WO2023136064A1 - Two-component curable polyurethane resin composition - Google Patents

Two-component curable polyurethane resin composition Download PDF

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Publication number
WO2023136064A1
WO2023136064A1 PCT/JP2022/047008 JP2022047008W WO2023136064A1 WO 2023136064 A1 WO2023136064 A1 WO 2023136064A1 JP 2022047008 W JP2022047008 W JP 2022047008W WO 2023136064 A1 WO2023136064 A1 WO 2023136064A1
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polyol
mass
component
polyurethane resin
resin composition
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PCT/JP2022/047008
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French (fr)
Japanese (ja)
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正拓 範國
一仁 高田
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第一工業製薬株式会社
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Publication of WO2023136064A1 publication Critical patent/WO2023136064A1/en

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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
    • C08G18/08—Processes
    • 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
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • 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
    • C08G18/62—Polymers of compounds having carbon-to-carbon double 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
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • 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
    • C08G18/69—Polymers of conjugated dienes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/05—Alcohols; Metal alcoholates
    • C08K5/053—Polyhydroxylic alcohols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L45/00—Compositions of homopolymers or copolymers of compounds having no unsaturated aliphatic radicals in side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic or in a heterocyclic ring system; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
    • H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
    • H01L23/31—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the arrangement or shape

Definitions

  • the present invention relates to a two-component curable polyurethane resin composition, electrical and electronic components using the same, and a polyol composition for the two-component curable polyurethane resin composition.
  • Patent Document 1 discloses an electrical insulating material composed of a hydroxyl group-containing liquid diene polymer, a polyisocyanate compound, a polycyclic aromatic hydrocarbon, and a petroleum resin.
  • Patent Literature 2 discloses a heat-resistant, wet-insulating paint containing a polymer obtained by reacting hydroxyl-containing polybutadiene, hydroxyl-containing hydrogenated polybutadiene and polyisocyanate, a tackifier, and a solvent.
  • Patent Document 3 describes a two-component curable polyurethane resin composition containing a first component containing a polyol containing polybutadiene polyol and a terpene resin, and a second component containing a polyisocyanate. It also describes that by using a terpene resin together with polybutadiene polyol, the compatibility is improved, the adhesion to substrates and the like is improved, and a polyurethane resin having a low dielectric constant can be obtained.
  • Patent Document 3 a two-part curable polyurethane resin composition that is excellent in compatibility, adhesion, and low dielectric properties is provided, but it cannot be said that it is sufficient in terms of tensile properties. It has been found.
  • an object of the embodiments of the present invention is to provide a two-part curable polyurethane resin composition capable of improving tensile properties.
  • the two-component curable polyurethane resin composition according to the present embodiment is a polyurethane resin composition containing a first component containing a polyol (A) and a terpene resin (B) and a second component containing a polyisocyanate (C).
  • the polyol (A) contains a polybutadiene polyol (A1-1) and/or a hydrogenated polybutadiene polyol (A1-2) and an alkylene polyol (A2) having 7 to 9 carbon atoms.
  • the polyol (A) contained in the first component includes polybutadiene polyol (A1-1) and/or hydrogenated polybutadiene polyol (A1-2) (both may be collectively referred to as "PB polyol (A1)” hereinafter). ) is used.
  • the polybutadiene polyol (A1-1) preferably has a 1,4-bonded, 1,2-bonded, or mixed polybutadiene structure in the molecule and at least two hydroxy groups, both ends of the polybutadiene structure. each having a hydroxy group is more preferred.
  • the hydroxyl value of the polybutadiene polyol (A1-1) may be, for example, 10-200 mgKOH/g, 15-150 mgKOH/g, or 20-120 mgKOH/g. From the viewpoint of adhesion and compatibility, the hydroxyl value of the polybutadiene polyol (A1-1) is preferably 25-100 mgKOH/g, more preferably 40-90 mgKOH/g. As used herein, the hydroxyl value is measured according to JIS K1557-1:2007 A method.
  • the hydrogenated polybutadiene polyol (A1-2) has a hydrogenated structure with respect to the polybutadiene polyol (A1-1), and some or all of the unsaturated double bonds contained in the polybutadiene polyol are water. attached.
  • the degree of hydrogenation of the hydrogenated polybutadiene polyol (A1-2) is not particularly limited.
  • the iodine value may be 50 g/100 g or less, or 30 g/100 g or less. As used herein, the iodine value is measured according to JIS K0070:1992.
  • the hydroxyl value of the hydrogenated polybutadiene polyol (A1-2) may be, for example, 10 to 200 mgKOH/g, 15 to 150 mgKOH/g, 20 to 120 mgKOH/g, 25 to 100 mgKOH/g, or 40 to 90 mgKOH. /g.
  • polybutadiene polyol (A1-1) As the PB polyol (A1).
  • Alkylene polyol (A2) For the polyol (A) contained in the first component, an alkylene polyol (A2) having 7 to 9 carbon atoms is used together with the PB polyol (A1). Addition of the alkylene polyol (A2) can improve tensile properties, particularly elongation.
  • the alkylene polyol (A2) having 7 to 9 carbon atoms may be a diol having two hydroxy groups in one molecule, or may have three or more hydroxy groups, but is preferably a diol.
  • Specific examples of the alkylene polyol (A2) having 7 to 9 carbon atoms include 1,7-heptanediol, 1,2-heptanediol, 2,3-heptanediol, 5-methyl-2,4-hexanediol, 2 -methyl-2,5-hexanediol, 2,4-dimethyl-2,4-pentanediol, 2,4-dimethyl-1,5-pentanediol, 2-ethyl-1,5-pentanediol, 2-ethyl -Heptanediol such as 1,3-pentanediol; 1,8-octanediol, 1,2-octanedio
  • the alkylene polyol (A2) it is preferable to use a diol having a hydroxy group bonded to a primary carbon atom and a hydroxy group bonded to a secondary carbon atom.
  • diols include 1,2-heptanediol, 2-ethyl-1,3-pentanediol, 1,2-octanediol, 1,3-octanediol, 1,4-octanediol, 2- methyl-1,3-heptanediol, 2-ethyl-1,3-hexanediol, 2-ethyl-1,5-hexanediol, 2,2,4-trimethyl-1,3-pentanediol, 1,2- nonanediol, 2-ethyl-1,4-heptanediol. Any one of these may be used, or two or more thereof may be used in combination.
  • Branched alkylenediols are alkylenediols having tertiary and/or quaternary carbon atoms in the molecule. Specifically, 2-ethyl-1,3-pentanediol, 2-methyl-1,3-heptanediol, 2-ethyl-1,3-hexanediol, 2-ethyl-1,5-hexanediol, 2 , 2,4-trimethyl-1,3-pentanediol and 2-ethyl-1,4-heptanediol. More preferably, diols having tertiary carbon atoms in the molecule and having hydroxy groups bonded to primary carbon atoms and hydroxy groups bonded to secondary carbon atoms are used.
  • the polyol (A) may further contain a castor oil-based polyol (A3).
  • a castor oil-based polyol (A3) By adding the castor oil polyol (A3), the effect of improving the tensile properties can be enhanced.
  • castor oil-based polyol (A3) castor oil, castor oil fatty acid, hydrogenated castor oil obtained by hydrogenating these, and polyol produced using hydrogenated castor oil fatty acid can be used.
  • castor oil-based polyols (A3) include, for example, castor oil, transesterified products of castor oil and other natural oils and fats, reaction products of castor oil and polyhydric alcohols, and esterification of castor oil fatty acids and polyhydric alcohols. Examples include reactants and polyols obtained by addition polymerization of alkylene oxide thereto.
  • the hydroxyl value of the castor oil-based polyol (A2) is not particularly limited, and may be, for example, 50-250 mgKOH/g or 100-180 mgKOH/g.
  • the polyol (A) may be composed only of the PB polyol (A1) and the alkylene polyol (A2), or may be composed only of the PB polyol (A1), the alkylene polyol (A2) and the castor oil-based polyol (A3). , In addition to these, other polyols (A4) may be contained.
  • the polyol (A) may be composed only of bifunctional ones, or may contain trifunctional or higher functional ones. It preferably contains a tri- or higher functional polyol to make it thermosetting.
  • polyols (A4) are compounds having multiple hydroxy groups in the molecule, and include various polyols other than PB polyols (A1), alkylene polyols (A2), and castor oil-based polyols (A3). Specific examples include polyether polyol, polyester polyol, polycarbonate polyol, dimer acid polyol, polycaprolactone polyol, acrylic polyol, polyisoprene polyol, and hydrogenated polyisoprene polyol.
  • low-molecular-weight polyols commonly used as cross-linking agents such as N,N-bis(2-hydroxypropyl)aniline, hydroquinone-bis( ⁇ -hydroxyethyl)ether, resorcinol-bis( ⁇ -hydroxyethyl)ether aromatic alcohols such as
  • the content of the PB polyol (A1) in 100% by mass of the polyol (A) is 40% by mass or more, more preferably 50% by mass or more, and still more preferably 60% by mass or more.
  • the content of the PB polyol (A1) is 40% by mass or more, it is possible to improve the adhesion to an electronic circuit board and the like, and to lower the dielectric constant.
  • the content of the PB polyol (A1) is 96% by mass or less, preferably 92% by mass or less, may be 90% by mass or less, may be 85% by mass or less, or may be 80% by mass or less.
  • the content of the alkylene polyol (A2) in 100% by mass of the polyol (A) is 4 to 15% by mass.
  • the content of the alkylene polyol (A2) is preferably 5% by mass or more, preferably 12% by mass or less, and more preferably 10% by mass or less.
  • the content of the castor oil-based polyol (A3) in 100% by mass of the polyol (A) may be, for example, 4 to 56% by mass, or 10 to 40% by mass. %, or 15 to 30% by mass.
  • the first component contains a terpene resin (B) together with a PB polyol (A1) and an alkylene polyol (A2). Since the terpene resin (B) has excellent compatibility with the PB polyol (A1), separation and turbidity of the first component can be suppressed. In addition, by blending the terpene resin (B) together with the PB polyol (A1) and the alkylene polyol (A2), it is possible to improve the adhesion to electronic circuit boards, etc. elongation rate) is improved.
  • the terpene resin (B) is a polymer containing terpene as a constituent monomer.
  • Terpenes also referred to as terpene monomers
  • Terpene monomers include, for example, ⁇ -pinene, ⁇ -pinene, limonene (including racemic dipentene), myrcene, alloocimene, ocimene, ⁇ -phellandrene, ⁇ -phellandrene, ⁇ - Monoterpenes such as terpinene, ⁇ -terpinene, and sabinene can be mentioned, and any one of them or two or more of them can be used in combination.
  • monocyclic monoterpenes such as ⁇ -pinene, ⁇ -pinene, limonene, ⁇ -phellandrene, ⁇ -phellandrene, ⁇ -terpinene, and ⁇ -terpinene are preferred, more preferably ⁇ -pinene, At least one selected from the group consisting of ⁇ -pinene and limonene.
  • terpene resin (B) examples include polyterpene resin (B1), which is a homopolymer or copolymer consisting of only a terpene monomer, aromatic modified terpene resin (B1), which is a copolymer of a terpene monomer and an aromatic monomer ( B2) and a terpene phenol resin (B3) which is a copolymer of a terpene monomer and a phenolic monomer. Any one of these may be used, or two or more thereof may be used in combination.
  • aromatic monomers constituting the aromatic modified terpene resin (B2) include styrene, ⁇ -methylstyrene, 4-methylstyrene, 2,4-dimethylstyrene, and the like.
  • phenol-based monomers constituting the terpene phenol resin (B3) include phenol, cresol, and xylenol.
  • terpene resin (B) examples include polyterpene resin (B1) which is at least one homopolymer or copolymer selected from the group consisting of ⁇ -pinene, ⁇ -pinene and limonene, ⁇ -pinene , Aromatic modified terpene resin (B2) which is a copolymer of at least one terpene monomer and styrene selected from the group consisting of ⁇ -pinene and limonene, ⁇ -pinene, ⁇ -pinene and limonene from the group consisting of A terpene phenol resin (B3) is a copolymer of at least one selected terpene monomer and phenol.
  • the content of the terpene resin (B) is 5 to 60 parts by mass with respect to 100 parts by mass of the polyol (A). When the content of the terpene resin (B) is 60 parts by mass or less, bleeding of the terpene resin (B) after curing of the polyurethane resin can be suppressed.
  • the content of the terpene resin (B) is preferably 10 parts by mass or more, more preferably 15 parts by mass or more, and still more preferably 20 parts by mass or more.
  • the content of the terpene resin (B) is preferably 50 parts by mass or less, and may be 45 parts by mass or less.
  • the first component may optionally include, for example, a catalyst, an antioxidant, a foam stabilizer, a diluent, a flame retardant, an ultraviolet absorber, a coloring agent, a filler, a plasticizer, and the like. can be added as long as the purpose of the present embodiment is not impaired.
  • metal catalysts such as organic tin catalysts, organic lead catalysts, and organic bismuth catalysts, and various urethane polymerization catalysts such as amine catalysts can be used.
  • the polyisocyanate (C) contained in the second component is not particularly limited, and various polyisocyanate compounds having two or more isocyanate groups in one molecule can be used.
  • Examples of the polyisocyanate (C) include aromatic polyisocyanate (C1), aliphatic polyisocyanate (C2), and alicyclic polyisocyanate (C3). More than one species may be used in combination.
  • aromatic polyisocyanate (C1) examples include tolylene diisocyanate (TDI, such as 2,4-TDI, 2,6-TDI), diphenylmethane diisocyanate (MDI, such as 2,2'-MDI, 2,4'- MDI, 4,4'-MDI), 4,4'-dibenzyl diisocyanate, 1,5-naphthylene diisocyanate, xylylene diisocyanate (XDI), 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, and these modified forms and polynuclear forms of.
  • TDI tolylene diisocyanate
  • MDI diphenylmethane diisocyanate
  • MDI such as 2,2'-MDI, 2,4'- MDI, 4,4'-MDI
  • XDI xylylene diisocyanate
  • 1,3-phenylene diisocyanate 1,4-phenylene diisocyanate
  • Aliphatic polyisocyanates include, for example, tetramethylene diisocyanate, dodecamethylene diisocyanate, hexamethylene diisocyanate (HDI), 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, lysine Examples include diisocyanate, 2-methylpentane-1,5-diisocyanate, 3-methylpentane-1,5-diisocyanate, modified products and polynuclear products thereof.
  • HDI hexamethylene diisocyanate
  • 2,2,4-trimethylhexamethylene diisocyanate 2,4,4-trimethylhexamethylene diisocyanate
  • lysine Examples include diisocyanate, 2-methylpentane-1,5-diisocyanate, 3-methylpentane-1,5-diisocyanate, modified products and polynuclear products thereof.
  • Examples of the alicyclic polyisocyanate (C3) include isophorone diisocyanate (IPDI), hydrogenated xylylene diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, 1,4-cyclohexane diisocyanate, methylcyclohexylene diisocyanate, 1,3- Bis(isocyanatomethyl)cyclohexane, modified products thereof and polynuclear products thereof can be mentioned.
  • IPDI isophorone diisocyanate
  • hydrogenated xylylene diisocyanate 4,4′-dicyclohexylmethane diisocyanate
  • 1,4-cyclohexane diisocyanate 1,4-cyclohexane diisocyanate
  • methylcyclohexylene diisocyanate 1,3- Bis(isocyanatomethyl)cyclohexane, modified products thereof and polynuclear products thereof can be mentioned.
  • modified compounds include isocyanurate modified products, allophanate modified products, burette modified products, adduct modified products, and carbodiimide modified products.
  • the polyisocyanate (C) preferably contains an aromatic polyisocyanate (C1).
  • the aromatic polyisocyanate (C1) By using the aromatic polyisocyanate (C1), the effect of improving the tensile properties can be enhanced.
  • the polyisocyanate (C) is at least one selected from the group consisting of diphenylmethane diisocyanate, its modified form and polynuclear form.
  • the content of the polyisocyanate (C) in the two-component curable polyurethane resin composition is not particularly limited. or 5 to 40 parts by mass.
  • the polyisocyanate (C) may be composed only of bifunctional ones, and may contain trifunctional or more functional ones. It preferably contains a tri- or higher functional polyisocyanate to make it thermosetting.
  • the ratio of the polyisocyanate (C) and the polyol (A) is not particularly limited, for example, the NCO/OH (index) may be 0.6 to 1.5, 0.7 to 1.4, It may be 0.8 to 1.3, or 0.9 to 1.2.
  • NCO/OH is the molar ratio of isocyanate groups contained in polyisocyanate (C) to hydroxy groups contained in polyol (A).
  • NCO/OH is calculated using the hydroxyl value of polyol (A) and the isocyanate value of polyisocyanate (C).
  • the second component may be composed only of polyisocyanate (C), and in addition to polyisocyanate (C), if necessary, for example, catalyst, antioxidant, foam stabilizer, diluent, flame retardant , UV absorbers, colorants, fillers, plasticizers, and other additives may be added to the extent that the purpose of the present embodiment is not impaired.
  • the two-component curable polyurethane resin composition according to the present embodiment is usually composed of the first component as the first component and the second component as the second component.
  • a third component containing the above-mentioned other components as optional components may be provided as the third liquid.
  • the two-component curable polyurethane resin composition can be produced by preparing the first component and the second component, respectively. good.
  • the first component and the second component filled in separate containers may be mixed at the time of use to form a polyurethane resin by reacting the polyol (A) and the polyisocyanate (C), which may be cured. At that time, it may be cured by heating.
  • the two-component curable polyurethane resin composition according to the embodiment may be obtained by mixing the first component and the second component, may be liquid before curing, or may be cured.
  • a polyol composition according to one embodiment is used as a polyol component of a two-part curable polyurethane resin composition, and the first component corresponds to this. Therefore, the polyol composition contains a polyol (A) and a terpene resin (B), the polyol (A) contains 40% by mass or more of polybutadiene polyol and/or hydrogenated polybutadiene polyol (A1), and the polyol (A ) further contains 4 to 15% by mass of an alkylene polyol (A2) having 7 to 9 carbon atoms, and the content of the terpene resin (B) is 5 to 60 parts by mass based on 100 parts by mass of the polyol (A).
  • the details of the polyol (A), the terpene resin (B) and other components are as described above, and their description is omitted.
  • the use of the two-part curable polyurethane resin composition according to the present embodiment is not particularly limited, but it is preferably used for sealing electrical and electronic parts.
  • electrical and electronic components include transformers such as transformer coils, choke coils and reactor coils, equipment control boards, sensors, and wireless communication components.
  • the two-part curable polyurethane resin composition has excellent low dielectric properties (that is, it has a low dielectric constant) and is less susceptible to radio waves. Therefore, the two-component curable polyurethane resin composition is preferably used as a sealing material for resin-sealing, that is, covering wireless communication parts for wireless communication in order to protect the wireless communication parts from the external environment. For example, it may be used as a sealing material for a sensor that transmits detected information by wireless communication.
  • Electrical and electronic components resin-sealed using the two-component curable polyurethane resin composition according to the present embodiment include, for example, electric washing machines, toilet seats, water heaters, water purifiers, baths, dishwashers, solar panels, Can be used for electric tools, automobiles, motorcycles, etc.
  • the two-component curable polyurethane resin composition will be described in detail below based on Examples and Comparative Examples, but the present invention is not limited thereto.
  • Polyol (A) ⁇ Polybutadiene polyol 1: hydroxyl value 47 mgKOH/g, product name: Poly bd R-45HT, manufactured by Idemitsu Kosan Co., Ltd.
  • Polybutadiene polyol 2 hydroxyl value 107 mgKOH/g, product name: Poly bd R-15HT, Idemitsu Kosan Co., Ltd.
  • Hydrogenated polybutadiene polyol hydroxyl value 49 mgKOH/g, product name: KRASOL H-LBH-2000, manufactured by Clay Valley Co.
  • Octanediol 2-ethyl-1,3-hexanediol, product name: octanediol, KH Trimethylolpropane manufactured by Neochem Co., Ltd.: manufactured by Tokyo Chemical Industry Co., Ltd., product code T0480 ⁇ 1,10-Decanediol: manufactured by Tokyo Chemical Industry Co., Ltd., product code D0014 ⁇ Ethylene glycol: manufactured by Nacalai Tesque Co., Ltd., product code 15208-95 ⁇ 1,4-butanediol: manufactured by Nacalai Tesque Co., Ltd., product code 05922-35 ⁇ Castor oil-based polyol: hydroxyl value 160 mgKOH / g, product name: castor oil, manufactured by Ito Oil Co., Ltd.
  • Terpene resin (B) ⁇ Terpene resin 1: limonene-styrene copolymer, active ingredient 50% by mass, product name: YS Resin LP, manufactured by Yasuhara Chemical Co., Ltd.
  • Terpene resin 2 pinene-dipentene copolymer, active ingredient 80% by mass, product name : Dymaron, manufactured by Yasuhara Chemical Co., Ltd.
  • Terpene resin 3 Phenol/ ⁇ -pinene copolymer, active ingredient 100% by mass, product name: YS POLYSTER T80, manufactured by Yasuhara Chemical Co., Ltd.
  • Aromatic polyisocyanate Polymeric MDI, product name: Millionate MR-200, manufactured by Tosoh Corporation
  • Examples 1 to 12 and Comparative Examples 1 to 7 Two-component curable polyurethane resin compositions of each example and each comparative example were prepared according to the formulations (parts by mass) shown in Tables 1 and 2 below.
  • a predetermined amount of the first component shown in Tables 1 and 2 was weighed, and stirred and mixed while being melted by heating appropriately. After mixing, the temperature was adjusted to 25°C.
  • the second component polyisocyanate (C)
  • C polyisocyanate
  • the degassed two-pack curable polyurethane resin composition was dropped about 1 cm in diameter, cured at 80° C. for 16 hours (overnight) and cured. Aiming at the boundary between the cured polyurethane resin and the epoxy substrate, the resin was scraped off with a cutter knife, and the polyurethane resin remaining on the substrate was visually confirmed. Cohesive failure was defined as the state in which the polyurethane resin part remained on the substrate, and interfacial peeling was defined as the state in which the polyurethane resin peeled off from the substrate. Evaluation was performed according to the standard. In addition, if the evaluation is D or higher, it can be said to have practical adhesion.
  • Examples 1 to 12 in which alkylene polyol (A2) was added, compatibility, adhesion and low dielectric properties were obtained, and tensile properties could be further improved.
  • Examples 1, 4 to 12 are excellent in compatibility, adhesion, and low dielectric properties, and are excellent in improving tensile properties. Further, Examples 1, 5, 7 to 11 are more A better effect was observed.
  • Example 3 the tensile strength was evaluated as D, but the elongation rate was evaluated as A, which was excellent, and the effect of improving the tensile properties as a whole was recognized.

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Abstract

The purpose of the present invention is to improve tensile properties. A two-component curable polyurethane resin composition according to one embodiment contains: a first component that contains a polyol and a terpene resin; and a second component that contains a polyisocyanate. The polyol contains 40 mass% or more of a polybutadiene polyol and/or a hydrogenated polybutadiene polyol, and also contains 4-15 mass% of an alkylene polyol having 7-9 carbon atoms. The content of the terpene resin is 5-60 parts by mass relative to 100 parts by mass of the polyol.

Description

二液硬化型ポリウレタン樹脂組成物Two-component curable polyurethane resin composition
　本発明は、二液硬化型ポリウレタン樹脂組成物、およびそれを用いた電気電子部品、ならびに、該二液硬化型ポリウレタン樹脂組成物のためのポリオール組成物に関する。 The present invention relates to a two-component curable polyurethane resin composition, electrical and electronic components using the same, and a polyol composition for the two-component curable polyurethane resin composition.
　従来、電子回路基板や電子部品は、外的要因から保護するためにポリウレタン樹脂組成物を用いて封止することが行われており、ポリウレタン樹脂組成物のポリオールとしてポリブタジエンポリオールを用いることが知られている。 Conventionally, electronic circuit boards and electronic components have been sealed using polyurethane resin compositions in order to protect them from external factors, and it is known to use polybutadiene polyol as the polyol of the polyurethane resin composition. ing.
　例えば、特許文献１には、水酸基含有液状ジエン系重合体、ポリイソシアネート化合物、多環芳香族炭化水素および石油樹脂からなる電気絶縁材料が開示されている。特許文献２には、水酸基含有ポリブタジエン、水酸基含有水素添加ポリブタジエンおよびポリイソシアネートを反応させて得られるポリマーと、粘着付与剤と、溶剤を含有してなる耐熱性湿絶縁塗料が開示されている。 For example, Patent Document 1 discloses an electrical insulating material composed of a hydroxyl group-containing liquid diene polymer, a polyisocyanate compound, a polycyclic aromatic hydrocarbon, and a petroleum resin. Patent Literature 2 discloses a heat-resistant, wet-insulating paint containing a polymer obtained by reacting hydroxyl-containing polybutadiene, hydroxyl-containing hydrogenated polybutadiene and polyisocyanate, a tackifier, and a solvent.
　特許文献３には、ポリブタジエンポリオールを含むポリオールおよびテルペン樹脂を含む第１成分と、ポリイソシアネートを含む第２成分と、を含む二液硬化型ポリウレタン樹脂組成物が記載されている。また、ポリブタジエンポリオールとともにテルペン樹脂を用いることにより、相溶性を改善するとともに、基板等との密着性を向上し、誘電率の低いポリウレタン樹脂が得られることが記載されている。 Patent Document 3 describes a two-component curable polyurethane resin composition containing a first component containing a polyol containing polybutadiene polyol and a terpene resin, and a second component containing a polyisocyanate. It also describes that by using a terpene resin together with polybutadiene polyol, the compatibility is improved, the adhesion to substrates and the like is improved, and a polyurethane resin having a low dielectric constant can be obtained.
特開昭６１－１９７６２０号公報JP-A-61-197620 特開平８－１６５４５４号公報JP-A-8-165454 特許第６９１６４０４号公報Japanese Patent No. 6916404
　上記のように特許文献３に記載の発明によれば、相溶性と密着性と低誘電特性に優れる二液硬化型ポリウレタン樹脂組成物が提供されるが、引張特性の点で十分とはいえないことが判明した。 As described above, according to the invention described in Patent Document 3, a two-part curable polyurethane resin composition that is excellent in compatibility, adhesion, and low dielectric properties is provided, but it cannot be said that it is sufficient in terms of tensile properties. It has been found.
　本発明の実施形態は、以上の点に鑑み、引張特性を改善することができる二液硬化型ポリウレタン樹脂組成物を提供することを目的とする。 In view of the above points, an object of the embodiments of the present invention is to provide a two-part curable polyurethane resin composition capable of improving tensile properties.
　本発明は以下に示される実施形態を含む。
［１］　ポリオールおよびテルペン樹脂を含む第１成分と、ポリイソシアネートを含む第２成分と、を含み、前記ポリオールは、ポリブタジエンポリオールおよび／または水添ポリブタジエンポリオールを４０質量％以上含み、前記ポリオールは、さらに炭素数が７以上９以下のアルキレンポリオールを４～１５質量％含み、前記テルペン樹脂の含有量が、前記ポリオール１００質量部に対して５～６０質量部である、二液硬化型ポリウレタン樹脂組成物。
［２］　前記アルキレンポリオールは、第一級炭素原子に結合したヒドロキシ基と第二級炭素原子に結合したヒドロキシ基とを有するジオールである、［１］に記載の二液硬化型ポリウレタン樹脂組成物。
［３］　前記ポリイソシアネートが芳香族ポリイソシアネートを含む、［１］または［２］に記載の二液硬化型ポリウレタン樹脂組成物。
［４］　前記ポリオールが、ひまし油系ポリオールをさらに含む、［１］～［３］のいずれか１項に記載の二液硬化型ポリウレタン樹脂組成物。
［５］　電気電子部品封止用である、［１］～［４］のいずれか１項に記載の二液硬化型ポリウレタン樹脂組成物。
［６］　［１］～［５］のいずれか１項に記載の二液硬化型ポリウレタン樹脂組成物を用いて樹脂封止された電気電子部品。
［７］　二液硬化型ポリウレタン樹脂組成物のポリオール成分として用いられるポリオール組成物であって、ポリオールおよびテルペン樹脂を含み、前記ポリオールは、ポリブタジエンポリオールおよび／または水添ポリブタジエンポリオールを４０質量％以上含み、前記ポリオールは、さらに炭素数が７以上９以下のアルキレンポリオールを４～１５質量％含み、前記テルペン樹脂の含有量が、前記ポリオール１００質量部に対して５～６０質量部である、ポリオール組成物。 The present invention includes embodiments shown below.
[1] A first component containing a polyol and a terpene resin, and a second component containing a polyisocyanate, wherein the polyol contains 40% by mass or more of polybutadiene polyol and/or hydrogenated polybutadiene polyol, and the polyol is Furthermore, a two-component curable polyurethane resin composition containing 4 to 15% by mass of an alkylene polyol having 7 to 9 carbon atoms, and the content of the terpene resin is 5 to 60 parts by mass with respect to 100 parts by mass of the polyol. thing.
[2] The two-component curable polyurethane resin composition according to [1], wherein the alkylene polyol is a diol having a hydroxy group bonded to a primary carbon atom and a hydroxy group bonded to a secondary carbon atom. .
[3] The two-part curable polyurethane resin composition according to [1] or [2], wherein the polyisocyanate contains an aromatic polyisocyanate.
[4] The two-component curable polyurethane resin composition according to any one of [1] to [3], wherein the polyol further contains a castor oil-based polyol.
[5] The two-component curable polyurethane resin composition according to any one of [1] to [4], which is used for encapsulating electrical and electronic parts.
[6] An electric/electronic component resin-sealed using the two-component curing type polyurethane resin composition according to any one of [1] to [5].
[7] A polyol composition used as a polyol component of a two-component curable polyurethane resin composition, comprising a polyol and a terpene resin, wherein the polyol contains 40% by mass or more of polybutadiene polyol and/or hydrogenated polybutadiene polyol. , the polyol further contains 4 to 15% by mass of an alkylene polyol having 7 to 9 carbon atoms, and the content of the terpene resin is 5 to 60 parts by mass relative to 100 parts by mass of the polyol. thing.
　本発明の実施形態によれば、引張特性を改善することができる二液硬化型ポリウレタン樹脂組成物を提供することができる。 According to the embodiment of the present invention, it is possible to provide a two-part curable polyurethane resin composition capable of improving tensile properties.
　本実施形態に係る二液硬化型ポリウレタン樹脂組成物は、ポリオール（Ａ）およびテルペン樹脂（Ｂ）を含む第１成分と、ポリイソシアネート（Ｃ）を含む第２成分と、を含むポリウレタン樹脂組成物であって、前記ポリオール（Ａ）が、ポリブタジエンポリオール（Ａ１－１）および／または水添ポリブタジエンポリオール（Ａ１－２）と、炭素数が７以上９以下のアルキレンポリオール（Ａ２）を含むものである。 The two-component curable polyurethane resin composition according to the present embodiment is a polyurethane resin composition containing a first component containing a polyol (A) and a terpene resin (B) and a second component containing a polyisocyanate (C). The polyol (A) contains a polybutadiene polyol (A1-1) and/or a hydrogenated polybutadiene polyol (A1-2) and an alkylene polyol (A2) having 7 to 9 carbon atoms.
　＜第１成分＞
　［ポリブタジエンポリオール（Ａ１－１）および／または水添ポリブタジエンポリオール（Ａ１－２）］
　第１成分に含まれるポリオール（Ａ）には、ポリブタジエンポリオール（Ａ１－１）および／または水添ポリブタジエンポリオール（Ａ１－２）（以下、両者をまとめて「ＰＢポリオール（Ａ１）」ということがある。）が用いられる。 <First component>
[Polybutadiene polyol (A1-1) and/or hydrogenated polybutadiene polyol (A1-2)]
The polyol (A) contained in the first component includes polybutadiene polyol (A1-1) and/or hydrogenated polybutadiene polyol (A1-2) (both may be collectively referred to as "PB polyol (A1)" hereinafter). ) is used.
　ポリブタジエンポリオール（Ａ１－１）としては、分子中に１，４－結合型、１，２－結合型またはそれらが混在したポリブタジエン構造と少なくとも２つのヒドロキシ基を有するものが好ましく、ポリブタジエン構造の両末端にそれぞれヒドロキシ基を有するものがより好ましい。 The polybutadiene polyol (A1-1) preferably has a 1,4-bonded, 1,2-bonded, or mixed polybutadiene structure in the molecule and at least two hydroxy groups, both ends of the polybutadiene structure. each having a hydroxy group is more preferred.
　ポリブタジエンポリオール（Ａ１－１）の水酸基価は、例えば１０～２００ｍｇＫＯＨ／ｇでもよく、１５～１５０ｍｇＫＯＨ／ｇでもよく、２０～１２０ｍｇＫＯＨ／ｇでもよい。密着性および相溶性を観点から、ポリブタジエンポリオール（Ａ１－１）の水酸基価は２５～１００ｍｇＫＯＨ／ｇであることが好ましく、より好ましくは４０～９０ｍｇＫＯＨ／ｇである。本明細書において、水酸基価はＪＩＳ　Ｋ１５５７－１：２００７のＡ法に準じて測定される。 The hydroxyl value of the polybutadiene polyol (A1-1) may be, for example, 10-200 mgKOH/g, 15-150 mgKOH/g, or 20-120 mgKOH/g. From the viewpoint of adhesion and compatibility, the hydroxyl value of the polybutadiene polyol (A1-1) is preferably 25-100 mgKOH/g, more preferably 40-90 mgKOH/g. As used herein, the hydroxyl value is measured according to JIS K1557-1:2007 A method.
　水添ポリブタジエンポリオール（Ａ１－２）は、ポリブタジエンポリオール（Ａ１－１）に対して水素添加した構造を持つものであり、ポリブタジエンポリオールに含まれている不飽和二重結合の一部又は全てが水添されている。水添ポリブタジエンポリオール（Ａ１－２）の水添の度合いは特に限定されず、例えばヨウ素価が５０ｇ／１００ｇ以下でもよく、３０ｇ／１００ｇ以下でもよい。本明細書において、ヨウ素価はＪＩＳ　Ｋ００７０：１９９２に準じて測定される。 The hydrogenated polybutadiene polyol (A1-2) has a hydrogenated structure with respect to the polybutadiene polyol (A1-1), and some or all of the unsaturated double bonds contained in the polybutadiene polyol are water. attached. The degree of hydrogenation of the hydrogenated polybutadiene polyol (A1-2) is not particularly limited. For example, the iodine value may be 50 g/100 g or less, or 30 g/100 g or less. As used herein, the iodine value is measured according to JIS K0070:1992.
　水添ポリブタジエンポリオール（Ａ１－２）の水酸基価は、例えば１０～２００ｍｇＫＯＨ／ｇでもよく、１５～１５０ｍｇＫＯＨ／ｇでもよく、２０～１２０ｍｇＫＯＨ／ｇでもよく、２５～１００ｍｇＫＯＨ／ｇでもよく、４０～９０ｍｇＫＯＨ／ｇでもよい。 The hydroxyl value of the hydrogenated polybutadiene polyol (A1-2) may be, for example, 10 to 200 mgKOH/g, 15 to 150 mgKOH/g, 20 to 120 mgKOH/g, 25 to 100 mgKOH/g, or 40 to 90 mgKOH. /g.
　ＰＢポリオール（Ａ１）としては、引張強度の観点からポリブタジエンポリオール（Ａ１－１）を用いることがより好ましい。 From the viewpoint of tensile strength, it is more preferable to use polybutadiene polyol (A1-1) as the PB polyol (A1).
　［アルキレンポリオール（Ａ２）］
　第１成分に含まれるポリオール（Ａ）には、上記ＰＢポリオール（Ａ１）とともに、炭素数７～９のアルキレンポリオール（Ａ２）が用いられる。アルキレンポリオール（Ａ２）を添加することにより、引張特性、特には伸び率を向上することができる。 [Alkylene polyol (A2)]
For the polyol (A) contained in the first component, an alkylene polyol (A2) having 7 to 9 carbon atoms is used together with the PB polyol (A1). Addition of the alkylene polyol (A2) can improve tensile properties, particularly elongation.
　炭素数７～９のアルキレンポリオール（Ａ２）は、１分子中にヒドロキシ基を２つ有するジオールでもよく、ヒドロキシ基を３つ以上有するものでもよいが、好ましくはジオールである。炭素数７～９のアルキレンポリオール（Ａ２）の具体例としては、１，７－ヘプタンジオール、１，２－ヘプタンジオール、２，３－ヘプタンジオール、５－メチル－２，４－ヘキサンジオール、２－メチル－２，５－ヘキサンジオール、２，４－ジメチル－２，４－ペンタンジオール、２，４－ジメチル－１，５－ペンタンジオール、２－エチル－１，５－ペンタンジオール、２－エチル－１，３－ペンタンジオールなどのヘプタンジオール；　１，８－オクタンジオール、１，２－オクタンジオール、１，３－オクタンジオール、１，４－オクタンジオール、２，４－オクタンジオール、２－メチル－１，２－ヘプタンジオール、２－メチル－１，３－ヘプタンジオール、２－メチル－２，３－ヘプタンジオール、２－エチル－１，２－ヘキサンジオール、２－エチル－１，３－ヘキサンジオール、２－エチル－１，５－ヘキサンジオール、２－エチル－１，６－ヘキサンジオール、２，５－ジメチル－２，５－ヘキサンジオール、３，４－ジメチル－３，４－ヘキサンジオール、２，５－ジメチル－３，４－ヘキサンジオール、２，２，４－トリメチル－１，３－ペンタンジオール、２－プロピル－１，２－ペンタンジオールなどのオクタンジオール；　１，９－ノナンジオール、１，２－ノナンジオール、２－メチル－１，８－オクタンジオール、２－エチル－１，４－ヘプタンジオール、２，６－ジメチル－３，５－ヘプタンジオール、２，６－ジメチル－２，６－ヘプタンジオール、２－ブチル－２－エチル－１，３－プロパンジオールなどのノナンジオールが挙げられる。これらはいずれか１種用いてもよく、２種以上併用してもよい。 The alkylene polyol (A2) having 7 to 9 carbon atoms may be a diol having two hydroxy groups in one molecule, or may have three or more hydroxy groups, but is preferably a diol. Specific examples of the alkylene polyol (A2) having 7 to 9 carbon atoms include 1,7-heptanediol, 1,2-heptanediol, 2,3-heptanediol, 5-methyl-2,4-hexanediol, 2 -methyl-2,5-hexanediol, 2,4-dimethyl-2,4-pentanediol, 2,4-dimethyl-1,5-pentanediol, 2-ethyl-1,5-pentanediol, 2-ethyl -Heptanediol such as 1,3-pentanediol; 1,8-octanediol, 1,2-octanediol, 1,3-octanediol, 1,4-octanediol, 2,4-octanediol, 2-methyl -1,2-heptanediol, 2-methyl-1,3-heptanediol, 2-methyl-2,3-heptanediol, 2-ethyl-1,2-hexanediol, 2-ethyl-1,3-hexane Diol, 2-ethyl-1,5-hexanediol, 2-ethyl-1,6-hexanediol, 2,5-dimethyl-2,5-hexanediol, 3,4-dimethyl-3,4-hexanediol, octanediol such as 2,5-dimethyl-3,4-hexanediol, 2,2,4-trimethyl-1,3-pentanediol, 2-propyl-1,2-pentanediol; 1,9-nonanediol, 1,2-nonanediol, 2-methyl-1,8-octanediol, 2-ethyl-1,4-heptanediol, 2,6-dimethyl-3,5-heptanediol, 2,6-dimethyl-2, nonanediol such as 6-heptanediol and 2-butyl-2-ethyl-1,3-propanediol; Any one of these may be used, or two or more thereof may be used in combination.
　アルキレンポリオール（Ａ２）としては、第一級炭素原子に結合したヒドロキシ基と第二級炭素原子に結合したヒドロキシ基とを有するジオールを用いることが好ましい。そのようなジオールとしては、例えば、１，２－ヘプタンジオール、２－エチル－１，３－ペンタンジオール、１，２－オクタンジオール、１，３－オクタンジオール、１，４－オクタンジオール、２－メチル－１，３－ヘプタンジオール、２－エチル－１，３－ヘキサンジオール、２－エチル－１，５－ヘキサンジオール、２，２，４－トリメチル－１，３－ペンタンジオール、１，２－ノナンジオール、２－エチル－１，４－ヘプタンジオールが挙げられる。これらはいずれか１種用いてもよく、２種以上併用してもよい。 As the alkylene polyol (A2), it is preferable to use a diol having a hydroxy group bonded to a primary carbon atom and a hydroxy group bonded to a secondary carbon atom. Examples of such diols include 1,2-heptanediol, 2-ethyl-1,3-pentanediol, 1,2-octanediol, 1,3-octanediol, 1,4-octanediol, 2- methyl-1,3-heptanediol, 2-ethyl-1,3-hexanediol, 2-ethyl-1,5-hexanediol, 2,2,4-trimethyl-1,3-pentanediol, 1,2- nonanediol, 2-ethyl-1,4-heptanediol. Any one of these may be used, or two or more thereof may be used in combination.
　これらの中でも分岐アルキレンジオールが好ましい。分岐アルキレンジオールとは、分子内に第三級炭素原子および／または第四級炭素原子を有するアルキレンジオールである。具体的には、２－エチル－１，３－ペンタンジオール、２－メチル－１，３－ヘプタンジオール、２－エチル－１，３－ヘキサンジオール、２－エチル－１，５－ヘキサンジオール、２，２，４－トリメチル－１，３－ペンタンジオール、２－エチル－１，４－ヘプタンジオールが挙げられる。より好ましくは、分子内に第三級炭素原子を有するとともに、第一級炭素原子に結合したヒドロキシ基と第二級炭素原子に結合したヒドロキシ基を有するジオールを用いることである。 Among these, branched alkylene diols are preferred. Branched alkylenediols are alkylenediols having tertiary and/or quaternary carbon atoms in the molecule. Specifically, 2-ethyl-1,3-pentanediol, 2-methyl-1,3-heptanediol, 2-ethyl-1,3-hexanediol, 2-ethyl-1,5-hexanediol, 2 , 2,4-trimethyl-1,3-pentanediol and 2-ethyl-1,4-heptanediol. More preferably, diols having tertiary carbon atoms in the molecule and having hydroxy groups bonded to primary carbon atoms and hydroxy groups bonded to secondary carbon atoms are used.
　［ひまし油系ポリオール（Ａ３）］
　ポリオール（Ａ）には、さらにひまし油系ポリオール（Ａ３）が含まれてもよい。ヒマシ油ポリオール（Ａ３）を添加することにより、引張特性の改善効果を高めることができる。ひまし油系ポリオール（Ａ３）としては、ひまし油、ひまし油脂肪酸、及びこれらに水素付加した水添ひまし油や水添ひまし油脂肪酸を用いて製造されたポリオールを使用することができる。より詳細には、ひまし油系ポリオール（Ａ３）としては、例えば、ひまし油、ひまし油とその他の天然油脂とのエステル交換物、ひまし油と多価アルコールとの反応物、ひまし油脂肪酸と多価アルコールとのエステル化反応物、及びこれらにアルキレンオキサイドを付加重合したポリオールなどが挙げられる。 [Castor oil-based polyol (A3)]
The polyol (A) may further contain a castor oil-based polyol (A3). By adding the castor oil polyol (A3), the effect of improving the tensile properties can be enhanced. As the castor oil-based polyol (A3), castor oil, castor oil fatty acid, hydrogenated castor oil obtained by hydrogenating these, and polyol produced using hydrogenated castor oil fatty acid can be used. More specifically, castor oil-based polyols (A3) include, for example, castor oil, transesterified products of castor oil and other natural oils and fats, reaction products of castor oil and polyhydric alcohols, and esterification of castor oil fatty acids and polyhydric alcohols. Examples include reactants and polyols obtained by addition polymerization of alkylene oxide thereto.
　ひまし油系ポリオール（Ａ２）の水酸基価は特に限定されず、例えば５０～２５０ｍｇＫＯＨ／ｇでもよく、１００～１８０ｍｇＫＯＨ／ｇでもよい。 The hydroxyl value of the castor oil-based polyol (A2) is not particularly limited, and may be, for example, 50-250 mgKOH/g or 100-180 mgKOH/g.
　［ポリオール（Ａ）］
　ポリオール（Ａ）は、ＰＢポリオール（Ａ１）およびアルキレンポリオール（Ａ２）のみで構成されてもよく、ＰＢポリオール（Ａ１）、アルキレンポリオール（Ａ２）およびひまし油系ポリオール（Ａ３）のみで構成されてもよく、また、これらに加えてさらに他のポリオール（Ａ４）を含有してもよい。ポリオール（Ａ）は、２官能のもののみで構成されてもよく、３官能以上のものを含んでもよいが、ポリイソシアネート（Ｃ）が２官能のもののみで構成される場合、ポリウレタン樹脂組成物を熱硬化性にするべく３官能以上のポリオールを含むことが好ましい。 [Polyol (A)]
The polyol (A) may be composed only of the PB polyol (A1) and the alkylene polyol (A2), or may be composed only of the PB polyol (A1), the alkylene polyol (A2) and the castor oil-based polyol (A3). , In addition to these, other polyols (A4) may be contained. The polyol (A) may be composed only of bifunctional ones, or may contain trifunctional or higher functional ones. It preferably contains a tri- or higher functional polyol to make it thermosetting.
　他のポリオール（Ａ４）は、分子内に複数のヒドロキシ基を持つ化合物であって、ＰＢポリオール（Ａ１）、アルキレンポリオール（Ａ２）およびひまし油系ポリオール（Ａ３）以外の各種ポリオールが挙げられる。具体的には、ポリエーテルポリオール、ポリエステルポリオール、ポリカーボネートポリオール、ダイマー酸ポリオール、ポリカプロラクトンポリオール、アクリルポリオール、ポリイソプレンポリオール、水添ポリイソプレンポリオールなどが挙げられる。また、一般に架橋剤として用いられている低分子量ポリオール、例えば、Ｎ，Ｎ－ビス（２－ヒドロキシプロピル）アニリン、ヒドロキノン－ビス（β－ヒドロキシエチル）エーテル、レゾルシノール－ビス（β－ヒドロキシエチル）エーテル等の芳香族アルコールが挙げられる。 Other polyols (A4) are compounds having multiple hydroxy groups in the molecule, and include various polyols other than PB polyols (A1), alkylene polyols (A2), and castor oil-based polyols (A3). Specific examples include polyether polyol, polyester polyol, polycarbonate polyol, dimer acid polyol, polycaprolactone polyol, acrylic polyol, polyisoprene polyol, and hydrogenated polyisoprene polyol. In addition, low-molecular-weight polyols commonly used as cross-linking agents, such as N,N-bis(2-hydroxypropyl)aniline, hydroquinone-bis(β-hydroxyethyl)ether, resorcinol-bis(β-hydroxyethyl)ether aromatic alcohols such as
　ポリオール（Ａ）１００質量％中におけるＰＢポリオール（Ａ１）の含有量は、４０質量％以上であり、より好ましくは５０質量％以上であり、さらに好ましくは６０質量％以上である。ＰＢポリオール（Ａ１）の含有量が４０質量％以上であることにより、電子回路基板等との密着性を向上することができ、また誘電率を低下させることができる。ＰＢポリオール（Ａ１）の含有量は、９６質量％以下であり、好ましくは９２質量％以下であり、９０質量％以下でもよく、８５質量％以下でもよく、８０質量％以下でもよい。 The content of the PB polyol (A1) in 100% by mass of the polyol (A) is 40% by mass or more, more preferably 50% by mass or more, and still more preferably 60% by mass or more. When the content of the PB polyol (A1) is 40% by mass or more, it is possible to improve the adhesion to an electronic circuit board and the like, and to lower the dielectric constant. The content of the PB polyol (A1) is 96% by mass or less, preferably 92% by mass or less, may be 90% by mass or less, may be 85% by mass or less, or may be 80% by mass or less.
　ポリオール（Ａ）１００質量％中におけるアルキレンポリオール（Ａ２）の含有量は、４～１５質量％である。アルキレンポリオール（Ａ２）の含有量が４質量％以上であることにより引張特性を改善することができ、また１５質量％以下であることにより、相溶性の悪化を抑えることができる。アルキレンポリオール（Ａ２）の含有量は、５質量％以上であることが好ましく、また、１２質量％以下であることが好ましく、より好ましくは１０質量％以下である。 The content of the alkylene polyol (A2) in 100% by mass of the polyol (A) is 4 to 15% by mass. When the content of the alkylene polyol (A2) is 4% by mass or more, tensile properties can be improved, and when it is 15% by mass or less, deterioration of compatibility can be suppressed. The content of the alkylene polyol (A2) is preferably 5% by mass or more, preferably 12% by mass or less, and more preferably 10% by mass or less.
　ポリオール（Ａ）にひまし油系ポリオール（Ａ３）を含有させる場合、ポリオール（Ａ）１００質量％中におけるひまし油系ポリオール（Ａ３）の含有量は、例えば、４～５６質量％でもよく、１０～４０質量％でもよく、１５～３０質量％でもよい。 When the polyol (A) contains the castor oil-based polyol (A3), the content of the castor oil-based polyol (A3) in 100% by mass of the polyol (A) may be, for example, 4 to 56% by mass, or 10 to 40% by mass. %, or 15 to 30% by mass.
　［テルペン樹脂（Ｂ）］
　第１成分には、ＰＢポリオール（Ａ１）およびアルキレンポリオール（Ａ２）とともにテルペン樹脂（Ｂ）が配合される。テルペン樹脂（Ｂ）はＰＢポリオール（Ａ１）との相溶性に優れるため、第１成分の分離や濁りを抑制することができる。また、ＰＢポリオール（Ａ１）およびアルキレンポリオール（Ａ２）とともにテルペン樹脂（Ｂ）を配合することにより、電子回路基板等との密着性を向上することができ、また低誘電特性や引張特性（特には伸び率）の向上に繋がる。 [Terpene resin (B)]
The first component contains a terpene resin (B) together with a PB polyol (A1) and an alkylene polyol (A2). Since the terpene resin (B) has excellent compatibility with the PB polyol (A1), separation and turbidity of the first component can be suppressed. In addition, by blending the terpene resin (B) together with the PB polyol (A1) and the alkylene polyol (A2), it is possible to improve the adhesion to electronic circuit boards, etc. elongation rate) is improved.
　テルペン樹脂（Ｂ）は、テルペンを構成モノマーとして含む重合体である。テルペン（テルペンモノマーともいう。）としては、例えば、α－ピネン、β－ピネン、リモネン（ラセミ体のジペンテンも含む。）、ミルセン、アロオシメン、オシメン、α－フェランドレン、β－フェランドレン、α－テルピネン、γ－テルピネン、およびサビネン等のモノテルペンが挙げられ、これらをいずれか１種または２種以上併用することができる。これらの中でも、α－ピネン、β－ピネン、リモネン、α－フェランドレン、β－フェランドレン、α－テルピネン、およびγ－テルピネン等の単環式のモノテルペンが好ましく、より好ましくはα－ピネン、β－ピネン、およびリモネンからなる群から選択される少なくとも１種である。 The terpene resin (B) is a polymer containing terpene as a constituent monomer. Terpenes (also referred to as terpene monomers) include, for example, α-pinene, β-pinene, limonene (including racemic dipentene), myrcene, alloocimene, ocimene, α-phellandrene, β-phellandrene, α- Monoterpenes such as terpinene, γ-terpinene, and sabinene can be mentioned, and any one of them or two or more of them can be used in combination. Among these, monocyclic monoterpenes such as α-pinene, β-pinene, limonene, α-phellandrene, β-phellandrene, α-terpinene, and γ-terpinene are preferred, more preferably α-pinene, At least one selected from the group consisting of β-pinene and limonene.
　テルペン樹脂（Ｂ）としては、構成モノマーがテルペンモノマーのみからなる単独重合体または共重合体であるポリテルペン樹脂（Ｂ１）、テルペンモノマーと芳香族モノマーとの共重合体である芳香族変性テルペン樹脂（Ｂ２）、テルペンモノマーとフェノール系モノマーとの共重合体であるテルペンフェノール樹脂（Ｂ３）が挙げられる。これらはいずれか１種用いても、２種以上併用してもよい。 Examples of the terpene resin (B) include polyterpene resin (B1), which is a homopolymer or copolymer consisting of only a terpene monomer, aromatic modified terpene resin (B1), which is a copolymer of a terpene monomer and an aromatic monomer ( B2) and a terpene phenol resin (B3) which is a copolymer of a terpene monomer and a phenolic monomer. Any one of these may be used, or two or more thereof may be used in combination.
　芳香族変性テルペン樹脂（Ｂ２）を構成する芳香族モノマーとしては、例えば、芳香族モノマーとしては、例えば、スチレン、α－メチルスチレン、４－メチルスチレン、２，４－ジメチルスチレン等が挙げられる。 Examples of aromatic monomers constituting the aromatic modified terpene resin (B2) include styrene, α-methylstyrene, 4-methylstyrene, 2,4-dimethylstyrene, and the like.
　テルペンフェノール樹脂（Ｂ３）を構成するフェノール系モノマーとしては、例えば、フェノール、クレゾール、キシレノール等が挙げられる。 Examples of phenol-based monomers constituting the terpene phenol resin (B3) include phenol, cresol, and xylenol.
　テルペン樹脂（Ｂ）の好適な例としては、α－ピネン、β－ピネンおよびリモネンからなる群から選択される少なくとも１種の単独重合体または共重合体であるポリテルペン樹脂（Ｂ１）、α－ピネン、β－ピネンおよびリモネンからなる群から選択される少なくとも１種のテルペンモノマーとスチレンとの共重合体である芳香族変性テルペン樹脂（Ｂ２）、α－ピネン、β－ピネンおよびリモネンからなる群から選択される少なくとも１種のテルペンモノマーとフェノールとの共重合体であるテルペンフェノール樹脂（Ｂ３）が挙げられる。 Preferable examples of the terpene resin (B) include polyterpene resin (B1) which is at least one homopolymer or copolymer selected from the group consisting of α-pinene, β-pinene and limonene, α-pinene , Aromatic modified terpene resin (B2) which is a copolymer of at least one terpene monomer and styrene selected from the group consisting of β-pinene and limonene, α-pinene, β-pinene and limonene from the group consisting of A terpene phenol resin (B3) is a copolymer of at least one selected terpene monomer and phenol.
　テルペン樹脂（Ｂ）の含有量は、ポリオール（Ａ）１００質量部に対して５～６０質量部である。テルペン樹脂（Ｂ）の含有量が６０質量部以下であることにより、ポリウレタン樹脂の硬化後におけるテルペン樹脂（Ｂ）のブリードを抑制することができる。テルペン樹脂（Ｂ）の含有量は、１０質量部以上であることが好ましく、より好ましくは１５質量部以上であり、さらに好ましくは２０質量部以上である。テルペン樹脂（Ｂ）の含有量は、５０質量部以下であることが好ましく、４５質量部以下でもよい。 The content of the terpene resin (B) is 5 to 60 parts by mass with respect to 100 parts by mass of the polyol (A). When the content of the terpene resin (B) is 60 parts by mass or less, bleeding of the terpene resin (B) after curing of the polyurethane resin can be suppressed. The content of the terpene resin (B) is preferably 10 parts by mass or more, more preferably 15 parts by mass or more, and still more preferably 20 parts by mass or more. The content of the terpene resin (B) is preferably 50 parts by mass or less, and may be 45 parts by mass or less.
　［その他の成分］
　第１成分には、上記した各成分の他に、必要に応じて、例えば、触媒、酸化防止剤、整泡剤、希釈剤、難燃剤、紫外線吸収剤、着色剤、充填剤、可塑剤などの各種添加剤を、本実施形態の目的を損なわない範囲で加えることができる。 [Other ingredients]
In addition to the components described above, the first component may optionally include, for example, a catalyst, an antioxidant, a foam stabilizer, a diluent, a flame retardant, an ultraviolet absorber, a coloring agent, a filler, a plasticizer, and the like. can be added as long as the purpose of the present embodiment is not impaired.
　触媒としては、例えば、有機スズ触媒、有機鉛触媒、有機ビスマス触媒などの金属触媒、アミン触媒などの各種ウレタン重合触媒を用いることができる。 As the catalyst, for example, metal catalysts such as organic tin catalysts, organic lead catalysts, and organic bismuth catalysts, and various urethane polymerization catalysts such as amine catalysts can be used.
　＜第２成分＞
　［ポリイソシアネート（Ｃ）］
　第２成分に含まれるポリイソシアネート（Ｃ）としては、特に限定されず、１分子中に２つ以上のイソシアネート基を有する種々のポリイソシアネート化合物を用いることができる。ポリイソシアネート（Ｃ）としては、例えば、芳香族ポリイソシアネート（Ｃ１）、脂肪族ポリイソシアネート（Ｃ２）、および、脂環式ポリイソシアネート（Ｃ３）が挙げられ、これらをいずれか１種用いても２種以上併用してもよい。 <Second component>
[Polyisocyanate (C)]
The polyisocyanate (C) contained in the second component is not particularly limited, and various polyisocyanate compounds having two or more isocyanate groups in one molecule can be used. Examples of the polyisocyanate (C) include aromatic polyisocyanate (C1), aliphatic polyisocyanate (C2), and alicyclic polyisocyanate (C3). More than one species may be used in combination.
　芳香族ポリイソシアネート（Ｃ１）としては、例えば、トリレンジイソシアネート（ＴＤＩ、例えば２，４－ＴＤＩ、２，６－ＴＤＩ）、ジフェニルメタンジイソシアネート（ＭＤＩ、例えば２，２’－ＭＤＩ、２，４’－ＭＤＩ、４，４’－ＭＤＩ）、４，４’－ジベンジルジイソシアネート、１，５－ナフチレンジイソシアネート、キシリレンジイソシアネート（ＸＤＩ）、１，３－フェニレンジイソシアネート、１，４－フェニレンジイソシアネート、並びにこれらの変性体および多核体が挙げられる。 Examples of the aromatic polyisocyanate (C1) include tolylene diisocyanate (TDI, such as 2,4-TDI, 2,6-TDI), diphenylmethane diisocyanate (MDI, such as 2,2'-MDI, 2,4'- MDI, 4,4'-MDI), 4,4'-dibenzyl diisocyanate, 1,5-naphthylene diisocyanate, xylylene diisocyanate (XDI), 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, and these modified forms and polynuclear forms of.
　脂肪族ポリイソシアネート（Ｃ２）としては、例えば、テトラメチレンジイソシアネート、ドデカメチレンジイソシアネート、ヘキサメチレンジイソシアネート（ＨＤＩ）、２，２，４－トリメチルヘキサメチレンジイソシアネート、２，４，４－トリメチルヘキサメチレンジイソシアネート、リジンジイソシアネート、２－メチルペンタン－１，５－ジイソシアネート、３－メチルペンタン－１，５－ジイソシアネート、並びにこれらの変性体および多核体が挙げられる。 Aliphatic polyisocyanates (C2) include, for example, tetramethylene diisocyanate, dodecamethylene diisocyanate, hexamethylene diisocyanate (HDI), 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, lysine Examples include diisocyanate, 2-methylpentane-1,5-diisocyanate, 3-methylpentane-1,5-diisocyanate, modified products and polynuclear products thereof.
　脂環式ポリイソシアネート（Ｃ３）としては、例えば、イソホロンジイソシアネート（ＩＰＤＩ）、水添キシリレンジイソシアネート、４，４’－ジシクロヘキシルメタンジイソシアネート、１，４－シクロヘキサンジイソシアネート、メチルシクロヘキシレンジイソシアネート、１，３－ビス（イソシアネートメチル）シクロヘキサン、並びにこれらの変性体および多核体が挙げられる。 Examples of the alicyclic polyisocyanate (C3) include isophorone diisocyanate (IPDI), hydrogenated xylylene diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, 1,4-cyclohexane diisocyanate, methylcyclohexylene diisocyanate, 1,3- Bis(isocyanatomethyl)cyclohexane, modified products thereof and polynuclear products thereof can be mentioned.
　上記変性体としては、例えば、イソシアヌレート変性体、アロファネート変性体、ビュレット変性体、アダクト変性体、カルボジイミド変性体などが挙げられる。 Examples of the modified compounds include isocyanurate modified products, allophanate modified products, burette modified products, adduct modified products, and carbodiimide modified products.
　一実施形態において、ポリイソシアネート（Ｃ）は、芳香族ポリイソシアネート（Ｃ１）を含むことが好ましい。芳香族ポリイソシアネート（Ｃ１）を用いることにより、引張特性の改善効果を高めることができる。より好ましくは、ポリイソシアネート（Ｃ）として、ジフェニルメタンジイソシアネート、並びにその変性体および多核体からなる群から選択される少なくとも１種を用いることである。 In one embodiment, the polyisocyanate (C) preferably contains an aromatic polyisocyanate (C1). By using the aromatic polyisocyanate (C1), the effect of improving the tensile properties can be enhanced. More preferably, the polyisocyanate (C) is at least one selected from the group consisting of diphenylmethane diisocyanate, its modified form and polynuclear form.
　二液硬化型ポリウレタン樹脂組成物におけるポリイソシアネート（Ｃ）の含有量は、特に限定されず、例えば、ポリオール（Ａ）１００質量部に対して、１～７０質量部でもよく、３～５０質量部でもよく、５～４０質量部でもよい。 The content of the polyisocyanate (C) in the two-component curable polyurethane resin composition is not particularly limited. or 5 to 40 parts by mass.
　ポリイソシアネート（Ｃ）は、２官能のもののみで構成されてもよく、３官能以上のものを含んでもよいが、ポリオール（Ａ）が２官能のもののみで構成される場合、ポリウレタン樹脂組成物を熱硬化性にするべく３官能以上のポリイソシアネートを含むことが好ましい。 The polyisocyanate (C) may be composed only of bifunctional ones, and may contain trifunctional or more functional ones. It preferably contains a tri- or higher functional polyisocyanate to make it thermosetting.
　ポリイソシアネート（Ｃ）とポリオール（Ａ）との比は、特に限定されず、例えば、ＮＣＯ／ＯＨ（インデックス）が、０．６～１．５でもよく、０．７～１．４でもよく、０．８～１．３でもよく、０．９～１．２でもよい。ここで、ＮＣＯ／ＯＨは、ポリオール（Ａ）に含まれるヒドロキシ基に対する、ポリイソシアネート（Ｃ）に含まれるイソシアネート基のモル比である。ＮＣＯ／ＯＨは、ポリオール（Ａ）の水酸基価とポリイソシアネート（Ｃ）のイソシアネート価を用いて算出される。イソシアネート価は、ＪＩＳ　Ｋ１６０３－１：２００７のＡ法に準拠して測定されるイソシアネート含有率を用いて、イソシアネート価＝｛（イソシアネート含有率）×５６１１０｝／（４２．０２×１００）により算出される。 The ratio of the polyisocyanate (C) and the polyol (A) is not particularly limited, for example, the NCO/OH (index) may be 0.6 to 1.5, 0.7 to 1.4, It may be 0.8 to 1.3, or 0.9 to 1.2. Here, NCO/OH is the molar ratio of isocyanate groups contained in polyisocyanate (C) to hydroxy groups contained in polyol (A). NCO/OH is calculated using the hydroxyl value of polyol (A) and the isocyanate value of polyisocyanate (C). The isocyanate value is calculated by isocyanate value = {(isocyanate content) x 56110}/(42.02 x 100) using the isocyanate content measured in accordance with JIS K1603-1:2007 A method. be.
　［その他の成分］
　第２成分はポリイソシアネート（Ｃ）のみで構成してもよく、また、ポリイソシアネート（Ｃ）の他に、必要に応じて、例えば、触媒、酸化防止剤、整泡剤、希釈剤、難燃剤、紫外線吸収剤、着色剤、充填剤、可塑剤などの各種添加剤を、本実施形態の目的を損なわない範囲で加えてもよい。 [Other ingredients]
The second component may be composed only of polyisocyanate (C), and in addition to polyisocyanate (C), if necessary, for example, catalyst, antioxidant, foam stabilizer, diluent, flame retardant , UV absorbers, colorants, fillers, plasticizers, and other additives may be added to the extent that the purpose of the present embodiment is not impaired.
　＜二液硬化型ポリウレタン樹脂組成物＞
　本実施形態に係る二液硬化型ポリウレタン樹脂組成物は、通常は、第１成分としての第１液と第２成分としての第２液とで構成されるが、第１成分および第２成分の他に、任意成分としての上記その他の成分を含む第３成分を第３液として備えてもよい。 <Two-component curable polyurethane resin composition>
The two-component curable polyurethane resin composition according to the present embodiment is usually composed of the first component as the first component and the second component as the second component. In addition, a third component containing the above-mentioned other components as optional components may be provided as the third liquid.
　該二液硬化型ポリウレタン樹脂組成物は、第１成分と第２成分をそれぞれ調製することにより製造することができ、すなわち、第１成分と第２成分はそれぞれ別の容器に充填されたものでもよい。別々の容器に充填された第１成分と第２成分は、使用時に混合されることによりポリオール（Ａ）とポリイソシアネート（Ｃ）が反応してポリウレタン樹脂が形成され、硬化してもよい。その際、加熱により硬化させてもよい。実施形態に係る二液硬化型ポリウレタン樹脂組成物は、第１成分と第２成分を混合して得られたものであってもよく、硬化前の液状でもよく、硬化していてもよい。 The two-component curable polyurethane resin composition can be produced by preparing the first component and the second component, respectively. good. The first component and the second component filled in separate containers may be mixed at the time of use to form a polyurethane resin by reacting the polyol (A) and the polyisocyanate (C), which may be cured. At that time, it may be cured by heating. The two-component curable polyurethane resin composition according to the embodiment may be obtained by mixing the first component and the second component, may be liquid before curing, or may be cured.
　＜ポリオール組成物＞
　一実施形態に係るポリオール組成物は、二液硬化型ポリウレタン樹脂組成物のポリオール成分として用いられるものであり、上記第１成分がこれに相当する。そのため、該ポリオール組成物は、ポリオール（Ａ）およびテルペン樹脂（Ｂ）を含み、該ポリオール（Ａ）がポリブタジエンポリオールおよび／または水添ポリブタジエンポリオール（Ａ１）を４０質量％以上含み、該ポリオール（Ａ）がさらに炭素数が７～９のアルキレンポリオール（Ａ２）を４～１５質量％含み、テルペン樹脂（Ｂ）の含有量がポリオール（Ａ）１００質量部に対して５～６０質量部である。ポリオール（Ａ）、テルペン樹脂（Ｂ）およびその他の成分についての詳細は上述したとおりであり、説明は省略する。 <Polyol composition>
A polyol composition according to one embodiment is used as a polyol component of a two-part curable polyurethane resin composition, and the first component corresponds to this. Therefore, the polyol composition contains a polyol (A) and a terpene resin (B), the polyol (A) contains 40% by mass or more of polybutadiene polyol and/or hydrogenated polybutadiene polyol (A1), and the polyol (A ) further contains 4 to 15% by mass of an alkylene polyol (A2) having 7 to 9 carbon atoms, and the content of the terpene resin (B) is 5 to 60 parts by mass based on 100 parts by mass of the polyol (A). The details of the polyol (A), the terpene resin (B) and other components are as described above, and their description is omitted.
　＜二液硬化型ポリウレタン樹脂組成物の用途＞
　本実施形態に係る二液硬化型ポリウレタン樹脂組成物の用途は、特に限定されないが、電気電子部品の封止のために用いられることが好ましい。電気電子部品としては、例えば、トランスコイル、チョークコイルおよびリアクトルコイルなどの変圧器、機器制御基板、センサ、無線通信部品などが挙げられる。該二液硬化型ポリウレタン樹脂組成物は、低誘電特性に優れ（すなわち誘電率が低く）電波の影響を受けにくい。そのため、該二液硬化型ポリウレタン樹脂組成物は、無線通信を行う無線通信部品を外部環境から保護するために当該無線通信部品を樹脂封止、すなわち被覆する封止材として用いられることが好ましい。例えば、検知した情報を無線通信により送信するセンサの封止材として用いてもよい。 <Application of two-component curing type polyurethane resin composition>
The use of the two-part curable polyurethane resin composition according to the present embodiment is not particularly limited, but it is preferably used for sealing electrical and electronic parts. Examples of electrical and electronic components include transformers such as transformer coils, choke coils and reactor coils, equipment control boards, sensors, and wireless communication components. The two-part curable polyurethane resin composition has excellent low dielectric properties (that is, it has a low dielectric constant) and is less susceptible to radio waves. Therefore, the two-component curable polyurethane resin composition is preferably used as a sealing material for resin-sealing, that is, covering wireless communication parts for wireless communication in order to protect the wireless communication parts from the external environment. For example, it may be used as a sealing material for a sensor that transmits detected information by wireless communication.
　本実施形態に係る二液硬化型ポリウレタン樹脂組成物を用いて樹脂封止された電気電子部品は、例えば、電気洗濯機、便座、湯沸し器、浄水器、風呂、食器洗浄機、太陽光パネル、電動工具、自動車、バイクなどに使用することができる。 Electrical and electronic components resin-sealed using the two-component curable polyurethane resin composition according to the present embodiment include, for example, electric washing machines, toilet seats, water heaters, water purifiers, baths, dishwashers, solar panels, Can be used for electric tools, automobiles, motorcycles, etc.
　以下、実施例及び比較例に基づいて、二液硬化型ポリウレタン樹脂組成物について詳細に説明するが、本発明はこれにより限定されない。 The two-component curable polyurethane resin composition will be described in detail below based on Examples and Comparative Examples, but the present invention is not limited thereto.
　実施例及び比較例において使用した原料を以下に示す。 The raw materials used in Examples and Comparative Examples are shown below.
　［ポリオール（Ａ）］
・ポリブタジエンポリオール１：水酸基価４７ｍｇＫＯＨ／ｇ、製品名：Ｐｏｌｙ　ｂｄ　Ｒ－４５ＨＴ、出光興産（株）製
・ポリブタジエンポリオール２：水酸基価１０７ｍｇＫＯＨ／ｇ、製品名：Ｐｏｌｙ　ｂｄ　Ｒ－１５ＨＴ、出光興産（株）製
・水添ポリブタジエンポリオール：水酸基価４９ｍｇＫＯＨ／ｇ、製品名：ＫＲＡＳＯＬ　Ｈ－ＬＢＨ－２０００、クレイバレー社製
・オクタンジオール：２－エチル－１，３－ヘキサンジオール、製品名：オクタンジオール、ＫＨネオケム（株）製
・トリメチロールプロパン：東京化成工業（株）製、製品コードＴ０４８０
・１，１０－デカンジオール：東京化成工業（株）製、製品コードＤ００１４
・エチレングリコール：ナカライテスク（株）製、製品コード１５２０８－９５
・１，４－ブタンジオール：ナカライテスク（株）製、製品コード０５９２２－３５
・ひまし油系ポリオール：水酸基価１６０ｍｇＫＯＨ／ｇ、製品名：ひまし油、伊藤製油（株）製 [Polyol (A)]
・Polybutadiene polyol 1: hydroxyl value 47 mgKOH/g, product name: Poly bd R-45HT, manufactured by Idemitsu Kosan Co., Ltd. ・Polybutadiene polyol 2: hydroxyl value 107 mgKOH/g, product name: Poly bd R-15HT, Idemitsu Kosan Co., Ltd. ) manufactured by Hydrogenated polybutadiene polyol: hydroxyl value 49 mgKOH/g, product name: KRASOL H-LBH-2000, manufactured by Clay Valley Co. Octanediol: 2-ethyl-1,3-hexanediol, product name: octanediol, KH Trimethylolpropane manufactured by Neochem Co., Ltd.: manufactured by Tokyo Chemical Industry Co., Ltd., product code T0480
・ 1,10-Decanediol: manufactured by Tokyo Chemical Industry Co., Ltd., product code D0014
・ Ethylene glycol: manufactured by Nacalai Tesque Co., Ltd., product code 15208-95
· 1,4-butanediol: manufactured by Nacalai Tesque Co., Ltd., product code 05922-35
・ Castor oil-based polyol: hydroxyl value 160 mgKOH / g, product name: castor oil, manufactured by Ito Oil Co., Ltd.
　［テルペン樹脂（Ｂ）］
・テルペン樹脂１：リモネン・スチレン共重合体、有効成分５０質量％、製品名：ＹＳレジンＬＰ、ヤスハラケミカル（株）製
・テルペン樹脂２：ピネン・ジペンテン共重合体、有効成分８０質量％、製品名：ダイマロン、ヤスハラケミカル（株）製
・テルペン樹脂３：フェノール・α－ピネン共重合体、有効成分１００質量％、製品名：ＹＳ　ＰＯＬＹＳＴＥＲ　Ｔ８０、ヤスハラケミカル（株）製 [Terpene resin (B)]
・ Terpene resin 1: limonene-styrene copolymer, active ingredient 50% by mass, product name: YS Resin LP, manufactured by Yasuhara Chemical Co., Ltd. ・ Terpene resin 2: pinene-dipentene copolymer, active ingredient 80% by mass, product name : Dymaron, manufactured by Yasuhara Chemical Co., Ltd. Terpene resin 3: Phenol/α-pinene copolymer, active ingredient 100% by mass, product name: YS POLYSTER T80, manufactured by Yasuhara Chemical Co., Ltd.
　［ポリイソシアネート（Ｃ）］
・芳香族ポリイソシアネート：ポリメリックＭＤＩ、製品名：ミリオネートＭＲ－２００、東ソー（株）製 [Polyisocyanate (C)]
・ Aromatic polyisocyanate: Polymeric MDI, product name: Millionate MR-200, manufactured by Tosoh Corporation
　［実施例１～１２及び比較例１～７］
　下記表１および表２に示す配合（質量部）により、各実施例及び各比較例の二液硬化型ポリウレタン樹脂組成物を調製した。調製に際しては、表１および表２に示す第１成分を所定量秤量し、適宜熱をかけて溶かし込みながら攪拌混合を行い、混合後、２５℃に調整した。続いて、この混合物に２５℃に調整した第２成分（ポリイソシアネート（Ｃ））を表１および表２に記載のとおりに加えて攪拌混合し、脱泡した。 [Examples 1 to 12 and Comparative Examples 1 to 7]
Two-component curable polyurethane resin compositions of each example and each comparative example were prepared according to the formulations (parts by mass) shown in Tables 1 and 2 below. For the preparation, a predetermined amount of the first component shown in Tables 1 and 2 was weighed, and stirred and mixed while being melted by heating appropriately. After mixing, the temperature was adjusted to 25°C. Subsequently, the second component (polyisocyanate (C)) adjusted to 25° C. was added to the mixture as shown in Tables 1 and 2, and the mixture was stirred and mixed to degas.
　各二液硬化型ポリウレタン樹脂組成物について、相溶性、密着性、誘電率、引張強度、および伸び率を測定・評価した。測定・評価方法は以下のとおりである。 Compatibility, adhesion, dielectric constant, tensile strength, and elongation were measured and evaluated for each two-component curing type polyurethane resin composition. The measurement and evaluation methods are as follows.
　［相溶性］
　第１成分を混合した後の液を用いて、直径３ｃｍのスクリュー管瓶（（株）マルエム製Ｎｏ．７）２本に、一方は高さが１０ｃｍになるよう、他方は高さが１ｃｍとなるように注いだ。各スクリュー管瓶を文字「Ｓ」（ＭＳゴシック、１２ポイント）が印刷された用紙の上に置き、上方からの文字の視認により下記Ａ～Ｃの３段階で相溶性を評価した。調製後に第１成分に分離が発生したものについては、ポリオールと樹脂との相溶性が不良であり、その後の二液硬化型ポリウレタン樹脂組成物としての測定・評価を実施することができないため、表中には評価結果をＤと記載し、以降の評価は実施しなかった。なお、評価がＣ以上であれば、実用上の相溶性を有するといえる。
　Ａ：透明（高さ１０ｃｍ、１ｃｍいずれのスクリュー管瓶でも下に記載された文字を読むことができる）
　Ｂ：微濁（高さ１０ｃｍのスクリュー管瓶の下に記載した文字を読むことができないが、高さ１ｃｍのスクリュー管瓶の下に記載された文字は読むことができる）
　Ｃ：白濁（高さ１０ｃｍ、１ｃｍいずれのスクリュー管瓶のでも下に記載された文字が読むことができない） [Compatibility]
The liquid after mixing the first component was poured into two screw vials (No. 7, manufactured by Maruem Co., Ltd.) with a diameter of 3 cm, one with a height of 10 cm and the other with a height of 1 cm. I poured it so that it would be Each screw tube bottle was placed on a sheet of paper printed with the letter "S" (MS Gothic, 12 points), and compatibility was evaluated in the following three grades from A to C by viewing the letters from above. For those in which separation occurred in the first component after preparation, the compatibility between the polyol and the resin was poor, and subsequent measurement and evaluation as a two-component curing type polyurethane resin composition could not be performed. Among them, the evaluation result was described as D, and the subsequent evaluation was not implemented. Incidentally, if the evaluation is C or higher, it can be said to have practical compatibility.
A: Transparent (The characters written below can be read in both 10 cm and 1 cm screw-type bottles.)
B: Slightly turbid (I can not read the letters written under the screw bottle with a height of 10 cm, but I can read the letters written under the screw bottle with a height of 1 cm)
C: Cloudy (I can't read the characters written on the bottom of both 10 cm and 1 cm screw-type vials)
　［密着性］
　市販されているＦＲ－４エポキシ基板上に、上記脱泡後の二液硬化型ポリウレタン樹脂組成物を直径１ｃｍほど垂らし、８０℃にて１６時間（一晩）養生し、硬化させた。硬化後のポリウレタン樹脂とエポキシ基板上の境目を狙い、カッターナイフにて樹脂を斫り、基板上に残ったポリウレタン樹脂を目視によって確認した。評価は、凝集破壊をポリウレタン樹脂部分が基板上に残っている状態、界面剥離を基板上からポリウレタン樹脂がはがれてしまう状態とし、両状態が混在している際は、その面積割合に応じて下記基準により評価を行った。なお、評価がＤ以上であれば、実用上の密着性を有するといえる。
　Ａ：凝集破壊１００％
　Ｂ：凝集破壊が７５％以上１００％未満、界面剥離が０％超２５％以下
　Ｃ：凝集破壊が５０％以上７５％未満、界面剥離が２５％超５０％以下
　Ｄ：凝集破壊が２５％以上５０％未満、界面剥離が５０％超７５％以下
　Ｅ：凝集破壊が２５％未満、界面剥離が７５％以上 [Adhesion]
On a commercially available FR-4 epoxy substrate, the degassed two-pack curable polyurethane resin composition was dropped about 1 cm in diameter, cured at 80° C. for 16 hours (overnight) and cured. Aiming at the boundary between the cured polyurethane resin and the epoxy substrate, the resin was scraped off with a cutter knife, and the polyurethane resin remaining on the substrate was visually confirmed. Cohesive failure was defined as the state in which the polyurethane resin part remained on the substrate, and interfacial peeling was defined as the state in which the polyurethane resin peeled off from the substrate. Evaluation was performed according to the standard. In addition, if the evaluation is D or higher, it can be said to have practical adhesion.
A: 100% cohesive failure
B: Cohesive failure is 75% or more and less than 100%, interfacial peeling is more than 0% and less than 25% C: Cohesive failure is 50% or more and less than 75%, interfacial peeling is more than 25% and 50% or less D: Cohesive failure is 25% or more Less than 50%, more than 50% and 75% or less of interfacial delamination E: Less than 25% of cohesive failure, 75% or more of interfacial delamination
　［誘電率］
　上記脱泡後の二液硬化型ポリウレタン樹脂組成物を厚み３ｍｍの金型に流し、８０℃にて１６時間（一晩）養生し、３ｍｍ厚の樹脂シートを作製した。該樹脂シートを５０ｍｍ×５０ｍｍ×３ｍｍのシートに切り分け、測定用サンプルとした。測定は、アジレント・テクノロジー（株）製の装置（本体の型式：Ｅ４９８０Ａ、名称：Ｐｒｅｃｉｓｉｏｎ　ＬＣＲ　Ｍｅｔｅｒ。電極部分の型式：１６４５１Ｂ、名称：ＤＩＥＬＥＣＴＲＩＣ　ＴＥＳＴ　ＦＩＸＴＵＲＥ）を用いて実施し、周波数１ＭＨｚ時の誘電率（比誘電率）の値を測定し、下記基準により評価した。
　Ａ：誘電率が２．８以下
　Ｂ：誘電率が２．８より大きく３．０以下
　Ｃ：誘電率が３．０より大きく３．２以下
　Ｄ：誘電率が３．２より大きく３．４以下
　Ｅ：誘電率が３．４より大きい [Permittivity]
The defoamed two-pack curable polyurethane resin composition was poured into a mold having a thickness of 3 mm and cured at 80° C. for 16 hours (overnight) to prepare a resin sheet having a thickness of 3 mm. The resin sheet was cut into sheets of 50 mm×50 mm×3 mm to obtain samples for measurement. The measurement was performed using an apparatus manufactured by Agilent Technologies, Inc. (body model: E4980A, name: Precision LCR Meter, electrode part model: 16451B, name: DIELECTRIC TEST FIXTURE), and the dielectric constant at a frequency of 1 MHz (relative dielectric constant) was measured and evaluated according to the following criteria.
A: permittivity is 2.8 or less B: permittivity is greater than 2.8 and 3.0 or less C: permittivity is greater than 3.0 and 3.2 or less D: permittivity is greater than 3.2 and 3.4 Below E: Dielectric constant greater than 3.4
　［引張強度、伸び率］
　上記脱泡後の二液硬化型ポリウレタン樹脂組成物を厚み３ｍｍの金型に流し、８０℃にて１６時間（一晩）養生し、３ｍｍ厚の樹脂シートを作製した。該樹脂シートをダンベル状３号型に打ち抜き、測定用サンプルとした。測定は、（株）島津製作所製の装置（本体の型式：ＡＧ－Ｘ　Ｐｌｕｓ、名称：島津精密万能試験機　オートグラフ）を用いて、引張速度を５００ｍｍ／ｍｉｎ、チャック間距離４０ｍｍに設定して３回実施し、引張強度（破断応力）・伸び率（破断伸び）の平均値を計算し、下記基準により評価した。
　（引張強度の評価基準）
　Ａ：引張強度が３．０ＭＰａ以上
　Ｂ：引張強度が２．５ＭＰａ以上で３．０ＭＰａ未満
　Ｃ：引張強度が２．０ＭＰａ以上で２．５ＭＰａ未満
　Ｄ：引張強度が１．５ＭＰａ以上で２．０ＭＰａ未満
　Ｅ：引張強度が１．５ＭＰａ未満
　（伸び率の評価基準）
　Ａ：伸び率が１３０％以上
　Ｂ：伸び率が１１０％以上で１３０％未満
　Ｃ：伸び率が９０％以上で１１０％未満
　Ｄ：伸び率が７０％以上で９０％未満
　Ｅ：伸び率が７０％未満 [Tensile strength, elongation]
The defoamed two-pack curable polyurethane resin composition was poured into a mold having a thickness of 3 mm and cured at 80° C. for 16 hours (overnight) to prepare a resin sheet having a thickness of 3 mm. The resin sheet was punched into a dumbbell-shaped No. 3 mold to obtain a sample for measurement. The measurement was performed using an apparatus manufactured by Shimadzu Corporation (main body model: AG-X Plus, name: Shimadzu Precision Universal Testing Machine Autograph), with the tensile speed set to 500 mm/min and the distance between chucks set to 40 mm. It was performed three times, and the average value of tensile strength (breaking stress) and elongation (breaking elongation) was calculated and evaluated according to the following criteria.
(Evaluation criteria for tensile strength)
A: Tensile strength is 3.0 MPa or more B: Tensile strength is 2.5 MPa or more and less than 3.0 MPa C: Tensile strength is 2.0 MPa or more and less than 2.5 MPa D: Tensile strength is 1.5 MPa or more and 2.0 MPa Less than E: Tensile strength less than 1.5 MPa (elongation rate evaluation criteria)
A: Elongation is 130% or more B: Elongation is 110% or more and less than 130% C: Elongation is 90% or more and less than 110% D: Elongation is 70% or more and less than 90% E: Elongation is 70 %less than
　結果は表１および表２に示すとおりである。比較例１では、ＰＢポリオール（Ａ１）とテルペン樹脂（Ｂ）を併用したことにより、相溶性に優れ、低誘電特性と基板との密着性にも優れていたが、アルキレンポリオール（Ａ２）を配合していないため、引張強度および伸び率が低く、引張特性に劣っていた。 The results are shown in Tables 1 and 2. In Comparative Example 1, the combined use of the PB polyol (A1) and the terpene resin (B) resulted in excellent compatibility, low dielectric properties, and excellent adhesion to the substrate, but the alkylene polyol (A2) was added. Therefore, the tensile strength and elongation were low, and the tensile properties were poor.
　これに対し、アルキレンポリオール（Ａ２）を添加した実施例１～１２では、相溶性、密着性および低誘電特性を有するとともに、さらに引張特性を改善することができた。特に実施例１，４～１２であると、相溶性、密着性および低誘電特性に優れるとともに、引張特性の改善効果に優れており、さらに、実施例１，５，７～１１であるとより一層優れた効果がみられた。なお、実施例３では、引張強度の評価はＤであるが、伸び率の評価がＡで優れており、トータルとして引張特性の改善効果が認められた。 On the other hand, in Examples 1 to 12 in which alkylene polyol (A2) was added, compatibility, adhesion and low dielectric properties were obtained, and tensile properties could be further improved. In particular, Examples 1, 4 to 12 are excellent in compatibility, adhesion, and low dielectric properties, and are excellent in improving tensile properties. Further, Examples 1, 5, 7 to 11 are more A better effect was observed. In Example 3, the tensile strength was evaluated as D, but the elongation rate was evaluated as A, which was excellent, and the effect of improving the tensile properties as a whole was recognized.
　比較例２～５では、炭素数７～９のアルキレンポリオール（Ａ２）の代わりに、他のアルキレンポリオールであるトリメチロールプロパン、デカンジオール、エチレングリコールまたはブタンジオールを添加した。これらの比較例では、相溶性が損なわれるか、相溶性が良好な比較例３でも引張特性の改善効果は得られなかった。 In Comparative Examples 2 to 5, trimethylolpropane, decanediol, ethylene glycol or butanediol, which is another alkylene polyol, was added instead of the alkylene polyol (A2) having 7 to 9 carbon atoms. In these comparative examples, the compatibility was impaired, or the effect of improving the tensile properties was not obtained even in Comparative Example 3, which had good compatibility.
　なお、明細書に記載の種々の数値範囲は、それぞれそれらの上限値と下限値を任意に組み合わせることができ、それら全ての組み合わせが好ましい数値範囲として本明細書に記載されているものとする。また、「Ｘ～Ｙ」との数値範囲の記載は、Ｘ以上Ｙ以下を意味する。 It should be noted that the various numerical ranges described in the specification can be arbitrarily combined with their upper and lower limits, and all combinations thereof are described in this specification as preferred numerical ranges. Further, the description of the numerical range "X to Y" means X or more and Y or less.
　以上、本発明のいくつかの実施形態を説明したが、これら実施形態は、例として提示したものであり、発明の範囲を限定することは意図していない。これら実施形態は、その他の様々な形態で実施されることが可能であり、発明の要旨を逸脱しない範囲で、種々の省略、置き換え、変更を行うことができる。これら実施形態やその省略、置き換え、変更などは、発明の範囲や要旨に含まれると同様に、特許請求の範囲に記載された発明とその均等の範囲に含まれるものである。 Although several embodiments of the present invention have been described above, these embodiments are presented as examples and are not intended to limit the scope of the invention. These embodiments can be implemented in various other forms, and various omissions, replacements, and modifications can be made without departing from the scope of the invention. These embodiments, their omissions, replacements, modifications, etc., are included in the invention described in the scope of claims and equivalents thereof, as well as being included in the scope and gist of the invention.

Claims (7)

  1. 　ポリオールおよびテルペン樹脂を含む第１成分と、　ポリイソシアネートを含む第２成分と、を含み、
    　前記ポリオールは、ポリブタジエンポリオールおよび／または水添ポリブタジエンポリオールを４０質量％以上含み、
    　前記ポリオールは、さらに炭素数が７以上９以下のアルキレンポリオールを４～１５質量％含み、
    　前記テルペン樹脂の含有量が、前記ポリオール１００質量部に対して５～６０質量部である、二液硬化型ポリウレタン樹脂組成物。     a first component comprising a polyol and a terpene resin; and a second component comprising a polyisocyanate;
    The polyol contains 40% by mass or more of polybutadiene polyol and/or hydrogenated polybutadiene polyol,
    The polyol further contains 4 to 15% by mass of an alkylene polyol having 7 to 9 carbon atoms,
    A two-pack curable polyurethane resin composition, wherein the content of the terpene resin is 5 to 60 parts by mass with respect to 100 parts by mass of the polyol.
  2. 　前記アルキレンポリオールは、第一級炭素原子に結合したヒドロキシ基と第二級炭素原子に結合したヒドロキシ基とを有するジオールである、請求項１に記載の二液硬化型ポリウレタン樹脂組成物。 The two-part curable polyurethane resin composition according to claim 1, wherein the alkylene polyol is a diol having a hydroxy group bonded to a primary carbon atom and a hydroxy group bonded to a secondary carbon atom.
  3. 　前記ポリイソシアネートが芳香族ポリイソシアネートを含む、請求項１または２に記載の二液硬化型ポリウレタン樹脂組成物。 The two-component curable polyurethane resin composition according to claim 1 or 2, wherein the polyisocyanate contains an aromatic polyisocyanate.
  4. 　前記ポリオールが、ひまし油系ポリオールをさらに含む、請求項１～３のいずれか１項に記載の二液硬化型ポリウレタン樹脂組成物。 The two-component curable polyurethane resin composition according to any one of claims 1 to 3, wherein the polyol further contains a castor oil-based polyol.
  5. 　電気電子部品封止用である、請求項１～４のいずれか１項に記載の二液硬化型ポリウレタン樹脂組成物。 The two-component curable polyurethane resin composition according to any one of claims 1 to 4, which is for sealing electrical and electronic parts.
  6. 　請求項１～５のいずれか１項に記載の二液硬化型ポリウレタン樹脂組成物を用いて樹脂封止された電気電子部品。 An electrical and electronic component resin-sealed using the two-component curing type polyurethane resin composition according to any one of claims 1 to 5.
  7. 　二液硬化型ポリウレタン樹脂組成物のポリオール成分として用いられるポリオール組成物であって、
    　ポリオールおよびテルペン樹脂を含み、
    　前記ポリオールは、ポリブタジエンポリオールおよび／または水添ポリブタジエンポリオールを４０質量％以上含み、
    　前記ポリオールは、さらに炭素数が７以上９以下のアルキレンポリオールを４～１５質量％含み、
    　前記テルペン樹脂の含有量が、前記ポリオール１００質量部に対して５～６０質量部である、ポリオール組成物。     A polyol composition used as a polyol component of a two-component curable polyurethane resin composition,
    including polyols and terpene resins,
    The polyol contains 40% by mass or more of polybutadiene polyol and/or hydrogenated polybutadiene polyol,
    The polyol further contains 4 to 15% by mass of an alkylene polyol having 7 to 9 carbon atoms,
    The polyol composition, wherein the content of the terpene resin is 5 to 60 parts by mass with respect to 100 parts by mass of the polyol.
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JPH1180306A (en) * 1997-09-08 1999-03-26 Yasuhara Chem Co Ltd Urethane resin composition
JP2008115348A (en) * 2006-10-31 2008-05-22 Yasuhara Chemical Co Ltd Urethane resin composition
WO2013137006A1 (en) * 2012-03-12 2013-09-19 昭和電工株式会社 Polymerizable composition, polymer, image display device, and method for producing same
JP6916404B1 (en) * 2021-03-05 2021-08-11 第一工業製薬株式会社 Two-component curable polyurethane resin composition

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Publication number Priority date Publication date Assignee Title
JPH0859784A (en) * 1994-08-19 1996-03-05 Nippon Shokubai Co Ltd Resin composition

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH1180306A (en) * 1997-09-08 1999-03-26 Yasuhara Chem Co Ltd Urethane resin composition
JP2008115348A (en) * 2006-10-31 2008-05-22 Yasuhara Chemical Co Ltd Urethane resin composition
WO2013137006A1 (en) * 2012-03-12 2013-09-19 昭和電工株式会社 Polymerizable composition, polymer, image display device, and method for producing same
JP6916404B1 (en) * 2021-03-05 2021-08-11 第一工業製薬株式会社 Two-component curable polyurethane resin composition

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