymerization) Triarylsulfonium salt (manufactured by San-Apro, "CPI-300" (trade name)) (photoinitiator for cationic polymerization))

[0075] (Example 18) (Component (A): Radical polymerizable compound) Isobornyl acrylate (monofunctional) (manufactured by Nippon Shokubai Co., Ltd.) (Component (B): Cationic polymerizable compound) 3’,4’-Epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate (manufactured by Daicel Corporation, "Celloxide 2021P" (trade name)) (Component (D): Photoinitiator for free radical polymerization) 1-Hydroxy-cyclohexyl-phenyl-ketone (manufactured by IGM Resins B.V., "omnirad184" (trade name)) (Component (E) (heat): Photoinitiator for cationic polymerization) Aromatic sulfonium salt (anion component: SbF6 - )(manufactured by Sanshin Chemical Industry Co., Ltd., "Sun-Aid SI-60L" (trade name)) (thermally latent photoinitiator for cationic polymerization))

[0076] (Comparative Example 1) (Component (A): Radical polymerizable compound) Isobornyl acrylate (monofunctional) (manufactured by Nippon Shokubai Co., Ltd.) (Component (D): Photoinitiator for free radical polymerization) 1-Hydroxy-cyclohexyl-phenyl-ketone (manufactured by IGM Resins B.V., "omnirad184" (trade name))

[0077] (Comparative Example 2) (Component (A): Radical polymerizable compound) Isobornyl acrylate (monofunctional) (manufactured by Nippon Shokubai Co., Ltd.) (Component (D): Photo radical polymerization initiator) 1-Hydroxy-cyclohexyl-phenyl-ketone ("omnirad184" (trade name) manufactured by IGM Resins B.V.) (Thermal radical polymerization initiator) Cumene hydroperoxide ("Perkyl H" (trade name) manufactured by NOF Corporation)

[0078] (Comparative Example 3) (Component (A): Radical polymerizable compound) Isobornyl acrylate (monofunctional) (manufactured by Nippon Shokubai Co., Ltd.) (Component (D): Photo radical polymerization initiator) 1-Hydroxy-cyclohexyl-phenyl-ketone ("omnirad184" (trade name) manufactured by IGM Resins B.V.) (Thermal radical polymerization initiator) Cumene hydroperoxide ("Perkyl H" (trade name) manufactured by NOF Corporation) (Redox catalyst) Copper(II) ethylhexanoate (manufactured by Fujifilm Wako Pure Chemical Corporation)

[0079] (Comparative Example 4) (Component (A): Radical polymerizable compound) Isobornyl acrylate (monofunctional) (manufactured by Nippon Shokubai Co., Ltd.) (Component (B): Cationic polymerizable compound) 3’,4’-Epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate (bifunctional epoxy) ("Celoxide 2021P" (trade name) manufactured by Daicel Corporation) (Thermal radical polymerization initiator) Cumene hydroperoxide ("Perkyl H" (trade name) manufactured by NOF Corporation) (Component (E) (light): Cationic polymerization initiator) Triarylsulfonium salt ("CPI-300" (trade name) manufactured by San-Apro Ltd.) (photo cationic polymerization initiator) (Component (E) (heat): Cationic polymerization initiator) Aromatic sulfonium salt (anion component: SbF6 - (manufactured by Sanshin Chemical Industry Co., Ltd., "Sun Aid SI-60L" (trade name)) (thermally latent cationic polymerization initiator))

[0080] It can be seen from Table 1 as follows. The composition of Comparative Example 1 contains a radically polymerizable compound (Component (A)) and a photoinitiator (Component (D)) 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)) defined in the present invention. Also, the composition of Comparative Example 1 does not contain a radically and cationically polymerizable compound (Component (C)). The wire harness produced using the composition of Comparative Example 1 is inferior in water stoppage between wires and internal curability. 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). Also, the composition of Comparative Example 2 does not contain Component (C). The composition of Comparative Example 2 is inferior in storage stability. Also, the wire harness produced using the composition of Comparative Example 2 is inferior in water stoppage between wires and internal curability. 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). Also, the composition of Comparative Example 3 does not contain Component (C). The composition of Comparative Example 3 is inferior in storage stability. Also, the wire harness produced using the composition of Comparative Example 3 is inferior in water stoppage between wires and internal curability. The composition of Comparative Example 4 contains Component (A), Component (B), Component (E), and a thermal radical polymerization initiator. However, the composition of Comparative Example 4 does not contain Component (D). Also, the composition of Comparative Example 4 does not contain Component (C). The composition of Comparative Example 4 is inferior in storage stability. Also, the wire harness produced using the composition of Comparative Example 4 is inferior in water stoppage between wires and internal curability. In contrast, the composition of the present invention has excellent storage stability, and both the wire harness and the wire with terminals produced using the composition of the present invention are excellent in water stoppage between wires, internal curability, and corrosion resistance (Examples 1 to 18).

Explanation of Signs

[0081] 1 Terminal 3 Terminal Body 4 Transition Portion 5 Crimping Portion 7 Conductor Crimping Portion 8 Inter-barrel Portion 9 Coating Crimping Portion 10 Wire with Terminal 11 Coated Conductor 13a, 13b Conductors 15 Coating Portion 17a, 17b Cured Products (Cured Products of Composition for Sealing Conductors) 18 Electric Wire 19 Joint Portion (Joint Portion Sealed with Cured Product of Composition for Sealing Conductors) 20 Wire Harness 21 Water Tank 22 Regulator F, G Indicate the flow of air.

Claims

1. A composition for wire encapsulation containing the following components (A), (B), (D) and (E), or the following components (C), (D) and (E), (A) A radically polymerizable compound (B) A cationically polymerizable compound (C) A radically and cationically polymerizable compound (D) A photoinitiator for radical polymerization (E) A cationic polymerization initiator Using (meth)acrylate as the component (A), an alicyclic epoxy compound as the component (B), and glycidyl methacrylate as the component (C), When the composition for wire encapsulation contains the components (A), (B), (D) and (E), in 100 parts by mass of the total content of the components (A) and (B), 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. A composition for wire encapsulation. (However, a composition for wire encapsulation containing an imide compound as a component other than the components (A) to (E) is excluded.)

2. The composition for wire encapsulation according to claim 1, wherein the component (E) contains a thermally latent cationic polymerization initiator.

3. A wire with a terminal in which a coated wire and a terminal are connected, The coated wire includes a coated portion and a wire exposed from the tip of the coated portion, The terminal has a terminal body and a crimping portion. The crimping portion includes a wire crimping portion where the wire is crimped, a coated crimping portion where the coated portion is crimped, and a barrel portion between the wire crimping portion and the coated crimping portion. At least, a part other than the crimping portion between the coated crimping portion and the end of the exposed wire is sealed with a cured product of the composition for wire encapsulation according to claim 1 or 2. A wire with a terminal.

4. A plurality of wires having a wire exposed portion and a wire coated portion are bundled together, A joint portion is formed by welding the wire exposed portions, The wire joint portion is sealed with a cured product of the composition for wire encapsulation according to claim 1 or 2. A wire harness.

5. A method for manufacturing a wire with a terminal in which a coated wire and a terminal are connected, The coated wire includes a coated portion and a wire exposed from the tip of the coated portion, The terminal has a terminal body and a crimping portion. The crimping portion includes a conductor crimping portion to which the conductor is crimped, a covering crimping portion to which the covering portion is crimped, and a barrel intermediate portion between the conductor crimping portion and the covering crimping portion. The method for manufacturing a wire with a terminal includes at least a step (1) of applying the composition for sealing a conductor according to claim 1 or 2 to a portion other than the crimping portion between the covering crimping portion and the exposed end portion of the conductor, and a step (2) of curing the composition for sealing a conductor.

6. The method for manufacturing a wire harness includes a step (1) of applying the composition for sealing a conductor according to claim 1 or 2 to a joint portion of conductors exposed from a plurality of wires, and a step (2) of curing the composition for sealing a conductor.

7. The method for manufacturing a wire harness according to claim 6, including ultrasonic welding of conductors exposed from a plurality of wires to form a joint portion of the exposed conductors.

8. The method for manufacturing 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 portion in the composition for sealing a conductor 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 ultraviolet rays in a ring shape from the outside of the insulating container.

Images