WO2014077688A1 - Composition de résine durcissable par rayonnement pour la formation d'une couche d'enrobage de fil - Google Patents

Composition de résine durcissable par rayonnement pour la formation d'une couche d'enrobage de fil Download PDF

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Publication number
WO2014077688A1
WO2014077688A1 PCT/NL2013/050822 NL2013050822W WO2014077688A1 WO 2014077688 A1 WO2014077688 A1 WO 2014077688A1 NL 2013050822 W NL2013050822 W NL 2013050822W WO 2014077688 A1 WO2014077688 A1 WO 2014077688A1
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meth
acrylate
mass
composition
formula
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PCT/NL2013/050822
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English (en)
Inventor
Hirokazu Imai
Sukenori YAMASHITA
Takahiko Kurosawa
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Dsm Ip Assets B.V.
Jsr Corporation
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Priority claimed from JP2013234839A external-priority patent/JP2014114444A/ja
Application filed by Dsm Ip Assets B.V., Jsr Corporation filed Critical Dsm Ip Assets B.V.
Publication of WO2014077688A1 publication Critical patent/WO2014077688A1/fr

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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
    • C08G18/67—Unsaturated compounds having active hydrogen
    • C08G18/671—Unsaturated compounds having only one group containing active hydrogen
    • C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
    • 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
    • C08F290/08—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 side groups
    • C08F290/14—Polymers provided for in subclass C08G
    • C08F290/147—Polyurethanes; Polyureas
    • 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
    • C08G18/08—Processes
    • C08G18/16—Catalysts
    • C08G18/22—Catalysts containing metal compounds
    • C08G18/24—Catalysts containing metal compounds of tin
    • C08G18/244—Catalysts containing metal compounds of tin tin salts of carboxylic acids
    • C08G18/246—Catalysts containing metal compounds of tin tin salts of carboxylic acids containing also tin-carbon bonds
    • 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
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/44—Polycarbonates
    • 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
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
    • C08G18/7621—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring being toluene diisocyanate including isomer mixtures
    • 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
    • C08G18/81—Unsaturated isocyanates or isothiocyanates
    • C08G18/8141—Unsaturated isocyanates or isothiocyanates masked
    • C08G18/815—Polyisocyanates or polyisothiocyanates masked with unsaturated compounds having active hydrogen
    • C08G18/8158—Polyisocyanates or polyisothiocyanates masked with unsaturated compounds having active hydrogen with unsaturated compounds having only one group containing active hydrogen
    • C08G18/8175—Polyisocyanates or polyisothiocyanates masked with unsaturated compounds having active hydrogen with unsaturated compounds having only one group containing active hydrogen with esters of acrylic or alkylacrylic acid having only one group containing active hydrogen
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
    • H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
    • H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
    • H01B3/302—Polyurethanes or polythiourethanes; Polyurea or polythiourea
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
    • H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
    • H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
    • H01B3/44—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins
    • H01B3/447—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins from acrylic compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/20—Applications use in electrical or conductive gadgets
    • C08L2203/202—Applications use in electrical or conductive gadgets use in electrical wires or wirecoating

Definitions

  • the invention relates to a radiation-curable resin composition for formation of a coating layer of wire, particularly high -voltage wire for automobiles and so forth.
  • the high -voltage wire used primarily for motor circuits in hybrid vehicles, electric cars and so forth (for example, the high-voltage wire stipulated in JIS 3405), copper wire, aluminum wire or the like having excellent electrical characteristics and transmission characteristics is used as the conductor (also called core conductor), and insulated wire (also called coated wire) that uses thermoplastic resin such as polyvinyl chloride (PVC) or polyethylene (PE) as a coating layer (also called insulator layer) which coats the conductor is often used.
  • PVC polyvinyl chloride
  • PE polyethylene
  • cables provided with a sheath cables provided with a sheath
  • the first aspect of the instant claimed invention is a
  • radiation-curable resin composition for wire coating layer formation comprising:
  • R represents, each independently, a bifunctional aliphatic hydrocarbon group or a hydrocarbon group having a
  • n is a number set such that the number average molecular weight of the compound of formula (1) is from 500 to 10 000 g/mol;
  • (meth)acrylate-based radiation-curable resin composition for developing wire coating material to replace conventional PVC and PE the present inventors discovered that a radiation-curable resin composition for wire coating layer formation that can form a coating layer having the excellent heat resistance required in high-voltage wire and having sufficient strength is obtained if a radiation polymerization initiator is combined with a certain urethane (meth)acrylate and a compound having a cyclic structure and one ethylenically unsaturated group, and they thereby achieved the present invention.
  • the present invention provides a radiation-curable resin
  • composition for wire coating layer formation comprising:
  • R represents, each independently, a bifunctional aliphatic hydrocarbon group or a hydrocarbon group having a
  • n is a number set such that the number average molecular weight of the compound of formula (1) is from 500 to 10 000 g/mol;
  • the urethane (meth)acrylate of component (A) used in the present invention is obtained by reacting a diol represented by the above-mentioned formula (1), a diisocyanate, and a hydroxy group -containing (meth)acrylate.
  • a diol represented by the above-mentioned formula (1) a diisocyanate, and a hydroxy group -containing (meth)acrylate.
  • Component (A) has a structure shown by the Formula (b) as below.
  • 'DIOL' is a structural unit derived from diol
  • 'DIC is a structural unit derived from diisocyanate
  • 'HYD' is a structural unit derived from
  • Component (A) where 'y' is 1 is denoted as Component (Al) and Component (A) where 'y' is 2 is denoted as
  • Component (A2) could consist of either Component (Al) or Component (A2), or a mixture of Component (Al) and Component (A2).
  • the diol is a polycarbonate diol, and in the above-mentioned formula (1), R is preferably a hydrocarbon group having from 1 to 12 carbons - for example, a bifunctional aliphatic hydrocarbon group such as — (CH2)m— wherein m is from 3 to 12 and preferably from 5 to 9,
  • R' is a single bond or an alkanediol group having from 1 to 3 carbons.
  • Examples of the alkanediol group of R' in the above-mentioned formula (a) include -CH 2 - -(CH 2 ) 2 -, -(CH 2 ) 3 - and -CH 2 -CH(CH 3 )-.
  • R examples include—(CH2)6— —(CH2)9—
  • a wire coating layer having excellent heat resistance can be formed due to the fact that the diol is a polycarbonate diol.
  • R having the structure described above, fracture elongation, particularly fracture elongation at low temperature, is improved, and a wire coating layer having excellent durability at low temperature can be formed. It is particular preferred if R has an aliphatic structure from the viewpoint of fracture elongation.
  • the number average molecular weight of the diol is preferably from 500 to 10 000 g/mol, more preferably from 1000 to 6000 g/mol, and particularly preferably from 1000 to 3000 g/mol.
  • the number average molecular weight of the diol is in the aforementioned range, a wire coating layer having excellent fracture elongation and heat resistance can be formed.
  • the number average molecular weight of the diol is the number average molecular weight based on polystyrene units measured by gel permeation chromatography (GPC).
  • the total of the molecular weights of y units of 'DIOL' in the above Formula (b) is; preferably 500-3000 g/mol, more preferably 1000-3000 g/mol where 'y' is 1, or preferably 2000-10 000 g/mol, more preferably 2000-6000 g/mol where 'y' is 2.
  • Examples of commercially available products of the polycarbonate diols represented by the above-mentioned formula (1) include: Duranol T6002 (compound of number average molecular weight 2000 g/mol in which R in formula (1) is— (CH2)6— ), T5650E (compound of number average molecular weight 500 g/mol in which R in formula (1) is— (CH2)5— and — (CH2)6— in a molar ratio of 1: 1), T5652 (compound of number average molecular weight 2000 g/mol in which R in formula (1) is— (CH2)5— and — (CH2)6— in a molar ratio of 1: 1), G3452 (compound of number average molecular weight 2000 g/mol in which R in formula (1) is— (CH2)3— and
  • UH-100 compound of number average molecular weight 1000 g/mol in which R in formula (1) is— (CH2)6—
  • UH-200 compound of number average molecular weight 2000 g/mol in which R in formula (1) is— (CH2)6—
  • UH-300 compound of number average molecular weight 3000 g/mol in which R in formula (1) is— (CH2)6—
  • UHC50-200 compound of number average molecular weight 2000 g/mol in which R in formula (1) is— (CH 2 )6— and -((CH 2 )5C02)m(CH 2 )6- in a molar ratio of 1: 1)
  • UHC50-100 compound of number average molecular weight 1000 g/mol in which R in formula (1) is -(CH 2 )e- and -((CH 2 )5C02)m(CH 2 )6- in a molar ratio of 1: 1)
  • UC-100 compound of number average molecular weight 1000
  • formula (a) is— CH 2 — in a molar ratio of 1: 1) (the above made by Ube Industries); Kuraray Polyol C-1065N (compound of number average molecular weight 1000 g/mol in which R in formula (1) is— (CH 2 )9— and -CH 2 C(CH 3 )H(CH 2 ) 6 - in a molar ratio of 65:35), C-2065N (compound of number average molecular weight 2000 g/mol in which R in formula (1) is -(CH 2 ) 9 - and -CH 2 C(CH 3 )H(CH 2 ) 6 - in a molar ratio of 65:35), C-1015N (compound of number average molecular weight 1000 g/mol in which R in formula (1) is -(CH 2 )g- and -CH 2 C(CH 3 )H(CH 2 ) 6 - in a molar ratio of 15:85), C-2015N (compound of number average molecular weight 1000 g
  • C-1050 compound of number average molecular weight 1000 g/mol in which R in formula (1) is -CH2CH2C(CH 3 )HCH 2 CH2- and -(CH 2 ) 6 - in a molar ratio of 1: 1)
  • C-2050 compound of number average molecular weight 2000 g/mol in which R in formula (1) is -CH2CH2C(CH 3 )HCH 2 CH2- and -(CH 2 ) 6 - in a molar ratio of 1: 1) (the above made by Kuraray).
  • polyisocyanates particularly diisocyanates
  • examples of polyisocyanates, particularly diisocyanates include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1,3-xylylene
  • These polyisocyanates may be used independently or in a combination of two or more types.
  • Examples of the hydroxy group -containing (meth)acrylate include 2 -hydroxy ethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate,
  • H 2 C C(R 1 )— COOCH 2 CH 2 — (OCOCH 2 CH2CH2CH 2 CH2)n— OH 2)
  • R 1 indicates a hydrogen atom or methyl group
  • n indicates a number from 1 to 15.
  • compounds obtained by an addition reaction of a glycidyl group -containing compound such as an alkyl glycidyl ether, allyl glycidyl ether or glycidyl (meth)acrylate with (meth)acrylic acid may be used.
  • hydroxy group -containing (meth)acrylate compounds may be used independently or in a combination of two or more types.
  • isocyanate groups contained in the polyisocyanate are from 1.2 to 1.8 equivalents and the hydroxy groups of the hydroxy group -containing
  • (meth)acrylate are from 0.2 to 0.8 equivalents with respect to 1 equivalent of the hydroxy groups contained in the diol.
  • polyisocyanate and hydroxy group-containing (meth)acrylate are added in a batch and reacted; a method in which the diol and polyisocyanate are reacted and then the hydroxy group -containing (meth)acrylate is reacted; a method in which the polyisocyanate and hydroxy group-containing
  • the dilute monomer may be something that does not react with the other components during urethane (meth)acrylate synthesis.
  • the dilute monomer may be optionally selected from (meth)acrylate compounds that do not have a hydroxy group.
  • reaction temperature is normally from 10 °C to 90 °C, and from 30 °C to 80 °C is particularly preferable.
  • the urethane (meth)acrylate of component (A) is preferably blended in an amount from 20 to 80 mass%, more preferably from 30 to 70 mass%, with respect to a total of 100 mass% of the composition.
  • the Component (A) consists solely of Component (Al)
  • the Component (Al) could be blended preferably 50-80 mass%, more preferably 55-75 mass%, with respect to a total of 100 mass% of the composition
  • Component (A) consists solely of Component (A2)
  • the Component (A2) could be blended preferably 20-70 mass%, more preferably 30-60 mass%, with respect to a total of 100 mass% of the composition.
  • the compound having one ethylenically unsaturated group which is component (B) is a polymerizable monofunctional compound other than component (A).
  • component (B) By using this compound as component (B), the strength, particularly the Young's modulus and fracture elongation, of the wire coating layer obtained by the composition of the present invention is improved.
  • Component (B) is even more preferably a compound having a cyclic structure and one ethylenically unsaturated group.
  • examples of cyclic structures include alicyclic structures, heterocyclic structures that include nitrogen atoms or oxygen atoms, aromatic rings and so forth, among which aliphatic structures and heterocyclic structures that include nitrogen atoms are particularly preferred.
  • Examples of such polymerizable monofunctional compounds (B) include 2 -hydroxy ethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate,
  • 2-ethylhexyl(meth)acrylate nonyl (meth)acrylate, decyl (meth)acrylate, isodecyl (meth)acrylate, undecyl (meth)acrylate, dodecyl (meth)acrylate, lauryl (meth)acrylate, octadecyl (meth)acrylate, stearyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, butoxyethyl (meth)acrylate,
  • methoxyethylene glycol (meth)acrylate methoxyethyl (meth)acrylate, methoxypolyethylene glycol (meth)acrylate, methoxypolypropylene glycol (meth)acrylate, dicyclopentadienyl (meth)acrylate, dicylcopentanyl
  • (meth)acrylate isobornyl (meth)acrylate, bornyl (meth)acrylate, diacetone (meth)acrylamide, isobutoxymethyl (meth)acrylamide, N-vinylpyrrolidone, N-vinylcaprolactam, N,N-dimethyl (meth)acrylamide, i-octyl
  • (meth)acrylamide dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, 7-amino-3,7-dimethyloctyl (meth)acrylate, and the
  • R 2 indicates a hydrogen atom or methyl group
  • R 3 indicates an alkylene group having from 2 to 8 carbons, preferably from 2 to 5 carbons
  • R 4 indicates a hydrogen atom or methyl group
  • p indicates a number preferably from 1 to 4,
  • R 5 , R 6 , R 7 and R 8 each independently indicate a hydrogen atom or methyl group; and q indicates an integer from 1 to 5.
  • Examples of compounds having a cyclic structure and one ethylenically unsaturated group include vinyl group-containing lactams such as N-vinylpyrrolidone and N-vinylcaprolactam; alicyclic
  • (meth)acrylates such as isobornyl (meth)acrylate, bornyl (meth)acrylate, tricyclodecanyl (meth)acrylate and dicyclopentanyl (meth)acrylate; benzyl (meth)acrylate, 4-butylcyclohexyl (meth)acrylate, (meth)acryloyl morpholine, vinyl imidazole, vinyl pyridine, and the aforementioned compounds expressed by formulas (4) through (6).
  • components (B) compounds that have a cyclic structure and one ethylenically unsaturated group are preferred, and isobornyl (meth)acrylate, bornyl (meth)acrylate, tricyclodecanyl
  • the monofunctional compounds having a cyclic structure which are these components (B) are preferably blended in an amount from 15 to 75 mass%, such as in the range of 20 to 50 mass% or in the range of 25 to 65 mass%, most preferably 25-45 mass% with respect to a total of 100 mass% of the composition.
  • the diol of formula (1), used for preparing the urethane (meth)acrylate component (A), has a number average molecular weight of 1000-6000 g/mol (preferably 1000-3000 g/mol) and the compound
  • composition an amount of 25-65 mass% (preferably 25-45 mass%) with respect to a total of 100 mass% of the composition.
  • (C) used in the present invention include 1-hydroxycyclohexyl phenyl ketone, 2,2-dimethoxy-2-phenylacetophenone, xanthone, fluorenone, benzaldehyde, fluorine, anthraquinone, triphenylamine, carbazole,
  • 2-chlorothioxanthone 2-methyl-l-[4-(methylthio)phenyl]- 2-morpholino-propan-l-one, 2,4,6-trimethylbenzoyl diphenyl phosphine oxide, bis-(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentyl phosphine oxide; Irgacure ® 184, 369, 651, 500, 907, CGI1700, CGI1750, CGI1850, CG24-61, Darocure ® 1116, 1173 (the above made by Ciba Geigy Specialty Chemicals; now part of BASF); Lucirin TPO (made by BASF); and Ebecryl ® P36 (made by UCB).
  • the radiation polymerization initiator of (C) is preferably blended in an amount from 0.1 to 10 mass%, more preferably from 0.3 to 7 mass%, with respect to a total of 100 mass% of the composition.
  • photosensitizers for example, triethylamine
  • Component (D) which is a compound having two or more ethylenically unsaturated groups, may be further blended in the
  • the compound having two or more ethylenically unsaturated groups (D) are polymerizable polyfunction al compounds.
  • Examples of the polymerizable polyfunctional compound (D) include trimethylolpropane tri(meth)acrylate, trimethylolpropane
  • dimethylol diacrylate di(meth)acrylate of polyol of ethylene oxide or propylene oxide adduct of bisphenol A, di(meth)acrylate of polyol of ethylene oxide or propylene oxide adduct of hydrogenated bisphenol A, epoxy
  • tripropylene glycol di(meth)acrylate is particularly preferred.
  • Yupimer UV, SA1002 (the above made by Mitsubishi Chemical), and Aronix M-215, M-315, M-325 (the above made by Toa Gosei) may be used.
  • Aronix TO- 1210 (made by Toa Gosei) may be used.
  • These compounds having two or more ethylenically unsaturated groups (D) are blended in an amount from 0 to 20 mass%, preferably from 0 to 10 mass%, more preferably from 0 to 5 mass%, and most preferably 0 mass%, with respect to a total of 100 mass% of the composition. If blended in an amount exceeding 20 mass%, fracture elongation of the wire coating layer, particularly fracture elongation in the low temperature region, is diminished.
  • non-silicone-based lubricants and agents that enhance adhesion with the conductor may be blended in the composition of the present invention.
  • non-silicone-based lubricants include liquid paraffin, paraffin, polyethylene powder, modified polyethylene powder, polytetrafluoroethylene (PTFE) powder, hydrocarbon-based oil and polyether-based oil.
  • PTFE polytetrafluoroethylene
  • agents that enhance adhesion with the conductor include phosphorous-containing (meth)acrylates other than components (A), (B) and (D), and silane coupling agents.
  • additives for example, antioxidants, dyes, UV absorbents, photostabilizers, thermal polymerization inhibitors, leveling agents, surfactants, preservation stabihzers, plasticizers, fillers, anti-aging agents, wettability improving agents, surface improving agents, heavy metal inactivation agents, fire retardants (preferably having a reactive group such as a (meth)acryloyl group) - may be blended in the composition of the present invention within a range such that the
  • the viscosity at 25 °C of the composition of the present invention is preferably from 1 to 1000 Pa s, more preferably from 5 to 300 Pa s. Due to the viscosity being within the aforementioned range, the coating layer of coated wire or cable is easily formed. This viscosity may be measured by a type-B viscometer.
  • the coating layer of coated wire or cable is produced by coating metal wire as the conductor with the composition of the present invention to form a coated layer, and curing it by irradiating the coated layer with radiation.
  • radiation means infrared rays, visible light rays, ultraviolet rays, X-rays, electron beams, -rays, ⁇ -rays, ⁇ -rays and so forth.
  • a uniformly strong wire coating layer is formed in a simple manner by irradiation with radiation such as ultraviolet rays, and also, because this coating layer is made up of a cured product having a cross-linked structure obtained by curing a radiation-curable resin composition rather than a thermoplastic resin, it does not melt at the temperature at which
  • the wire coating layer formed using the composition of the present invention is strong against external stress because it has a high Young's modulus, and the coating layer is not easily broken even when the wire is bent with large curvature because fracture elongation is high.
  • the Young's modulus at 23 °C of the cured product obtained by curing the composition of the present invention is preferably from 1 to 1500 MPa, more preferably from 5 to 500 MPa.
  • the Young's modulus at -40 °C is preferably from 50 to 5000 MPa, more preferably from 300 to 3000 MPa.
  • Fracture strength is preferably from 10 to 150 MPa, more preferably from 30 to 80 MPa.
  • Fracture elongation at 23 °C is preferably from 50 to 600 %, more preferably from 80 to 500 %. Fracture elongation at -40 °C is preferably from 5 to 300 %, more preferably from 10 to 130 %. Also, it is preferred that the change in fracture elongation at 23 °C after 10 days at 180 °C is small compared to the value of fracture elongation at 23 °C before exposure to 180 °C. Specifically, from 50 to 400 % is preferred, and from 70 to 200 % is more preferred.
  • Young's modulus, fracture strength and fracture elongation of the cured product being in the aforementioned ranges, a tough wire coating layer that is not often broken even when the wire is bent with large curvature under strong external force can be obtained.
  • Young's modulus and fracture strength are measured at 23 °C 50 % RH or -40 °C according to JIS K 7127/5/50.
  • Young's modulus is the value determined from tensile strength at 2.5 % strain.
  • composition of the present invention is useful as a
  • radiation-curable resin composition that is for forming a coating layer of coated wire and cable, particularly high-voltage wire for vehicles, more preferably for automobiles and so forth. Furthermore, it is useful as a radiation-curable resin composition for formation of a sheath layer that contacts the outside of the shield of wire having a core conductor and shield (concealment layer). By applying the composition of the present invention and then irradiating it with radiation, a uniformly strong wire coating layer that does not melt at high temperature is formed in a simple manner.
  • 2,6-di-i-butyl-p-cresol and 220 g of 2,4-tolylene diisocyanate were added and cooled or heated until the liquid temperature reached 25 °C.
  • 0.400 g of dibutyltin dilaurate was added, 147 g of hy droxyethyl acrylate was added drop-wise while controlling the liquid temperature to 40 °C or below while stirring, and then this was stirred and reacted for 1 hour at approximately 30 °C.
  • 2,6-di-i-butyl-p-cresol and 135 g of 2,4-tolylene diisocyanate were added and cooled or heated until the liquid temperature reached 25 °C.
  • 0.400 g of dibutyltin dilaurate was added, 89.9 g of hydroxyethyl acrylate was added drop -wise while controlling the liquid temperature to 40 °C or below while stirring, and then this was stirred and reacted for 1 hour at approximately 30 °C.
  • 2,6-di-i-butyl-p-cresol and 135 g of 2,4-tolylene diisocyanate were added and cooled or heated until the liquid temperature reached 25 °C.
  • 0.400 g of dibutyltin dilaurate was added, 89.9 g of hydroxyethyl acrylate was added drop -wise while controlling the liquid temperature to 40 °C or below while stirring, and then this was stirred and reacted for 1 hour at approximately 30 °C.
  • 775 g of polypropylene glycol of number average molecular weight 2000 g/mol was added, and this was stirred and reacted for 6 hours at a liquid temperature of approximately 70 °C.
  • 2,6-di-i-butyl-p-cresol and 135 g of 2,4-tolylene diisocyanate were added, and 774 g of polytetramethylene glycol of number average molecular weight 2000 g/mol was added, and these were stirred until homogeneous. Then, 0.56 g of dibutyltin dilaurate was added drop-wise while cooling the reaction vessel such that the liquid temperature did not reach 60 °C or above, and this was stirred for 1 hour at a liquid temperature from 55 to 60 °C.
  • Examples 1 and 2 and 3 and 4 and 5 and comparative examples 1 and 2 [0060] The components of each composition shown in Table 1, parts 1 and 2 were put into a reaction vessel equipped with a stirrer, and this was stirred for 1 hour while controlling the liquid temperature to 60 °C, and radiation-curable resin compositions were obtained. Note that the blended quantities in Table 1 are in parts by mass. Test example
  • the radiation-curable resin composition was spread on a glass sheet using an applicator bar to a thickness of 15 mil (equivalent to coated film thickness of approximately 200 ⁇ ), and this was cured by irradiation with ultraviolet rays of energy 500 mJ/cm 2 in nitrogen to obtain a film for measurement. After letting stand for 1 day at 23 °C 50 % RH, this film underwent tensile testing at 23 °C 50 % RH or -40 °C according to
  • Young's modulus was determined from tensile strength at 2.5 % strain.
  • the film for measurement produced in (1) was stored for 10 days at 180 °C, and then fracture elongation was measured at 23 °C 50 % RH in the same manner as (1).
  • a 3 mm x 35 mm test piece was cut out from the film for measurement produced in (1), and dynamic viscosity was measured by Rheovibron DDV-0 IFP made by Orientec.
  • the glass transition temperature was evaluated as defined by the temperature at which the maximum value of loss tangent (tan ⁇ ) at oscillation frequency 3.5 Hz was exhibited.

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Abstract

La présente invention porte sur une composition de résine durcissable par rayonnement pour la formation d'une couche d'enrobage de fil, en particulier de fil à haute tension pour des automobiles et analogues. La composition de résine durcissable par rayonnement pour la formation d'une couche d'enrobage de fil comprend : (A) un uréthane-(méth)acrylate qui est le produit réactionnel d'un diol représenté par la formule (1) mentionnée ci-dessous, d'un diisocyanate et d'un (méth)acrylate contenant des groupes hydroxy : dans la formule (1), chaque R représentant indépendamment un groupe hydrocarboné aliphatique bifonctionnel ou un groupe hydrocarboné ayant une structure alicyclique bifonctionnelle et n représentant un nombre fixé de façon à ce que la masse moléculaire moyenne en nombre du composé de formule (1) soit de 500 à 10 000 g/mole ; (B) un composé ayant un groupe à insaturation éthylénique ; et (C) un initiateur de polymérisation par rayonnement.
PCT/NL2013/050822 2012-11-16 2013-11-15 Composition de résine durcissable par rayonnement pour la formation d'une couche d'enrobage de fil WO2014077688A1 (fr)

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
JP2012-252719 2012-11-16
JP2012252719 2012-11-16
EP13157746.2 2013-03-05
EP13157746 2013-03-05
JP2013234839A JP2014114444A (ja) 2012-11-16 2013-11-13 電線被覆層形成用放射線硬化性樹脂組成物
JP2013-234839 2013-11-13

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016080829A1 (fr) * 2014-11-19 2016-05-26 Dsm Ip Assets B.V. Revêtement secondaire d1563 durcissable par rayonnement pour fibres optiques
US10516070B2 (en) 2015-07-08 2019-12-24 Lg Electronics Inc. Solar cell module
US11104758B2 (en) 2018-06-29 2021-08-31 3M Innovative Properties Company Orthodontic articles prepared using a polycarbonate diol, and methods of making same
US20210301042A1 (en) * 2018-06-29 2021-09-30 3M Innovative Properties Company Photopolymerizable compositions including a polyurethane methacrylate polymer prepared using a polycarbonate diol, articles, and methods
US11584817B2 (en) 2018-06-29 2023-02-21 3M Innovative Properties Company Orthodontic articles comprising cured free-radically polymerizable composition with improved strength in aqueous environment
US11945900B2 (en) 2018-06-29 2024-04-02 3M Innovative Properties Company Orthodontic articles prepared using a polycarbonate diol, polymerizable compositions, and methods of making the articles

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Publication number Priority date Publication date Assignee Title
WO2008120982A1 (fr) * 2007-03-30 2008-10-09 Dsm Ip Assets B.V. Compositions de résine durcissables par rayonnement pour revêtements de fil électrique
JP2008251435A (ja) * 2007-03-30 2008-10-16 Jsr Corp 電線被覆用放射線硬化性樹脂組成物
EP2100907A1 (fr) * 2006-12-26 2009-09-16 Asahi Kasei Chemicals Corporation Composition de résine pour une plaque d'impression
EP2145930A1 (fr) * 2007-05-09 2010-01-20 Idemitsu Technofine Co. Ltd Agent de revêtement durcissable par rayonnement ultraviolet et article moulé
EP2431437A1 (fr) * 2010-09-20 2012-03-21 Nitto Denko Corporation Feuille adhésive sensible à la pression

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2100907A1 (fr) * 2006-12-26 2009-09-16 Asahi Kasei Chemicals Corporation Composition de résine pour une plaque d'impression
WO2008120982A1 (fr) * 2007-03-30 2008-10-09 Dsm Ip Assets B.V. Compositions de résine durcissables par rayonnement pour revêtements de fil électrique
JP2008251435A (ja) * 2007-03-30 2008-10-16 Jsr Corp 電線被覆用放射線硬化性樹脂組成物
EP2145930A1 (fr) * 2007-05-09 2010-01-20 Idemitsu Technofine Co. Ltd Agent de revêtement durcissable par rayonnement ultraviolet et article moulé
EP2431437A1 (fr) * 2010-09-20 2012-03-21 Nitto Denko Corporation Feuille adhésive sensible à la pression

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016080829A1 (fr) * 2014-11-19 2016-05-26 Dsm Ip Assets B.V. Revêtement secondaire d1563 durcissable par rayonnement pour fibres optiques
US10370557B2 (en) 2014-11-19 2019-08-06 Dsm Ip Assets B.V. D1563 radiation curable secondary coating for optical fibers
US10516070B2 (en) 2015-07-08 2019-12-24 Lg Electronics Inc. Solar cell module
US11104758B2 (en) 2018-06-29 2021-08-31 3M Innovative Properties Company Orthodontic articles prepared using a polycarbonate diol, and methods of making same
US20210301042A1 (en) * 2018-06-29 2021-09-30 3M Innovative Properties Company Photopolymerizable compositions including a polyurethane methacrylate polymer prepared using a polycarbonate diol, articles, and methods
US11225535B2 (en) 2018-06-29 2022-01-18 3M Innovative Properties Company Photopolymerizable compositions including a polyurethane methacrylate polymer prepared using a polycarbonate diol, articles, and methods
US11584817B2 (en) 2018-06-29 2023-02-21 3M Innovative Properties Company Orthodontic articles comprising cured free-radically polymerizable composition with improved strength in aqueous environment
US11708428B2 (en) 2018-06-29 2023-07-25 3M Innovative Properties Company Photopolymerizable compositions including a polyurethane methacrylate polymer prepared using a polycarbonate diol, articles, and methods
US11945900B2 (en) 2018-06-29 2024-04-02 3M Innovative Properties Company Orthodontic articles prepared using a polycarbonate diol, polymerizable compositions, and methods of making the articles

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