WO2014112157A1 - 硬化材料、ワイヤーハーネス及びその製造方法 - Google Patents
硬化材料、ワイヤーハーネス及びその製造方法 Download PDFInfo
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- WO2014112157A1 WO2014112157A1 PCT/JP2013/075673 JP2013075673W WO2014112157A1 WO 2014112157 A1 WO2014112157 A1 WO 2014112157A1 JP 2013075673 W JP2013075673 W JP 2013075673W WO 2014112157 A1 WO2014112157 A1 WO 2014112157A1
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- WIPO (PCT)
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- resin
- plasticizer
- meth
- curable material
- acrylate
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- H—ELECTRICITY
- H02—GENERATION; CONVERSION OR DISTRIBUTION OF ELECTRIC POWER
- H02G—INSTALLATION OF ELECTRIC CABLES OR LINES, OR OF COMBINED OPTICAL AND ELECTRIC CABLES OR LINES
- H02G1/00—Methods or apparatus specially adapted for installing, maintaining, repairing or dismantling electric cables or lines
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
- C08F290/06—Polymers provided for in subclass C08G
- C08F290/067—Polyurethanes; Polyureas
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4825—Polyethers containing two hydroxy groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/73—Polyisocyanates or polyisothiocyanates acyclic
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
- C09D175/16—Polyurethanes having carbon-to-carbon unsaturated bonds having terminal carbon-to-carbon unsaturated bonds
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
- H01B13/003—Apparatus or processes specially adapted for manufacturing conductors or cables using irradiation
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
- H01B13/06—Insulating conductors or cables
- H01B13/16—Insulating conductors or cables by passing through or dipping in a liquid bath; by spraying
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B7/00—Insulated conductors or cables characterised by their form
- H01B7/17—Protection against damage caused by external factors, e.g. sheaths or armouring
- H01B7/28—Protection against damage caused by moisture, corrosion, chemical attack or weather
- H01B7/282—Preventing penetration of fluid, e.g. water or humidity, into conductor or cable
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- H—ELECTRICITY
- H02—GENERATION; CONVERSION OR DISTRIBUTION OF ELECTRIC POWER
- H02G—INSTALLATION OF ELECTRIC CABLES OR LINES, OR OF COMBINED OPTICAL AND ELECTRIC CABLES OR LINES
- H02G15/00—Cable fittings
- H02G15/003—Filling materials, e.g. solid or fluid insulation
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- H—ELECTRICITY
- H02—GENERATION; CONVERSION OR DISTRIBUTION OF ELECTRIC POWER
- H02G—INSTALLATION OF ELECTRIC CABLES OR LINES, OR OF COMBINED OPTICAL AND ELECTRIC CABLES OR LINES
- H02G15/00—Cable fittings
- H02G15/02—Cable terminations
- H02G15/04—Cable-end sealings
- H02G15/043—Cable-end sealings with end caps, e.g. sleeve closed at one end
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- H—ELECTRICITY
- H02—GENERATION; CONVERSION OR DISTRIBUTION OF ELECTRIC POWER
- H02G—INSTALLATION OF ELECTRIC CABLES OR LINES, OR OF COMBINED OPTICAL AND ELECTRIC CABLES OR LINES
- H02G15/00—Cable fittings
- H02G15/08—Cable junctions
- H02G15/18—Cable junctions protected by sleeves, e.g. for communication cable
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- H—ELECTRICITY
- H02—GENERATION; CONVERSION OR DISTRIBUTION OF ELECTRIC POWER
- H02G—INSTALLATION OF ELECTRIC CABLES OR LINES, OR OF COMBINED OPTICAL AND ELECTRIC CABLES OR LINES
- H02G3/00—Installations of electric cables or lines or protective tubing therefor in or on buildings, equivalent structures or vehicles
- H02G3/02—Details
- H02G3/04—Protective tubing or conduits, e.g. cable ladders or cable troughs
- H02G3/0406—Details thereof
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01R—ELECTRICALLY-CONDUCTIVE CONNECTIONS; STRUCTURAL ASSOCIATIONS OF A PLURALITY OF MUTUALLY-INSULATED ELECTRICAL CONNECTING ELEMENTS; COUPLING DEVICES; CURRENT COLLECTORS
- H01R4/00—Electrically-conductive connections between two or more conductive members in direct contact, i.e. touching one another; Means for effecting or maintaining such contact; Electrically-conductive connections having two or more spaced connecting locations for conductors and using contact members penetrating insulation
- H01R4/22—End caps, i.e. of insulating or conductive material for covering or maintaining connections between wires entering the cap from the same end
Definitions
- the present invention relates to a curable material, a wire harness, and a method for manufacturing the same, and more specifically, as an adhesive material, a coating material, a sealing material, a molding material, etc., such as an automobile member, an electric / electronic device, and an aircraft member.
- the present invention relates to a curable material to be used, a wire harness mounted on an automobile or the like using the curable material as a waterproofing agent, and a method for manufacturing the wire harness.
- a self-adhesive tape or the like is formed by laminating a pressure-sensitive adhesive (adhesive) layer on the surface of a soft vinyl chloride resin support.
- a plasticizer is added to the vinyl chloride resin.
- the adhesive described in Patent Document 1 is composed of a curable resin containing polyacrylate and polyalkyl vinyl ether containing 40% by mass or more of C1 to C18-alkyl (meth) acrylate, a photopolymerization initiator, and the like.
- the resin used for the above waterproofing treatment is liquid from the viewpoint of ease of application and handling, and the shape is maintained by being applied and immersed in the splice part and cured.
- a thermosetting type a thermosetting type, a two-component mixed reaction curing type, a moisture curing type, a photocuring type and the like can be mentioned.
- photocurable resins particularly ultraviolet curable resins, are often used because of their fast curing time and simple process.
- the adhesive composition described in Patent Document 1 above is a UV-curable curable material, it is a hot-melt adhesive, so that it must be melted at a high temperature during use.
- the problem to be solved by the present invention is to provide a curable material that does not need to be melted at a high temperature, can suppress the migration of the plasticizer, and can be cured in a short time.
- the present invention provides a wire harness having a good waterproof performance and a method for manufacturing the same, by sufficiently curing even in a place where the irradiation light does not reach the waterproof agent and suppressing the transition of the plasticizer to the resin. is there.
- the curable material of the present invention is: A curable material containing at least a chain transfer agent,
- the chain transfer agent contains (a) a polyether structure, a compound containing two or more urethane bonds or two or more urea bonds in the molecule, and (b) a metal-containing compound.
- the solubility parameter of the curable material is not less than 9.4;
- the gist is that when the curable material is used in contact with a resin containing a plasticizer, the plasticizer can be inhibited from moving to the curable material.
- the curable material is a photo-curable material and has a dark-part curable property capable of curing a portion that does not reach irradiation light by the chain transfer agent.
- the (a) polyether structure preferably has three or more oxygen atoms.
- the (b) metal-containing compound is preferably a compound containing at least one metal selected from tin, copper, zinc, cobalt, and nickel.
- the resin containing the plasticizer is preferably one selected from a polyvinyl chloride resin, an acrylic resin, a polyurethane resin, a polyolefin resin, a phenol resin, and a polyamide resin.
- the wire harness of the present invention uses a cured product of the above-mentioned cured material.
- the wire harness of the present invention is It is a wire harness using a cured product of the above curable material as a waterproofing agent, A wire bundle in which a plurality of insulated wires whose conductors are covered with a covering material made of an insulator are bundled, A portion of the covering material is removed and a conductor exposed portion where an internal conductor is exposed is covered with the waterproofing agent, Having a waterproof part in which the surface of the waterproofing agent is covered with a light-transmitting protective member;
- the gist of the invention is that the protective member is a resin containing a plasticizer, and the plasticizer of the protective member can be suppressed from shifting to the waterproofing agent.
- a part of the covering material of the wire bundle in which a plurality of insulated wires covered with a covering material made of an insulator is bundled is removed to expose the internal conductor.
- the above-mentioned curable material is supplied to the conductor exposed portion, and the cured material is irradiated with light in a state where the surface of the curable material is covered with a protective member formed of a resin containing a plasticizer and having light transmittance.
- the gist is to form a waterproof part by curing.
- the protective member is preferably a sheet or tube formed from one selected from polyvinyl chloride resin, acrylic resin, polyurethane resin, polyolefin resin, phenol resin, and polyamide resin. .
- the curable material of the present invention can suppress the migration of the plasticizer in the resin from the resin containing the plasticizer in contact with the curable material to the curable material by setting the solubility parameter to 9.4 or more. Furthermore, since the curable material contains a chain transfer agent, it can be cured at room temperature in a short time by irradiation with ultraviolet rays, for example.
- the wire harness of the present invention uses the above-mentioned curable material, for example, even when the covering material such as an electric wire is in a state where the resin containing the plasticizer and the cured product of the curable material are in contact with each other, the plasticizer is cured as described above. Since it is possible to suppress the transition to a product, the physical properties of the cured product of the cured material do not deteriorate, and good characteristics can be maintained for a long period of time.
- the wire harness using the cured product of the above-described curable material of the present invention as a waterproofing agent is covered with the waterproofing agent with a conductor exposed portion where a part of the covering material of the wire bundle is removed and the internal conductor is exposed, Since the surface of the waterproofing agent has a waterproof part covered with a light-transmitting protective member, and the protective member is a resin containing a plasticizer, the plasticizer of the protective member is transferred to the waterproofing agent. Can be suppressed, and good waterproof performance can be obtained.
- a part of the covering material of the wire bundle in which a plurality of insulated wires covered with a covering material made of an insulator is bundled is removed to expose the internal conductor.
- the above-mentioned curable material is supplied to the conductor exposed portion, and the cured material is irradiated with light in a state where the surface of the curable material is covered with a protective member formed of a resin containing a plasticizer and having light transmittance.
- FIG. 1 is an external perspective view showing an example of the wire harness of the present invention.
- FIG. 2 is a horizontal sectional view taken along line AA in FIG.
- FIGS. 3A to 3C are process diagrams showing the vicinity of the splice for explaining the method of manufacturing the wire harness of the present invention.
- FIG. 4 is an explanatory view showing an example of a wire harness having a terminal splice portion.
- FIGS. 5A to 5D are explanatory views of a method of manufacturing a wire harness having a terminal splice portion.
- a photocurable material can be comprised from compositions, such as (A) photocurable component, (B) chain transfer agent, (C) photoinitiator, for example.
- the solubility parameter (Solubility Parameter; SP value) of the photocuring material is 9.4 or more.
- the solubility parameter of the present invention uses the Small method. That is, it is a numerical value obtained by estimating the solubility parameter from the molecular structure using the small calculation method.
- the solubility parameter of the curable material is less than 9.4, the curable material easily becomes compatible with the plasticizer, and the plasticizer of the resin in contact with the curable material is easily transferred into the curable material.
- the preferred curable material solubility parameter is 10 or more.
- the solubility parameter of the curable material can be adjusted to be in the above range by appropriately selecting the molecular structure of each component such as a curable component and a chain transfer agent blended in the curable material.
- the photo-curable component a photo-curing material capable of obtaining a cured product when irradiated with light such as ultraviolet rays can be used.
- the photocuring material includes those from which a cured product can be obtained by visible light, infrared rays, or the like.
- an ultraviolet curable material can be used as the photocurable material.
- an existing ultraviolet curable material can be used.
- a curable monomer such as (meth) acrylate, an oligomer or the like and (C) a photopolymerization initiator are mixed and used as long as a cured product is obtained by irradiation with ultraviolet rays. it can.
- the description of “(meth) acrylate” means acrylate and / or methacrylate.
- the curing principle of ultraviolet curable materials is that the photopolymerization initiator absorbs ultraviolet rays (ultraviolet light) to generate active species such as radical species, and the active species is a carbon-carbon double layer such as (meth) acrylate.
- the bond is radically polymerized and cured.
- the portion where the ultraviolet rays are shielded is uncured by ordinary ultraviolet curing.
- the chain transfer agent (B) the radicals generated by the irradiation of ultraviolet rays are transmitted to the places where the ultraviolet rays are shielded and no radicals are generated, and the polymerization reaction is started and advanced.
- the dark part where ultraviolet rays are shielded can be cured. That is, by adding the chain transfer agent (B), it is possible to impart dark part curability that can cure a portion that does not reach irradiation light.
- the photocuring material can be applied to a resin having fluidity at room temperature and containing a plasticizer, and can be cured at room temperature.
- the photocurable material has fluidity at room temperature and can be cured, it is not necessary to heat to a high temperature as compared with a hot melt adhesive, and coating and curing can be easily performed.
- the (meth) acrylate compound a conventionally known compound can be used without any particular limitation as long as it is a compound having one or more (meth) acrylate groups in the molecule.
- Specific examples of the (meth) acrylate compound include isobornyl (meth) acrylate, bornyl (meth) acrylate, tricyclodecanyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, and cyclohexyl.
- (Meth) acrylate (meth) acrylic acid, benzyl (meth) acrylate, 4-butylcyclohexyl (meth) acrylate, (meth) acryloylmorpholine, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, octyl (meth) acrylate , Isooctyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (me
- the chain transfer agent is composed of (a) a polyether structure, a nitrogen-containing compound containing two or more urethane bonds or two or more urea bonds in the molecule, and (b) a metal-containing compound.
- the polyether structure of the nitrogen-containing compound (a) preferably has 3 or more oxygen atoms.
- the nitrogen-containing compound (a) contains at least one urea bond part represented by the following (formula 1) or at least one urea bond part represented by the following (formula 2) in one molecule, and is a polyether. If it has a structure, a conventionally well-known thing can be used, without being restrict
- the nitrogen-containing compound as the component (a) include polyurethane using a polyether polyol, polyurea compound, and the like.
- the polyurethane and polyurea are obtained by reacting an isocyanate-containing compound with a polyether polyol hydroxyl group (—OH) -containing compound, amine (—NH 2 ) -containing compound, and the like.
- isocyanate-containing compound examples include the following compounds. Methylene diisocyanate, ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), dodecamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, lysine diisocyanate (LDI), 1,3,6-hexamethylene triisocyanate, etc. Aliphatic isocyanate.
- Hydrogenated-4,4'-diphenylmethane diisocyanate (hydrogenated MDI), hydrogenated-xylylene diisocyanate (hydrogenated XDI), 1,4-cyclohexane diisocyanate, hydrogenated-2,4-tolylene diisocyanate (hydrogenated TDI) , Cycloaliphatic isocyanates such as isophorone diisocyanate (IPDI) and norbornene diisocyanate (NBDI).
- Aromatic aliphatic isocyanates such as xylylene diisocyanate (XDI) and tetramethylxylylene diisocyanate (TMXDI); 1,4-diphenyl diisocyanate, 2,4 or 2,6-tolylene diisocyanate (TDI), 2,4 or 4,4-diphenylmethane diisocyanate (MDI), 1,5-naphthalene diisocyanate (NDI), 3,3 ′ -Polyisocyanates such as aromatic isocyanates such as dimethyl-4,4'-diphenylmethane diisocyanate, O-tolidine diisocyanate, polyphenylmethane polyisocyanate (crude MDI), triphenylmethane triisocyanate, tris (isocyanatephenyl) thiophosphate.
- XDI xylylene diisocyanate
- TXDI tetramethylxylylene diisocyanate
- Examples of the isocyanate-containing compound include biuret-type polyisocyanates obtained by reacting these polyisocyanates with water, adduct-type polyisocyanates obtained by reacting with polyhydric alcohols such as trimethylolpropane, and some of the polyisocyanates are polyesters.
- Examples include liquid prepolymers polymerized with polyether derivatives, multimers obtained by isocyanuration, and the like. These may be used alone or in combination of two or more.
- Polyether polyols to be reacted with isocyanate-containing compounds to obtain various polyurethanes include polyethylene oxide having a hydroxyl group at both ends, polypropylene oxide, random polyethylene oxide and polypropylene oxide, block copolymer, polyoxyethylene glycol, polyoxy Examples include diols such as propylene glycol and polyoxytetramethylene glycol, and triols such as polyoxyalkylene polyol having three hydroxyl groups.
- the polyether polyol preferably has three or more oxygen atoms in one molecule.
- the polyether polyurethane is not necessarily required to be in a liquid state, as long as it is finally dissolved or suspended when mixed in the curable material, but it is preferably in a liquid state for ease of mixing.
- the hydroxyl group-containing compound used at this time is preferably a liquid compound having a molecular weight of 100,000 or less.
- amine-containing compounds include amines having 1 to 30 carbon chains having a primary or secondary amino group at the terminal, (poly) ethylene glycol as a terminal diamine, (poly) propylene glycol as a terminal diamine, (poly ) Hexamethylene glycol, (poly) caprolactone of terminal diamine, (poly) ester (poly) ol of terminal diamine, (poly) amide of terminal diamine, (poly) ester of terminal diamine, and the like.
- polyurethane and polyurea compounds may have an alkyl group or a terminal group after polymerization by (thio) ether, (thio) ester, amide, (thio) urethane, (thio) urea, N-alkyl bond, etc., if necessary.
- the urethane bond or urea bond may be contained in the molecule even when a plurality of types are bonded or by combining end groups.
- the metal of the metal-containing compound as the component (b) constituting the chain transfer agent one kind or a plurality of kinds of metals selected from tin, copper, zinc, cobalt and nickel are preferably used.
- the component (b) metal-containing compound is not particularly limited as long as one or more kinds of the above metals are contained in the constituent molecules in the form of metal salts or complexes, and those conventionally known are used. Can be used.
- metal salt examples include metal salt forms such as carboxylate, phosphate, sulfonate, hydrochloride, bromate, and (per) (sub) chlorate of the metal species.
- the metal complex is not particularly limited as long as it is coordinated with an organic ligand capable of forming a coordination bond with the metal species and 1: 1 to 1: 4 (metal: ligand) and stabilized. A well-known thing can be used without this.
- the metal-containing compound of the component (b) include bis (2,4-pentanedionato) tin, dibutyltin bis (trifluoromethanesulfonate), dibutyltin diacetate, dibutyltin dilaurate, dibutyltin maleate, phthalocyanine tin (IV) Dichloride, tetrabutylammonium difluorotriphenyltin, phthalocyanine tin (II), tributyl (2-pyridyl) tin, tributyl (2-thienyl) tin, tributyltin acetate, tributyl (trimethylsilylethynyl) tin, trimethyl (2-pyridyl) ) Tin, bis (hexafluoroacetylacetonato) copper (II), bis (2,4-pentanedionato) copper (II), bis (1,3-
- the form of the metal-containing compound of the component (b) it is only necessary to finally be in a uniform state with the photo-curing material, so it is not always necessary to have high solubility in organic matter, but easy mixing and storage In order to prevent precipitation, an organic acid salt or a metal complex is preferable.
- the metal-containing compound of the component (b) can constitute a chain transfer agent by complexing with the polyether structure of the component (a) and a compound containing a urethane bond or a urea bond.
- the method for combining the component (a) and the component (b) is not particularly limited as long as both components are mixed at room temperature or under heating conditions. It is preferable to use a method in which the mixture is sufficiently stirred or kneaded using an agitator such as a mixing mixer at an appropriate temperature in an active gas atmosphere and dissolved or uniformly dispersed.
- an agitator such as a mixing mixer at an appropriate temperature in an active gas atmosphere and dissolved or uniformly dispersed.
- the photopolymerization initiator is not particularly limited as long as it is a compound that absorbs ultraviolet rays and initiates radical polymerization, and conventionally known ones can be used.
- the photopolymerization initiator include 1-hydroxycyclohexyl phenyl ketone, 2,2-dimethoxy-2-phenylacetophenone, xanthone, fluorenone, benzaldehyde, fluorene, anthraquinone, ethylanthraquinone, triphenylamine, carbazole, 3 -Methylacetophenone, 4-chlorobenzophenone, 4,4'-dimethoxybenzophenone, 4,4'-diaminobenzophenone, Michler's ketone, benzoin propyl ether, benzoin ethyl ether, benzyl dimethyl ketal, 1- (4-isopropylphenyl) -2- Hydroxy-2-methylpropan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, thioxanthone, diethylthioxanthone, 2-isopropyl Oxanthone, 2-
- photopolymerization initiator commercially available products such as IRGACURE184, 369, 651, 500, 907, CGI1700, CGI1750, CGI1850, CG24-61; Etc.) can be used.
- the mixing method for adding the chain transfer agent to the photo-curing material is not particularly limited, and it is sufficient to use a stirring device such as a mixing mixer at a suitable temperature under reduced pressure or in an inert gas atmosphere such as nitrogen. And stirring or kneading to dissolve or uniformly disperse the mixture.
- a stirring device such as a mixing mixer at a suitable temperature under reduced pressure or in an inert gas atmosphere such as nitrogen. And stirring or kneading to dissolve or uniformly disperse the mixture.
- the blending amount of the chain transfer agent with respect to the photo-curing material is not particularly limited, and may be appropriately added according to the type of the photo-curing material, the required dark part curability, and the like.
- the photo-curing material can contain various additives as required.
- the additive include stabilizers, softeners, pigments, dyes, antistatic agents, flame retardants, sensitizers, dispersants, solvents, antibacterial and antifungal agents.
- Each additive can be used in combination as appropriate.
- the composition can be obtained by mixing the above components.
- a stirring apparatus such as a mixing mixer under a reduced pressure or in an inert gas atmosphere such as nitrogen, and dissolved or uniformly dispersed.
- the method of making it preferable is.
- a polyvinyl chloride resin (it may describe as PVC resin), an acrylic resin, a polyurethane resin, polyolefin resin, a phenol resin And polyamide resin.
- the plasticizer is not particularly limited, and a known plasticizer can be used.
- the plasticizer include phthalic acid derivatives such as dimethyl phthalate, diethyl phthalate, dibutyl phthalate, dihexyl phthalate, diethyl hexyl phthalate, diisononyl phthalate, diisodecyl phthalate, ditridecyl phthalate, butyl benzyl phthalate, dioctyl adipate, diisononyl adipate, diisodecyl adipate, Adipic acid derivatives such as butyl diglycol adipate, sebacic acid derivatives such as dibutyl sebacate and dioctyl sebacate, azelaic acid derivatives such as dioctyl azelate, tricresyl phosphate, tributyl phosphate, trioctyl phosphate, tributoxyethyl
- tributoxyethyl phosphate SP value 8.6
- dioctyl sebacate SP value 8.7
- trioctyl trimellitate SP value 8.7
- Phthalic acid-based polyester SP value 9.0 or the like is preferable because the solubility parameter is lower than 9.4 and is separated.
- the cured material of the present invention When the cured material of the present invention is used for an application in contact with a resin including a plasticizer in an adhesive material, a coating material, a sealing material, a molding material, etc., such as an automobile member, an electric / electronic device, an aircraft member, The effect that the plasticizer from the resin can be prevented from transferring to a cured product of the curable material can be exhibited.
- the curable material can be suitably used for a wire harness.
- the wire harness is configured by combining one or a plurality of electric wires with terminals whose terminals are connected to the ends of the covered electric wires.
- the covered electric wire of a wire harness the circumference
- a resin containing a plasticizer such as a soft vinyl chloride resin is used.
- cured using the said photocuring material in the part which touches a covered electric wire is arrange
- Examples of the member using the photocuring material used for the wire harness include a waterproofing agent, an anticorrosive agent, a fixing member for an exterior product, a path regulating member, and an adhesive.
- a plurality of covered electric wires may be bundled by tape winding, or may be covered with an external part such as a round tube, a corrugated tube, or a protector.
- the electric wire conductor of the covered electric wire a stranded wire or a single wire formed by twisting a plurality of strands is used.
- the stranded wire may be composed of one type of metal strand or may be composed of two or more types of metal strand.
- the twisted wire may contain the strand etc. which consist of organic fibers other than a metal strand.
- “consisting of one type of metal strand” means that all the metal strands constituting the stranded wire are made of the same metal material, and “consisting of two or more types of metal strands” This means that the wire includes metal wires made of different metal materials.
- the stranded wire may include a reinforcing wire (tension member) for reinforcing the covered electric wire.
- Examples of the material of the metal wire constituting the conductor include copper, copper alloy, aluminum, aluminum alloy, and materials obtained by applying various platings to these materials.
- Examples of the material of the metal strand as the reinforcing wire include copper alloy, titanium, tungsten, and stainless steel.
- Examples of the organic fiber as the reinforcing wire include aromatic polyamide fibers such as poly- (p-phenylene terephthalamide).
- the covering material of the above-mentioned covered electric wire in addition to a soft vinyl chloride resin, for example, as a covering material for an insulated electric wire such as polyolefin, such as rubber, polyethylene, polypropylene, thermoplastic elastomer, other thermoplastic resin, curable resin, etc. Any resin can be used without particular limitation. These may be used alone or in combination of two or more.
- the covering material may be either a resin containing a plasticizer or a resin not containing a plasticizer.
- Various additives may be appropriately added to the material of the covering material. Examples of the additive include a flame retardant, a filler, a colorant and the like. Even if the covering material is a resin containing a plasticizer such as a soft vinyl chloride resin, the waterproofing agent has an effect of preventing the migration of the plasticizer. Good waterproofness can be obtained by preventing a decrease in adhesion and the like.
- the conditions for ultraviolet irradiation when the photocuring material is cured can be appropriately selected according to the composition of the photocuring material.
- an irradiation apparatus used for ultraviolet irradiation a known apparatus can be used.
- the irradiation device for example, a light source such as a bulb-type UV lamp or an LED-UV lamp in which Hg, Hg / Xe, a metal halide compound, or the like is sealed can be used.
- the ultraviolet irradiation device may use a condensing UV irradiation device that collects and irradiates light from the light source with a reflection mirror.
- the wire harness of the present invention is suitable for wiring in vehicles such as automobiles.
- FIG. 1 is an external perspective view showing an example of the wire harness of the present invention
- FIG. 2 is a horizontal sectional view taken along line AA in FIG.
- the curable material can be used as a waterproofing agent for the intermediate splice part of the wire harness.
- the wire harness 1 is composed of a wire bundle in which four insulated wires 4 covered with a covering material 3 made of an insulator are bundled around a conductor 2 made of a core wire. Yes.
- the intermediate splice portion 20 of the wire harness 1 has a conductor exposed portion 5 in which the insulated wire 3 of the bundle of wires is peeled off and the internal conductor 2 is exposed.
- the conductor exposed portion 5 the conductors 2, 2, 2, 2 of the plurality (4) of insulated wires 4, 4, 4, 4 are joined together, and the insulated wires are electrically connected.
- the intermediate splice part 20 has the exposed conductor part 5 covered with a waterproofing agent 40. Furthermore, the surface of the waterproofing agent 40 is covered with a protective sheet 30 having optical transparency with respect to the irradiation light for curing the photocurable material, and the waterproofing unit 10 is configured.
- the waterproofing agent 40 is cured by using the above-described photocuring material as a waterproofing agent composition.
- the protective sheet 30 is used as a protective member for holding it at a predetermined location until the waterproofing agent 40 of the waterproof part 10 is cured.
- the protective member is not limited to a sheet material such as the protective sheet 30 and may be formed in a tube shape such as a protective tube described later.
- the protective sheet 30 has a flexibility that can be deformed following the deformation of the surface of the waterproofing agent 40 of the waterproof part 10.
- the protective sheet 30 covers the periphery of the waterproofing agent 40 in a state of being in close contact with the surface of the waterproofing agent 40.
- the waterproofing agent 40 of the waterproof part 10 penetrates into the conductor exposed part 5 of the insulated wire 4 and hardens to a part where the penetrated inside irradiation light does not reach.
- the waterproofing agent 40 of the waterproof part 10 is cured in a state of being in close contact with the surface of the covering material 3 of the insulated wire 4 adjacent to the conductor exposed part 5. Further, in the waterproof part 10, the waterproofing agent 40 covers the covering parts 6 before and after the conductor 4 adjacent to the conductor exposed part 5 of the insulated wire 4. Since the waterproofing agent 40 covers the covering portion 6 in this way, moisture can be prevented from entering from the gap between the end portion of the covering material 3 on the intermediate splice portion 20 side and the conductor 2 to obtain a waterproof effect. be able to.
- FIGS. 3A to 3C are process diagrams showing the vicinity of the splice for explaining the method of manufacturing the wire harness of the present invention.
- the waterproofing agent composition 40a composed of a photo-curing material penetrates into the splice portion 20 when heated, so that the insulators 3 of the insulated wire 4 are in contact with each other.
- the conductor 2 has fluidity so as to be able to cross the gap between the wires constituting the conductor 2 and between the conductors 2 to fill the gap.
- the protective sheet 30 covers the surface of the waterproofing agent 40 in a state of being in close contact with the surface of the waterproofing agent 40.
- the protective sheet 30 has transparency (light permeability) to irradiation light such as ultraviolet rays when the photocuring material of the waterproofing agent 40 is cured.
- the light transmittance of the protective sheet 30 is preferably, for example, an ultraviolet transmittance of 50% or more, and more preferably an ultraviolet transmittance of 90% or more.
- the thickness of the protective sheet 30 is preferably 100 ⁇ m or less, more preferably 5 to 50 ⁇ m.
- a wrap sheet of olefin resin such as polyethylene, polypropylene, polyvinyl chloride, polyvinylidene chloride, and polyvinylidene fluoride, or a wrap sheet of general-purpose resin such as polyester, polyethylene terephthalate, and nylon can be used.
- a resin containing a plasticizer is used as the protective sheet 30 .
- the protective sheet 30 is preferably a sheet of polyvinyl chloride resin, polyvinylidene chloride resin, or polyvinylidene fluoride resin that has particularly good self-adhesion (adhesion).
- the protective sheet 30 has a Young's modulus (value at room temperature in the measurement direction according to JIS-K7113) in the range of 50 to 500 MPa when the thickness is less than 50 ⁇ m, and 10 to 100 MPa when the thickness is 50 to 100 ⁇ m. When the thickness exceeds 100 ⁇ m, it is preferably less than 10 MPa. Further, the protective sheet 30 has an elongation at break of preferably 20% or more, more preferably 50% or more.
- the protective sheet 30 preferably has a self-adhesive strength represented by peel adhesive strength (value at room temperature in a measuring method according to JIS-Z0237 or JIS-K6854) in the range of 0.5 to 10 N / m.
- the protective sheet 30 is deformed following the deformation of the surface of the waterproofing agent 40, and the waterproofing agent 40 is cured in a state where the waterproofing agent 40 surface and the protective sheet 30 are in close contact with each other.
- the protective sheet 30 has a high self-adhesive force, the protective sheet 30 can be easily covered when the protective sheet 30 is wound around the intermediate splice portion 20 and the waterproofing agent 40, and is excellent in workability.
- an adhesive layer made of a weak adhesive having a thickness of 10 ⁇ m or less may be formed on the surface of the protective sheet 30.
- the thickness of the pressure-sensitive adhesive layer is preferably 5 ⁇ m or less.
- a method for manufacturing the wire harness of FIG. 1 will be described.
- a wire bundle 7 in which an intermediate splice portion 20 is formed in advance using a plurality of insulated wires is prepared.
- the wire bundle 7 has a conductor exposed portion 5 where the covering material 3 of the insulated wire 4 is removed and the internal conductor 2 is exposed.
- a protective sheet 30 large enough to cover the intermediate splice portion 20 is prepared, and the intermediate splice portion 20 of the wire bundle 5 is placed on the protective sheet.
- the above-described waterproofing agent composition 40 a is supplied onto the intermediate splice part 20.
- the waterproofing agent composition 40a can be cured where light does not reach and contains a photocurable resin and a chain transfer agent.
- the waterproofing agent composition 40a is discharged and supplied from the nozzle 60 of the discharge device by a predetermined amount.
- the waterproofing agent composition 40a may be supplied at normal temperature or in a heated state.
- the waterproofing agent composition 40a is supplied not to the intermediate splice part 20, but to the surface of the protective sheet 30, and then the intermediate splice part 20 of the wire bundle is placed on the waterproofing agent composition 40a. May be.
- the folded back side of the protective sheet 30 wraps around the intermediate splice part 20 and the waterproofing agent composition 40 a, and the protective sheets 30 overlap each other in the part where the intermediate splice part 20 is not present.
- the protective sheet 30 is bent so that the overlapping portion 32 is obtained.
- the overlapping portion 32 of the protective sheet 30 is maintained in an overlapped state by the self-adhesiveness of the protective sheet 30.
- the protective sheet 30 is wound around the surface of the waterproofing agent composition 40a of the intermediate splice part 20 so that the protective sheet 30 is filled with the waterproofing agent composition 40a.
- the overlapping portion of the protective sheet 30 is rubbed with the roll 51, and the waterproofing agent composition 40 a of the overlapping portion 32 is pushed toward the intermediate splice portion 20.
- the overlapping portion 32 of the protective sheet 30 is wound around the waterproof portion 10 to be in close contact therewith.
- the overlapping portion of the protective sheet 30 is wound around the intermediate splice portion 20 and the waterproofing agent 40.
- the waterproof part 10 is pressed from the outside of the protective sheet 30 and wound around the intermediate splice part 20 and the waterproofing agent composition 40a.
- the waterproofing agent composition 40a locally present around the intermediate splice part 20 is extruded and travels between the outer peripheral part of the intermediate splice part 20 and the protective sheet 30, and the intermediate splice part 20 Cover the entire outer periphery.
- the protective sheet 30 is maintained in a state of being wound around the waterproof portion 10 by self-adhesion.
- the waterproof part 10 is also maintained in a state where it is pressed from the outside of the protective sheet 30.
- the intermediate splice portion is wound around the outer periphery of the intermediate splice portion 20 and the waterproofing agent composition 40a using the ultraviolet irradiation device 52. 20 is irradiated with ultraviolet rays 53 to cure the waterproofing agent composition 40 a to obtain the waterproofing agent 40.
- the ultraviolet rays 53 irradiated to the intermediate splice part 20 are transmitted through the protective sheet 30 and irradiated to the waterproofing agent composition 40a.
- the irradiation of ultraviolet rays is performed under irradiation conditions that allow the composition 40a of the waterproofing agent to be cured. Since the composition 40a of the waterproofing agent contains a chain transfer agent, the portion where the irradiation light reaches can be cured, and the portion where the irradiation light does not reach can be cured, and the waterproofing agent 40 is cured to the inside.
- the waterproof part 10 is obtained.
- the entire waterproof part 10 can be cured only by light irradiation such as ultraviolet rays, a step of heating and post-curing after the light irradiation is unnecessary.
- the intermediate splice part 20 is heated using a heating device or the like to reduce the viscosity of the waterproofing agent composition 40a, and the gap between the strands of the conductor 2 is reduced. Or it may be easy to penetrate into the gaps between the insulated wires 4.
- a heating device for example, a ceramic heater, a hot air jet heater, a pipe electromagnetic heater, a halogen lamp heater, a contact rubber heater, or the like can be used.
- FIG. 4 is an explanatory view showing an example of a wire harness having a terminal splice portion.
- the wire harness 1 before forming the waterproof portion has the wire bundle 11 of the four insulated wires 14, and the covering material 13 at the end portion of each insulated wire 14 is removed, and the conductor 12 has a conductor exposed portion 15 exposed. Further, the conductor exposed portion 15 has a terminal splice portion 21 where the ends of the conductor 12 are joined.
- the insulated wires of the wire bundle 11 are electrically connected to each other by the terminal splice portion 21.
- the terminal splice part 21 is joined by a known joining method such as crimping or welding.
- the conductor exposed portion 15 is covered with a waterproofing agent formed from the above-mentioned curable material. Furthermore, the surface of the waterproofing agent is covered with a protective tube 31 as a light-transmitting protective material, and constitutes the waterproof part 10.
- the protective tube 31 is formed from a resin containing a plasticizer. The protective tube 31 can use the same resin as the above-described protective sheet.
- the protective tube 31 is formed in a cap shape with one end closed and the other end opened.
- the conductor exposed portion 15 there is a gap between the conductors 12 except for the terminal splice portion 21. This gap is also filled with a waterproofing agent 40. Further, the waterproofing agent 40 and the protective tube 31 cover the conductor exposed portion 15 to the surface of the covering material 13 at the end of the wire bundle 11.
- FIG. 5 is an explanatory diagram of a method of manufacturing a wire harness having a terminal splice part.
- the waterproof portion 10 in the wire harness 1 first, as shown in FIG. 5A, the covering material at the end of the wire bundle 11 in which a plurality of insulated wires are bundled is peeled off and insulated. A conductor exposed portion 15 in which the conductor inside the electric wire is exposed is formed, and end portions of the conductor are joined to form a terminal splice portion 21.
- a protective tube 31 in which the above-described photocuring material 40a is placed is prepared.
- the electric wire bundle 11 is immersed in the hardening material 40a inside this protection tube 31, and the composition 40a of a waterproofing agent is supplied to an electric wire bundle.
- the terminal splice part 21 and the conductor exposed part 15 as a whole and a part of the covering material 13 of the wire bundle 11 are covered.
- Light irradiation is performed with the surface of the light curable material covered with a protective member (protective tube 31) made of a resin containing a plasticizer and having light permeability, and the curable material is cured to form a waterproof part.
- a wire harness having a waterproof part in which the terminal splice part 21 is covered with a waterproofing agent 40 and the surface of the waterproofing agent is covered with a protective tube 31 is obtained.
- the terminal splice portion 21 is covered with a waterproofing agent obtained by curing the waterproofing agent composition using the above-described photocuring material, and the protective tube 31 in contact with the waterproofing agent contains a plasticizer. It can suppress that the plasticizer of the protection tube 31 transfers to the waterproofing agent 40.
- Each component of (A) (meth) acrylate (photocuring material), (B) chain transfer agent, and (C) photopolymerization initiator is blended in the composition (parts by mass) shown in Tables 1 and 2, and a stirrer is used. Using, mixing, dissolving or dispersing, photocured materials of Examples 1 to 6 and Comparative Examples 1 to 5 were obtained. The SP values of the photocuring materials are shown in Tables 1 and 2 together.
- the content of residual isocyanate groups was calculated from the absorption area of FT-IR, and the reaction was terminated when there was no change after decreasing to about 15% compared to before the reaction, and a colorless transparent viscous liquid was obtained. . Furthermore, 9.84 g (84.8 mmol) of 2-hydroxyethyl acrylate, 0.05 g of dibutyltin dilaurate, and 0.02 g of pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] were charged. The liquid temperature was raised from room temperature to 50 ° C. over 1 hour with stirring.
- the content of residual isocyanate groups was calculated from the absorption area of FT-IR, and the reaction was terminated when there was no change after decreasing to about 15% compared to before the reaction, and a colorless transparent viscous liquid was obtained. . Furthermore, 9.84 g (84.8 mmol) of 2-hydroxyethyl acrylate, 0.05 g of dibutyltin dilaurate, and 0.02 g of pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] were charged. The liquid temperature was raised from room temperature to 50 ° C. over 1 hour with stirring.
- CT-1 Urethane acrylate UP-1, 100 g, was heated to 50 ° C. while stirring, 0.3 g of zinc acetylacetone was added as a metal-containing compound, and the mixture was stirred for 30 minutes while maintaining 50 ° C. Dispersed.
- CT-2 0.3 g of copper acetylacetone was used instead of the zinc acetylacetone of CT-1.
- CT-3 Urethane acrylate UP-2, 100 g, was heated to 50 ° C. while stirring, 0.3 g of zinc acetylacetone was added as a metal-containing compound, and the mixture was stirred and dispersed for 30 minutes while maintaining 50 ° C.
- CT-4 0.3 g of copper acetylacetone was used instead of zinc acetylacetone of CT-3.
- the plasticizer migration evaluation and the non-irradiation part curability evaluation were performed on the curable materials of Examples and Comparative Examples. An evaluation result is combined with Table 1 and Table 2, and is shown. The evaluation method is as follows.
- This sample was subjected to a tear test at 20 mm / min, and the tear strength was measured. A value obtained by dividing the stress at the time of tearing by the half of the circumference of the PVC resin was taken as the tear strength, unit N / m. The test was performed when the test sample was prepared (initial stage) and after heat treatment at 120 ° C. for 5 days (after heat resistance), and the tear strength was compared.
- plasticizer migration amount The migration amount of plasticizer was measured using FT-IR.
- FT-IR trimellitic acid tris (2-ethylhexyl)
- TOTM trimellitic acid tris (2-ethylhexyl)
- FT-IR FT-IR of a cured product obtained by curing the curable material. Measurements were made to create a calibration curve showing the relationship between the plasticizer peak area and the plasticizer content. Based on the absorption of NH in urethane near 775 cm ⁇ 1, the absorption of the aromatic ring of TOTM near 752 cm ⁇ 1 was determined by comparison.
- the cured product after heat treatment at 120 ° C. for 5 days used for the measurement of the tear strength was measured for FT-IR, and the amount of plasticizer migration (%) was calculated based on the calibration curve.
- Non-irradiation part curability evaluation Put each cured material of Examples and Comparative Examples in a glass tube having an inner diameter of 5 mm and a height of 50 mm so that the liquid level is 20 mm, and wrap the upper half (10 mm) of the contents with aluminum foil to block light. Created a part. Then, 25-second ring ultraviolet irradiation was performed from the side with a UV lamp (100 mW / cm 2 manufactured by SEN Special Light Company).
- the waterproof performance test of the wire harness which used the material of an Example and a comparative example as a waterproofing agent was done.
- the test produced the wire harness which formed the waterproof middle splice part shown in FIG. 1, and evaluated waterproof performance.
- the details of the test are as follows.
- a transparent PVC wrap film (PVC wrap film) having a UV transmittance of 94% is used as a protective sheet, and an example and a comparative example are provided as a waterproofing agent in the center on the PVC wrap film.
- the PVC wrap film After applying 1.1 g of the composition of the curable material and placing the intermediate splice part of the intermediate splice work, the PVC wrap film is bonded and squeezed, and the bonded PVC wrap film is further wound to form the intermediate splice part. It was formed in a shape covering about 16 mm length of the surface of the covering material.
- the PVC wrap film contains 30 parts by mass of bis (2-ethylhexyl) phthalate (DOP) as a plasticizer.
- DOP bis (2-ethylhexyl) phthalate
- the tear strength in the plasticizer migration evaluation is good both in the initial stage and after heat resistance, there is no decrease in strength after heat resistance, and the plasticizer migration amount is 5 % Or less, and the plasticizer migration can be suppressed.
- the non-irradiation part curing distance was 3 mm or more, and dark part curing was confirmed.
- the wire harness of the example suppressed the migration of the plasticizer from the PVC, and could be cured at a place where the ultraviolet rays did not reach, and a good waterproof performance was obtained.
- the strength reduction of the tear strength after heat resistance was large, the amount of plasticizer transferred exceeded 10%, and the waterproof performance after heat resistance was poor.
- the comparative example 4 can suppress the migration of the plasticizer, it does not contain a chain transfer agent, and thus has no curability in the non-irradiated part. Therefore, the initial waterproof performance was poor.
- the photo-curing material of the above example uses (A) a curable material and (B) a chain transfer agent. If (B) the chain transfer agent is a curable material, the (A) curable material is used. May not be used.
- the wire harness of the said Example demonstrated as an example the wire bundle which bundled four electric wires, the wire bundle should just be a some electric wire and may use wires other than four.
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Abstract
Description
少なくとも連鎖移動剤を含有する硬化材料であって、
前記連鎖移動剤が、(a)ポリエーテル構造と、2つ以上のウレタン結合又は2つ以上の尿素結合を分子中に含む化合物と(b)含金属化合物を含有し、
該硬化材料の溶解度パラメータが9.4以上であり、
該硬化材料が可塑剤を含む樹脂と接する用途で使用された場合に、前記可塑剤が該硬化材料に移行するのを抑制可能であることを要旨とするものである。
上記の硬化材料の硬化物を防水剤として用いたワイヤーハーネスであって、
導体が絶縁体からなる被覆材により被覆された絶縁電線が複数本束ねられた電線束を有し、
前記被覆材の一部が除去されて内部の導体が露出した導体露出部が前記防水剤により被覆され、
前記防水剤の表面が光透過性の保護部材により被覆されている防水部を有し、
前記保護部材が可塑剤を含む樹脂であり、前記保護部材の可塑剤が、前記防水剤に移行するのを抑制可能であることを要旨とするものである。
δ=ΣFi/V=ρΣFi/M
(δは溶解度パラメータ、Fiはモル吸引力、Vはモル容積、ρは密度、Mは分子量)
秋山三郎らによる『ポリマーブレンド』(1981年、シーエムシー)P125~P144参照
-NH-COO-
(式2)
-NH-CO-NH-
(A)(メタ)アクリレート
・IBA:イソボルニルアクリレート
・HPGA:ヘプタプロピレングリコールジアクリレート
・HPA:ヒドロキシプロピルジアクリレート
・TEGA:テトラエチレングリコールジアクリレート
・UP-1:ポリプロピレングリコールを用いて合成したウレタンアクリレート(合成品、合成法は後述する。)
・UP-2:1,10-デカンジオールを用いて合成したウレタンアクリレー(合成品、合成法は後述する)
攪拌機を備えた反応容器に、数平均分子量が400のポリプ口ピレングリコール80g(200mmol)、ヘキサメチレンジイソシアネー卜40g(238mmol)
とジブチルスズジラウレート0.05gを仕込み、攪拌しながら液温度を室温から50℃まで1時間かけて上げた。その後少量をサンプリングしFT-IRを測定して2300cm-1付近のイソシアネー卜基の吸収を確認しながら、50℃にて攪拌を続けた。FT-IRの吸収面積から残留イソシアネー卜基の含有量を計算し、反応前と比較して約15%まで減少して変化が無くなった時を反応終了とし、無色透明粘調性液体を得た。更に2-ヒドロキシエチルアクリレート9.84g(84.8mmol)、ジブチルスズジラウレート0.05g、ペンタエリスリトールテトラキス[3-(3,5-ジ-tert-ブチル-4-ヒドロキシフェニル)プロピオナート]0.02gを仕込み、攪拌しながら液温度を室温から50℃まで1時間かけて上げた。その後少量をサンプリングしFT-IRを測定して2300cm-1付近のイソシアネー卜基の吸収を確認しながら、50℃にて攪拌を続けた。FT-IRの吸収面積から残留イソシアネー卜基の含有量見積り、その吸収が消失した時を反応終了とし、無色透明粘調性液体を得た。これをUP-1とする。両末端がアクリレートでポリエーテル構造を持つウレタンアクリレートである。
攪拌機を備えた反応容器に、分子量が174.28の 1,10デカンジオール35g(200mmol)、ヘキサメチレンジイソシアネー卜40g(238mmol)
とジブチルスズジラウレート0.05gを仕込み、攪拌しながら液温度を室温から80℃まで1時間かけて上げた。その後少量をサンプリングしFT-IRを測定して2300cm-1付近のイソシアネー卜基の吸収を確認しながら、80℃にて攪拌を続けた。FT-IRの吸収面積から残留イソシアネー卜基の含有量を計算し、反応前と比較して約15%まで減少して変化が無くなった時を反応終了とし、無色透明粘調性液体を得た。更に2-ヒドロキシエチルアクリレート9.84g(84.8mmol)、ジブチルスズジラウレート0.05g、ペンタエリスリトールテトラキス[3-(3,5-ジ-tert-ブチル-4-ヒドロキシフェニル)プロピオナート]0.02gを仕込み、攪拌しながら液温度を室温から50℃まで1時間かけて上げた。その後少量をサンプリングしFT-IRを測定して2300cm-1付近のイソシアネー卜基の吸収を確認しながら、50℃にて攪拌を続けた。FT-IRの吸収面積から残留イソシアネー卜基の含有量見積り、その吸収が消失した時を反応終了とし、無色透明粘調性液体を得た。これをUP-2とする。両末端がアクリレートで、ポリエーテル構造を持たないウレタンアクリレートである。
・CT-1:ウレタンアクリレートUP-1、100gを撹拌しながら50℃に加温し、含金属化合物として亜鉛アセチルアセトンを0.3g加え、50℃を保ったまま30分間撹拌分散させた。
・CT-2:上記CT-1の亜鉛アセチルアセトンの代わりに銅アセチルアセトンを0.3g用いた。
・CT-3:ウレタンアクリレートUP-2、100gを撹拌しながら50℃に加温し、含金属化合物として亜鉛アセチルアセトンを0.3g加え、50℃を保ったまま30分間撹拌分散させた。
・CT-4:上記CT-3の亜鉛アセチルアセトンの代わりに銅アセチルアセトンを0.3g用いた。
・HCHPK: 1-ヒド口キシシク口ヘキシルフェニルケトン
・引裂き強度測定
可塑剤としてトリメリット酸トリス(2-エチルヘキシル)(TOTM)を含む直径3mmのPVC樹脂2本を被覆材が接触した状態で平行に並べ、その上に硬化材料を塗布し、UVランプ(SEN特殊光源社製、100mW/cm2)を用いて紫外線照射を25秒間行った。その後、20分間室温で放置して室温にし、裏側にも同様に硬化材料を塗布し硬化させ、引裂き試験用サンプルを作製した。このサンプルを20mm/分で引裂き試験を行い、引裂き強度を測定した。引裂き時の応力をPVC樹脂の円周の半分で割った値を引裂き強度、単位N/mとした。試験は試験用サンプル作製時(初期)と、120℃5日間熱処理した後(耐熱後)について行って、引裂き強度を比較した。
FT-IRを用いて、可塑剤の移行量を測定した。先ず合成した上記ウレタンアクリレートUP-1に可塑剤としてトリメリット酸トリス(2-エチルヘキシル)(TOTM)を所定量加えた硬化材料を数点調製し、硬化材料を硬化させた硬化物のFT-IR測定を行い、可塑剤ピーク面積と可塑剤含有量の関係を示す検量線を作成した。775cm-1付近のウレタンのNHの吸収を基準とし、752cm-1付近のTOTMの芳香環の吸収を比較して求めた。前記引裂き強度測定の際に用いた120℃5日間熱処理後の硬化物について、FT-IRを測定し、上記検量線を基に、可塑剤移行量(%)を算出した。
実施例、比較例の各硬化材料を、内径5mm、高さ50mmのガラス管に、液面の高さが20mmになるように入れ、内容物の上部半分(10mm)をアルミ箔で包み、遮光部分を作成した。その後、側面からUVランプ(SEN特殊光源社製100mW/cm2)で25秒環紫外線照射を行った。その後、室温まで戻すため20分間室温で放置した後、上部から1.5mm径のガラス棒を挿入し、指触にて判断できる硬化部の確認を行うことによって、紫外線照射面と遮光面の境界から上部(非照射部)に進んだ硬化部の距離を計測した。
外径4.4mmのポリ塩化ビニル(PVC)被覆電線を本線とし、外径3.6mmのPVC被覆電線2本を枝線とする中間スプライスワークを作製した。上記PVC被覆電線は、被覆材のPVCは可塑剤としてトリメリット酸トリス(2-エチルヘキシル)(TOTM)を全体の20質量部含有するものである。
図3(a)に示すように、紫外線透過率94%の透明なPVC製のラップフィルム(PVCラップフィルム)を保護シートとし、該PVCラップフィルム上の中央に、防水剤として実施例、比較例の硬化材料の組成物を1.1g塗布し、上記中間スプライスワークの中間スプライス部を載せた後、PVCラップフィルムを貼り合わせて絞り込み、更に貼り合わせたPVCラップフィルムを巻き込んで、中間スプライス部と被覆材表面の約16mm長を覆う形に形成した。上記PVCラップフィルムは、可塑剤として、フタル酸ビス(2-エチルヘキシル)(DOP)を全体の30質量部含有するものである。
中心波長が385nmのLED照射機(LED-UVランプ)を用い、上記PVCラップフィルムで巻き込んだ防水剤の組成物に、紫外線を照射して硬化させて防水部を形成して、ワイヤーハーネスを作製した。
耐圧試験は、ワイヤーハーネスの防水中間スプライス部全体を水中に浸漬した状態で、このハーネスの両端の電線全てからエアー圧200kPaの圧力を1分間加え、エアリークの有無を観察して初期の防水性能を評価した。評価基準は、エアリークがなかった場合を良好(○)とし、エアー圧200kPaを1分間加圧する途中でエアリークが確認された場合を不良(×)とした。また、防水中間スプライス部全体を120℃の恒温槽に入れて240時間加熱した後のワイヤーハーネスについても上記耐圧試験を行って、耐熱後の防水性能を評価した。評価基準は初期の試験と同じである。防水性能試験の結果を表1、表2に合わせて示す。
Claims (9)
- 少なくとも連鎖移動剤を含有する硬化材料であって、
前記連鎖移動剤が、(a)ポリエーテル構造と、2つ以上のウレタン結合又は2つ以上の尿素結合を分子中に含む化合物と(b)含金属化合物を含有し、
該硬化材料の溶解度パラメータが9.4以上であり、
該硬化材料が可塑剤を含む樹脂と接する用途で使用された場合に、前記可塑剤が該硬化材料に移行するのを抑制可能であることを特徴とする硬化材料。 - 前記硬化材料が、光硬化材料であり、前記連鎖移動剤により照射光の届かない部分の硬化が可能な暗部硬化性を有することを特徴とする請求項1記載の硬化材料。
- 前記(a)ポリエーテル構造が、3個以上の酸素原子を持つことを特徴とする請求項1又は2記載の硬化材料。
- 前記(b)含金属化合物が、スズ、銅、亜鉛、コバルト、ニッケルから選択される少なくとも1種の金属を含む化合物であることを特徴とする請求項1~3のいずれか1項に記載の硬化材料。
- 前記可塑剤を含む樹脂が、ポリ塩化ビニル樹脂、アクリル樹脂、ポリウレタン樹脂、ポリオレフィン樹脂、フェノール樹脂、ポリアミド樹脂から選択される1種であることを特徴とする請求項1~4のいずれか1項に記載の硬化材料。
- 請求項1~5のいずれか1項に記載の硬化材料の硬化物を用いたことを特徴とするワイヤーハーネス。
- 請求項1~5のいずれか1項に記載の硬化材料の硬化物を防水剤として用いたワイヤーハーネスであって、
導体が絶縁体からなる被覆材により被覆された絶縁電線が複数本束ねられた電線束を有し、
前記被覆材の一部が除去されて内部の導体が露出した導体露出部が前記防水剤により被覆され、
前記防水剤の表面が光透過性の保護部材により被覆されている防水部を有し、
前記保護部材が可塑剤を含む樹脂であり、前記保護部材の可塑剤が、前記防水剤に移行するのを抑制可能であることを特徴とするワイヤーハーネス。 - 導体が絶縁体からなる被覆材により被覆された絶縁電線が複数本束ねられた電線束の前記被覆材の一部を除去して内部の導体を露出させた導体露出部に、請求項1~5のいずれか1項に記載の硬化材料を供給し、該硬化材料の表面を可塑剤を含み光透過性を有する樹脂から形成された保護部材により被覆した状態で光照射を行い、前記硬化材料を硬化させて防水部を形成することを特徴とするワイヤーハーネスの製造方法。
- 前記保護部材が、ポリ塩化ビニル樹脂、アクリル樹脂、ポリウレタン樹脂、ポリオレフィン樹脂、フェノール樹脂、ポリアミド樹脂から選択される1種から形成されたシート又はチューブであることを特徴とする請求項8記載のワイヤーハーネスの製造方法。
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