WO2023286595A1 - Polyurethane resin composition - Google Patents

Polyurethane resin composition Download PDF

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Publication number
WO2023286595A1
WO2023286595A1 PCT/JP2022/025875 JP2022025875W WO2023286595A1 WO 2023286595 A1 WO2023286595 A1 WO 2023286595A1 JP 2022025875 W JP2022025875 W JP 2022025875W WO 2023286595 A1 WO2023286595 A1 WO 2023286595A1
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Prior art keywords
containing compound
butylene oxide
polyurethane resin
resin composition
mass
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PCT/JP2022/025875
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French (fr)
Japanese (ja)
Inventor
梓 金井
勝紀 竹田
望 繁中
愛 石野
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第一工業製薬株式会社
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Publication of WO2023286595A1 publication Critical patent/WO2023286595A1/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
    • C08G18/28—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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • 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
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
    • C08G18/78—Nitrogen
    • C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
    • 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

  • An embodiment of the present invention relates to a polyurethane resin composition.
  • Patent Document 1 discloses a polyurethane resin composition containing a hydroxyl group-containing compound, an isocyanate group-containing compound, a metal hydroxide and a plasticizer, wherein the hydroxyl group-containing compound contains polybutadiene polyol and castor oil-based polyol, A polyurethane resin composition is disclosed wherein the metal hydroxide is aluminum hydroxide and/or magnesium hydroxide.
  • An object of the embodiments of the present invention is to provide a polyurethane resin composition that is excellent in heat and humidity resistance.
  • a polyurethane resin composition comprising a butylene oxide-based polyol (A2) in which the above is a butylene oxide unit, and wherein the butylene oxide-based polyol (A2) has a number average molecular weight of 400 or more and 3,000 or less.
  • the butylene oxide-based polyol (A2) has a number average molecular weight of 600 or more and 1600 or less, and the content of the butylene oxide-based polyol (A2) in 100% by mass of the hydroxyl group-containing compound (A) is 20% by mass or more.
  • the polyurethane resin composition according to this embodiment contains a hydroxyl group-containing compound (A) and an isocyanate group-containing compound (B).
  • hydroxyl group-containing compound (A) As the hydroxyl group-containing compound (A), a polyol compound having two or more hydroxyl groups in one molecule can be used.
  • the hydroxyl group-containing compound (A) is a polybutadiene polyol (A1) and a butylene oxide and a polyol (A2).
  • the polybutadiene polyol (A1) is not particularly limited, and preferably has a 1,4-bonded type, 1,2-bonded type, or a mixture of these polybutadiene structures and at least two hydroxyl groups in the molecule. More preferably, both ends of the polybutadiene structure have hydroxyl groups.
  • the polybutadiene polyol (A1) may be a hydrogenated polybutadiene polyol in which some or all of its unsaturated double bonds are hydrogenated, or a combination of non-hydrogenated and hydrogenated polybutadiene polyols. Moreover, two or more polybutadiene polyols having different molecular weights and functional group numbers may be used in combination.
  • the molecular weight of the polybutadiene polyol (A1) is not particularly limited. good.
  • the number of functional groups of polybutadiene polyol (A1) is not particularly limited, and may be, for example, 2.0 to 4.0 or 2.0 to 2.5.
  • the hydroxyl value of the polybutadiene polyol (A1) is not particularly limited, and 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.
  • the number average molecular weight (Mn) of polybutadiene polyol (A1) is a value measured by the GPC method (gel permeation chromatography method) and calculated using a standard polystyrene calibration curve.
  • GPC conditions are, for example, column: "TSKgel GMHHR-H” manufactured by Tosoh Corporation, solvent: THF, flow rate: 0.6 mL/min, measurement temperature: 40°C.
  • the hydroxyl value of polybutadiene polyol (A1) is a value measured according to A method of JIS K1557-1:2007. Potassium hydroxide ( KOH) in mg.
  • the number of functional groups of polybutadiene polyol (A1) is a value calculated by the following formula.
  • the content of the polybutadiene polyol (A1) is not particularly limited, but is preferably 20 to 90% by mass, more preferably 40 to 80% by mass, based on 100% by mass of the hydroxyl group-containing compound (A). It is preferably 50 to 80% by mass.
  • the butylene oxide-based polyol (A2) is a polyol in which 50 mol % or more of the alkylene oxide units are butylene oxide units. More specifically, the butylene oxide-based polyol (A2) is a polyalkylene glycol in which 50 mol% or more of the total alkylene oxide used to form the polyol is butylene oxide, and is a broadly defined polybutylene glycol. .
  • the moist heat resistance of the polyurethane resin composition can be improved.
  • the amount of butylene oxide units relative to all alkylene oxide units is preferably 60 mol% or more, more preferably 60 mol% or more, from the viewpoint of wet heat resistance and compatibility with the polybutadiene polyol (A1). It may be 70 mol % or more, may be 80 mol % or more, may be 90 mol % or more, or may be 100 mol %.
  • the other alkylene oxide units are not particularly limited, and examples include ethylene oxide units and/or propylene oxide units.
  • the butylene oxide-based polyol (A2) may be a polybutylene glycol composed of 100 mol% of alkylene oxide units and of butylene oxide units.
  • a butylene oxide-based polyol (A2) having a number average molecular weight (Mn) of 400 to 3000 is used.
  • Mn number average molecular weight
  • the butylene oxide polyol (A2) preferably has a number average molecular weight of 600 or more, more preferably 800 or more.
  • the number average molecular weight is preferably 2000 or less, more preferably 1600 or less, and may be 1300 or less.
  • the hydroxyl value of the butylene oxide-based polyol (A2) is not particularly limited, and may be, for example, 37-500 mgKOH/g, 50-300 mgKOH/g, or 60-200 mgKOH/g.
  • the number average molecular weight (Mn) of the butylene oxide-based polyol (A2) is a value converted from the hydroxyl value and the number of functional groups according to the following formula.
  • the hydroxyl value of the butylene oxide polyol (A2) is a value (mgKOH/g) measured according to A method of JIS K1557-1:2007. .
  • the number of functional groups of the butylene oxide-based polyol (A2) is obtained from the number of active hydrogen atoms in the active hydrogen atom-containing compound as an initiator as described below.
  • the structure of the butylene oxide-based polyol (A2) is not particularly limited.
  • it has a structure obtained by addition polymerization of an alkylene oxide containing butylene oxide to a compound having 2 to 8 active hydrogen atoms as an initiator.
  • the butylene oxide 1,2-butylene oxide and/or 2,3-butylene oxide are used, preferably 1,2-butylene oxide.
  • a bifunctional butylene oxide polyol (A2) can be obtained. If a compound (diol) having two active hydrogen atoms such as ethylene glycol or propylene glycol is used as the initiator, a bifunctional butylene oxide polyol (A2) can be obtained. If a compound (triol) having three active hydrogen atoms such as glycerin or trimethylolpropane is used as the initiator, a trifunctional butylene oxide polyol (A2) can be obtained. Since it is believed that tri-functionality cures faster than di-functionality, a tri-functional butylene oxide polyol (A2) may be used when faster curing is desired.
  • the number of functional groups of the butylene oxide-based polyol (A2) is not particularly limited, and may be 2-8 or 2-4.
  • the butylene oxide-based polyol (A2) is bifunctional or trifunctional, and a combination of bifunctional and trifunctional may be used.
  • butylene oxide when butylene oxide is copolymerized with other alkylene oxide, random copolymerization or block copolymerization may be used.
  • a terminal ethylene oxide-added polybutylene glycol having a structure in which butylene oxide is added to an initiator and then ethylene oxide is added to the end of the polybutylene oxide chain may be used. Curability can be enhanced by adding ethylene oxide to the terminal.
  • butylene oxide-based polyol (A2) any one of those having the above structure may be used, or two or more of those having different number average molecular weights, structures, etc. may be used in combination.
  • the content of the butylene oxide-based polyol (A2) is not particularly limited, it is preferably 10 to 80% by mass with respect to 100% by mass of the hydroxyl group-containing compound (A).
  • the content of the butylene oxide-based polyol (A2) is 10% by mass or more, the mixed viscosity during production of the polyurethane resin composition can be lowered. Further, when the content is 80% by mass or less, the curability can be improved.
  • the content of the butylene oxide-based polyol (A2) is more preferably 20 to 60% by mass, still more preferably 20 to 50% by mass.
  • the mass ratio of the polybutadiene polyol (A1) and the butylene oxide polyol (A2) is not particularly limited, but (A2)/(A1) is preferably 0.1 to 3.5, more preferably 0.2. ⁇ 1.0.
  • the hydroxyl group-containing compound (A) may consist only of the polybutadiene polyol (A1) and the butylene oxide-based polyol (A2), but may also contain other hydroxyl group-containing compounds.
  • the total amount (A1+A2) of the polybutadiene polyol (A1) and the butylene oxide polyol (A2) relative to 100% by mass of the hydroxyl group-containing compound (A) is not particularly limited, it is preferably 70% by mass or more, more preferably 80% by mass. It is at least 90% by mass, more preferably at least 90% by mass, and may be 100% by mass.
  • polyols are used as the other hydroxyl group-containing compound, and there is no particular limitation.
  • examples thereof include castor oil, castor oil fatty acids, hydrogenated castor oils obtained by hydrogenating these, and castor oil-based polyols produced using hydrogenated castor oil fatty acids.
  • other polyester polyols, polyether polyols, polycarbonate polyols, dimer acid polyols, polycaprolactone polyols, acrylic polyols, polyisoprene polyols, and the like are included.
  • low-molecular-weight polyols that are commonly used as cross-linking agents may be used.
  • N,N-bis(2-hydroxypropyl)aniline hydroquinone-bis( ⁇ -hydroxyethyl)ether, resorcinol-bis( ⁇ -hydroxyethyl) ether, and aliphatic alcohols such as ethylene glycol, 1,4-butanediol, octanediol, trimethylolpropane, and triisopropanolamine.
  • isocyanate group-containing compound (B) Various polyisocyanate compounds having two or more isocyanate groups in one molecule can be used as the isocyanate group-containing compound (B).
  • examples of the isocyanate group-containing compound (B) include an aliphatic polyisocyanate compound (B1), an alicyclic polyisocyanate compound (B2), an aromatic polyisocyanate compound (B3), and modified and polynuclear compounds thereof. Any one of them may be used, or two or more may be used in combination.
  • Examples of the aliphatic polyisocyanate compound (B1) include tetramethylene diisocyanate, dodecamethylene diisocyanate, hexamethylene diisocyanate (HDI), 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, 2-methylpentane-1,5-diisocyanate, 3-methylpentane-1,5-diisocyanate and the like.
  • HDI hexamethylene diisocyanate
  • 2,2,4-trimethylhexamethylene diisocyanate 2,4,4-trimethylhexamethylene diisocyanate
  • lysine diisocyanate 2-methylpentane-1,5-diisocyanate
  • 3-methylpentane-1,5-diisocyanate 3-methylpentane-1,5-diisocyanate and the like.
  • Examples of the alicyclic polyisocyanate compound (B2) include isophorone diisocyanate (IPDI), hydrogenated xylylene diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, 1,4-cyclohexane diisocyanate, methylcyclohexylene diisocyanate, 1,3 -Bis(isocyanatomethyl)cyclohexane and the like.
  • 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 and the like.
  • aromatic polyisocyanate compound (B3) 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, etc. mentioned.
  • 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, etc. mentioned.
  • Modified products of these polyisocyanate compounds (B1) to (B3) include, for example, isocyanurate modified products, allophanate modified products, biuret modified products, adduct modified products, and carbodiimide modified products.
  • the isocyanate group-containing compound (B) preferably contains an isocyanurate modified product.
  • the modified isocyanurate By using the modified isocyanurate, it has excellent miscibility with the hydroxyl group-containing compound (A), and can improve uniformity of hardness of the cured polyurethane resin composition.
  • the isocyanurate modified product include an isocyanurate modified product of the aliphatic polyisocyanate compound (B1), an isocyanurate modified product of the alicyclic polyisocyanate compound (B2), and an isocyanurate modified product of the aromatic polyisocyanate compound (B3). mentioned.
  • Preferred is the isocyanurate modified form of the aliphatic polyisocyanate compound (B1), and more preferred is HDI isocyanurate.
  • the isocyanate group-containing compound (B) preferably contains HDI.
  • HDI and the modified isocyanurate may be used in combination, or HDI and HDI isocyanurate may be used in combination.
  • the isocyanate group-containing compound (B) may contain MDI.
  • MDI may be monomeric MDI or polymeric MDI (crude MDI).
  • MDI and the above HD I and/or modified isocyanurate preferably HDI isocyanurate may be used in combination.
  • the content of the isocyanate group-containing compound (B) in the polyurethane resin composition is not particularly limited. parts, 10 to 40 parts by mass, or 15 to 30 parts by mass.
  • the ratio of the hydroxyl group-containing compound (A) and the isocyanate group-containing compound (B) is not particularly limited.
  • the ratio NCO/OH (index) may be from 0.6 to 1.5, from 0.7 to 1.3, or from 0.8 to 1.2.
  • the polyurethane resin composition according to the present embodiment may optionally contain, for example, a catalyst, an antioxidant, a foam stabilizer, a diluent, a flame retardant, an ultraviolet absorber, a colorant, Various additives such as fillers and plasticizers can be added as long as the purpose of the present embodiment is not impaired.
  • 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.
  • the content of the catalyst is not particularly limited, and may be, for example, 0.0001 to 0.1% by mass or 0.001 to 0.01% by mass with respect to 100% by mass of the polyurethane resin composition.
  • the polyurethane resin composition according to the present embodiment is configured as a two-component polyurethane resin composition containing a first liquid containing a hydroxyl group-containing compound (A) and a second liquid containing an isocyanate group-containing compound (B).
  • A a hydroxyl group-containing compound
  • B an isocyanate group-containing compound
  • Such a two-pack type polyurethane resin composition may further comprise a third liquid containing the other components as well as the first and second liquids.
  • the two-component polyurethane resin composition can be produced by preparing a first liquid and a second liquid, respectively, that is, the first liquid and the second liquid may be filled in separate containers. .
  • the first liquid and the second liquid filled in separate containers are mixed at the time of use, whereby the hydroxyl group-containing compound (A) and the isocyanate group-containing compound (B) react to form a polyurethane resin, which is cured. good too. At that time, it may be cured by heating.
  • the polyurethane resin composition according to this embodiment may be obtained by mixing the first liquid and the second liquid, may be in a liquid state before curing, or may be in a cured state.
  • the first liquid may be composed only of the hydroxyl group-containing compound (A), and in addition to the hydroxyl group-containing compound (A), if necessary, for example, a catalyst, an antioxidant, a foam stabilizer, a diluent , flame retardants, ultraviolet absorbers, colorants, fillers, plasticizers, and other additives.
  • the first liquid contains a hydroxyl group-containing compound (A) and a catalyst.
  • the second liquid may be composed only of the isocyanate group-containing compound (B), and in addition to the isocyanate group-containing compound (B), if necessary, for example, an antioxidant, a foam stabilizer, a diluent , flame retardants, ultraviolet absorbers, colorants, fillers, plasticizers, and other additives.
  • an antioxidant for example, an antioxidant, a foam stabilizer, a diluent , flame retardants, ultraviolet absorbers, colorants, fillers, plasticizers, and other additives.
  • the use of the polyurethane resin composition according to the present embodiment is not particularly limited, but it is preferably used as an electrical insulating sealant in electrical and electronic parts.
  • electric/electronic components include, but are not limited to, transformers such as transformer coils, choke coils and reactor coils, equipment control boards, sensors, and wireless communication components.
  • Electrical and electronic components resin-sealed using the polyurethane resin composition according to the present embodiment include, for example, electric washing machines, toilet seats, water heaters, water purifiers, baths, dishwashers, solar panels, power tools, and automobiles. , can be used for motorcycles, etc.
  • polyurethane resin composition will be described in detail below based on Examples and Comparative Examples, but the present invention is not limited thereto.
  • Polybutadiene polyol 1 number average molecular weight 2800, hydroxyl value 47 mgKOH / g, functional group number 2.3, product name: Poly bd R-45HTLO, manufactured by Clay Valley ⁇
  • Polybutadiene polyol 2 number average molecular weight 1600, hydroxyl value 80 mgKOH / g
  • Azeotropic mixture 105 containing 150 parts by mass of 1,3-butadiene, 88% by mass of isopropanol and 12% by mass of water in a stirred reactor in which the system is purged with nitrogen, with a functional group number of 2.3.
  • Parts by mass and 30 parts by mass of a 60% aqueous hydrogen peroxide solution were charged.
  • the contents of the reactor were heated to 120° C. with continuous stirring and maintained at 120° C. to 130° C. with stirring for 2 hours to carry out the polymerization reaction.
  • the reactor contents are cooled, the reaction product is removed from the reactor, unreacted monomer is removed from the reaction product, and the product is washed with water to remove residual isopropanol and unreacted hydrogen peroxide. removed.
  • This product was vacuum dried to obtain a polybutadiene polyol having a viscosity of 5000 mPa ⁇ s at 25°C.
  • BO-based polyol 1 Polybutylene glycol obtained by addition polymerization of butylene oxide using propylene glycol as an initiator according to Synthesis Example 1 below (number average molecular weight: 3000, number of functional groups: 2, butylene oxide units among all alkylene oxide units amount of 100 mol%)
  • Synthesis Example 1 2.53 parts by mass of propylene glycol, 0.55 parts by mass of 48% KOH and 10.8 parts by mass of 1,2-butylene oxide (BO) were charged into a stainless steel autoclave, and after replacing with nitrogen, the pressure in the autoclave was reduced. and heated. After the BO introduction reaction was carried out at 120 ⁇ 5° C. and the maximum pressure of 0.2 MPa, the BO aging reaction was carried out at 120 ⁇ 5° C.
  • BO-based polyol 2 In Synthesis Example 1 above, the amount of BO added after the BO aging reaction in the first stage was set to 40 parts by mass, and the others were the same as in Synthesis Example 1, butylene oxide was added using propylene glycol as an initiator. Polybutylene glycol obtained by addition polymerization (number average molecular weight: 1600, number of functional groups: 2, amount of butylene oxide units in all alkylene oxide units: 100 mol%) BO-based polyol 3: In Synthesis Example 1 above, the amount of BO added after the BO ripening reaction in the first stage was set to 13.3 parts by mass, and the other methods were the same as in Synthesis Example 1, butylene glycol was used as an initiator.
  • Polybutylene glycol obtained by addition polymerization of oxide (number average molecular weight 800, number of functional groups 2, amount of butylene oxide units in all alkylene oxide units 100 mol%)
  • BO-based polyol 4 Polybutylene glycol obtained by addition polymerization of butylene oxide using propylene glycol as an initiator according to Synthesis Example 2 below (number average molecular weight: 400, number of functional groups: 2, butylene oxide units among all alkylene oxide units amount of 100 mol%)
  • Synthesis Example 2 19 parts by mass of propylene glycol, 0.83 parts by mass of 48% KOH and 81 parts by mass of 1,2-butylene oxide (BO) were charged into a stainless steel autoclave and replaced with nitrogen. bottom.
  • the BO introduction reaction was carried out at 120 ⁇ 5° C. and the maximum pressure of 0.2 MPa
  • the BO aging reaction was carried out at 120 ⁇ 5° C. for 240 minutes.
  • the pressure was reduced to 20 mmHg (2.7 kPa) at 100 ⁇ 5° C., followed by purification and filtration to obtain bifunctional polybutylene glycol.
  • BO-based polyol 5 According to Synthesis Example 3 below, butylene oxide was addition-polymerized using propylene glycol as an initiator, and ethylene oxide was added to the end of the polybutylene glycol with EO added (number average molecular weight: 1250, functional radix 2, amount of butylene oxide units in all alkylene oxide units: 57 mol%, amount of ethylene oxide units: 43 mol%)
  • Synthesis Example 3 6.08 parts by mass of propylene glycol, 0.55 parts by mass of 48% KOH, and 25.9 parts by mass of 1,2-butylene oxide (BO) were charged into a stainless steel autoclave, and after purging with nitrogen, the pressure in the autoclave was reduced. and heated.
  • the BO aging reaction was carried out at 120 ⁇ 5° C. for 240 minutes. Then, after cooling to 80°C, it was withdrawn, and the pressure was reduced to 10 mmHg or less at 90 to 110°C. After that, 38.0 parts by mass of BO was added, and after performing BO introduction reaction at 120 ⁇ 5° C. and maximum pressure of 0.4 MPa, BO aging reaction was performed at 120 ⁇ 5° C. for 360 minutes.
  • ethylene oxide ethylene oxide
  • 30.0 parts by mass of ethylene oxide (EO) was added, and an EO introduction reaction was performed at 120 ⁇ 5°C and a maximum pressure of 0.4 MPa, and then an EO aging reaction was performed at 120 ⁇ 5°C for 360 minutes. .
  • the pressure was reduced to 20 mmHg (2.7 kPa) at 100 ⁇ 5° C., followed by purification and filtration to obtain EO-terminated polybutylene glycol.
  • BO-based polyol 6 Polybutylene glycol obtained by addition polymerization of butylene oxide using glycerin as an initiator according to Synthesis Example 4 below (number average molecular weight of 1100, number of functional groups of 3, number of butylene oxide units in all alkylene oxide units amount 100 mol%)
  • Synthesis Example 4 To 8.37 parts by mass of glycerin, 0.5 parts by mass of 48% KOH and 28.1 parts by mass of 1,2-butylene oxide (BO) were charged into a stainless steel autoclave, and after purging with nitrogen, the pressure in the autoclave was reduced. , raised the temperature. After the BO introduction reaction was carried out at 120 ⁇ 5° C.
  • the BO aging reaction was carried out at 120 ⁇ 5° C. for 240 minutes. After cooling to 80°C, the pressure was reduced to 10 mmHg or less at 90 to 110°C. After that, 63.62 parts by mass of BO was added, and after performing BO introduction reaction at 120 ⁇ 5° C. and maximum pressure of 0.4 MPa, BO aging reaction was performed at 120 ⁇ 5° C. for 360 minutes. After cooling, the pressure was reduced to 20 mmHg (2.7 kPa) at 100 ⁇ 5° C., followed by purification and filtration to obtain trifunctional polybutylene glycol.
  • - BO-based polyol 7 According to Synthesis Example 5 below, butylene oxide is addition-polymerized using glycerin as an initiator, and ethylene oxide is added to the end of the polybutylene glycol (number average molecular weight: 1,120, number of functional groups 3, the amount of butylene oxide units in all alkylene oxide units is 84 mol%, and the amount of ethylene oxide units is 16 mol%)
  • Synthesis Example 5 In Synthesis Example 4 above, 55.24 parts by mass of BO was added in the second-stage BO aging reaction, 10.2 parts by mass of ethylene oxide (EO) was added, and the temperature was adjusted to 120°C ⁇ 5°C and the maximum pressure of 0.
  • EO ethylene oxide
  • EO aging reaction was performed at 120 ⁇ 5° C. for 360 minutes. After cooling without EO, the pressure was reduced to 20 mmHg (2.7 kPa) at 100 ⁇ 5° C., followed by purification and filtration to obtain trifunctional EO-terminated polybutylene glycol.
  • ⁇ PO polyol 1 number average molecular weight 700, functional group 2 polypropylene glycol, product name: Hiflex D-700, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.
  • PO polyol 2 number average molecular weight 1000, functional group 2 Polypropylene glycol, product name: Hiflex D-1000, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.
  • PO-based polyol 3 polyoxyethylene polyoxypropylene glycol with a number average molecular weight of 1,300 and a number of functional groups of 2, product name: Epan 410, No. Ichi Kogyo Seiyaku Co., Ltd.
  • PO polyol 4 number average molecular weight 1000, functional group 3 polypropylene glycol, product name: X-2116, Daiichi Kogyo Seiyaku Co., Ltd.
  • PO polyol 5 number average molecular weight 3000 , Polypropylene glycol with a functional number of 3, Product name: Hiflex G-3000, Daiichi Kogyo Seiyaku Co., Ltd.
  • Castor oil-based polyol Number average molecular weight 938, Functional group number 2.7, Product name: Castor oil D, Ito oil ( Co., Ltd. [catalyst] ⁇ Catalyst: dioctyl tin, product name: Neostan U-810, manufactured by Nitto Kasei Co., Ltd.
  • the defoamed polyurethane resin composition was poured into a mold of 5 cm long ⁇ 5 cm wide ⁇ 1 cm high and cured in a curing furnace at 80° C. for 48 hours to prepare resin pieces.
  • the resin piece was treated in a high temperature and high humidity bath at a temperature of 121 ° C., a humidity of 100%, and a humidity of 2 atm, and after 500 hours and 1000 hours, the hardness was measured with a type A durometer in accordance with JIS K6253-3. The change from 0.01 to 0.000 was confirmed and evaluated according to the following criteria.
  • a resin piece having the same durability as described above was prepared, and the resin piece was treated in a high-temperature and high-humidity bath at a temperature of 121 ° C., a humidity of 100%, and 2 atm.
  • the specific resistance was measured according to JIS K6911 (measured voltage: 500 V) and evaluated according to the following criteria.
  • a JIS type 2 comb-shaped electrode substrate was placed on a glass petri dish, and an anode and a cathode were wired.
  • the defoamed polyurethane resin composition was poured onto the mold and cured in a curing oven at 80° C. for 48 hours to prepare a test piece.
  • the test piece was subjected to a migration test by applying a voltage of 100 V in a moist heat bath at a temperature of 85° C. and a humidity of 85%, and whether or not the current was applied within 1000 hours was evaluated according to the following criteria. As the amount of water around the electrode increases, copper ions are eluted from the anode, migrate to the cathode, and deposit on the cathode side. If the deposit grows, it causes insulation failure, and finally short-circuits between wiring patterns. This is a test of whether or not such a short circuit occurs.
  • Comparative Examples 1 to 5 using PO-based polyols 1 to 5 as polyols used in combination with polybutadiene polyol were excellent in durability (hardness change) after wet heat treatment, but the volume resistivity after wet heat treatment was excellent. The deterioration was large, the migration property was poor, and the wet heat resistance was poor.
  • Comparative Example 6 in which a castor oil-based polyol was used as the polyol used in combination with the polybutadiene polyol, the migration properties after the wet heat treatment were excellent, but the durability (hardness change) after the wet heat treatment was poor, and the volume resistivity was poor. also showed a downward trend. Moreover, when a castor oil-based polyol was used, curability was also inferior.
  • Examples 1 to 10 in which polybutadiene polyol and BO-based polyol were used in combination were excellent in durability (hardness change), volume resistivity and migration properties after wet heat treatment, and were superior to Comparative Examples 1 to 6. It was excellent in heat and humidity resistance.

Abstract

Provided is a polyurethane resin composition having excellent resistance to wet heat. A polyurethane resin composition according to one embodiment contains a hydroxyl group-containing compound (A) and an isocyanate group-containing compound (B). The hydroxyl group-containing compound (A) includes a polybutadiene polyol (A1) and a butylene oxide-based polyol (A2) in which 50 mol% or more of alkylene oxide units are butylene oxide units. The number average molecular weight of the butylene oxide-based polyol (A2) is 400-3000 inclusive.

Description

ポリウレタン樹脂組成物Polyurethane resin composition
　本発明の実施形態は、ポリウレタン樹脂組成物に関する。 An embodiment of the present invention relates to a polyurethane resin composition.
　従来、例えば、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, for example, electronic circuit boards and electronic components are sealed using a polyurethane resin composition in order to protect them from external factors, and polybutadiene polyol can be used as the polyol of the polyurethane resin composition. Are known.
　例えば、特許文献１には、水酸基含有化合物、イソシアネート基含有化合物、金属水酸化物および可塑剤を含有するポリウレタン樹脂組成物であって、前記水酸基含有化合物がポリブタジエンポリオールおよびひまし油系ポリオールを含有し、前記金属水酸化物が水酸化アルミニウムおよび／または水酸化マグネシウムである、ポリウレタン樹脂組成物が開示されている。 For example, Patent Document 1 discloses a polyurethane resin composition containing a hydroxyl group-containing compound, an isocyanate group-containing compound, a metal hydroxide and a plasticizer, wherein the hydroxyl group-containing compound contains polybutadiene polyol and castor oil-based polyol, A polyurethane resin composition is disclosed wherein the metal hydroxide is aluminum hydroxide and/or magnesium hydroxide.
特開２０１６－２０４３９公報Japanese Patent Application Laid-Open No. 2016-20439
　電気電子部品においては、その長寿命化に伴い、長期にわたって湿熱下で使用されることから、優れた耐湿熱性が求められており、例えば電気絶縁用の封止剤として用いられるポリウレタン樹脂組成物にも更なる耐湿熱性の向上が望まれる。 In electrical and electronic parts, as they are used for a long time under moist heat, along with the extension of their life, excellent moist heat resistance is required. For example, polyurethane resin compositions used as sealants for electrical insulation are required. Further improvement in wet heat resistance is desired.
　本発明の実施形態は、耐湿熱性に優れるポリウレタン樹脂組成物を提供することを目的とする。 An object of the embodiments of the present invention is to provide a polyurethane resin composition that is excellent in heat and humidity resistance.
　本発明は以下に示される実施形態を含む。
［１］　水酸基含有化合物（Ａ）およびイソシアネート基含有化合物（Ｂ）を含むポリウレタン樹脂組成物であって、前記水酸基含有化合物（Ａ）が、ポリブタジエンポリオール（Ａ１）と、アルキレンオキシド単位の５０モル％以上がブチレンオキシド単位であるブチレンオキシド系ポリオール（Ａ２）とを含み、前記ブチレンオキシド系ポリオール（Ａ２）の数平均分子量が４００以上３０００以下である、ポリウレタン樹脂組成物。
［２］　前記水酸基含有化合物（Ａ）１００質量％における前記ブチレンオキシド系ポリオール（Ａ２）の含有量が１０質量％以上８０質量％以下である、［１］に記載のポリウレタン樹脂組成物。
［３］　前記ブチレンオキシド系ポリオール（Ａ２）の数平均分子量が６００以上１６００以下であり、前記水酸基含有化合物（Ａ）１００質量％における前記ブチレンオキシド系ポリオール（Ａ２）の含有量が２０質量％以上６０質量％以下である、［１］または［２］に記載のポリウレタン樹脂組成物。
［４］　前記イソシアネート基含有化合物（Ｂ）がイソシアヌレート変性体を含む、［１］～［３］のいずれか１項に記載のポリウレタン樹脂組成物。
［５］　前記水酸基含有化合物（Ａ）を含む第１液と、前記イソシアネート基含有化合物（Ｂ）を含む第２液と、を含む二液型である、［１］～［４］のいずれか１項に記載のポリウレタン樹脂組成物。
［６］　電気絶縁用封止剤として用いられる［１］～［５］のいずれか１項に記載のポリ
ウレタン樹脂組成物。 The present invention includes embodiments shown below.
[1] A polyurethane resin composition containing a hydroxyl group-containing compound (A) and an isocyanate group-containing compound (B), wherein the hydroxyl group-containing compound (A) is a polybutadiene polyol (A1) and 50 mol% of alkylene oxide units A polyurethane resin composition comprising a butylene oxide-based polyol (A2) in which the above is a butylene oxide unit, and wherein the butylene oxide-based polyol (A2) has a number average molecular weight of 400 or more and 3,000 or less.
[2] The polyurethane resin composition according to [1], wherein the content of the butylene oxide-based polyol (A2) in 100% by mass of the hydroxyl group-containing compound (A) is 10% by mass or more and 80% by mass or less.
[3] The butylene oxide-based polyol (A2) has a number average molecular weight of 600 or more and 1600 or less, and the content of the butylene oxide-based polyol (A2) in 100% by mass of the hydroxyl group-containing compound (A) is 20% by mass or more. The polyurethane resin composition according to [1] or [2], which is 60% by mass or less.
[4] The polyurethane resin composition according to any one of [1] to [3], wherein the isocyanate group-containing compound (B) contains an isocyanurate modified product.
[5] Any one of [1] to [4], which is a two-pack type containing a first liquid containing the hydroxyl group-containing compound (A) and a second liquid containing the isocyanate group-containing compound (B). 2. The polyurethane resin composition according to item 1.
[6] The polyurethane resin composition according to any one of [1] to [5], which is used as an electrical insulating sealant.
　本発明の実施形態によれば、耐湿熱性に優れる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 polyurethane resin composition with excellent resistance to moist heat.
　本実施形態に係るポリウレタン樹脂組成物は、水酸基含有化合物（Ａ）と、イソシアネート基含有化合物（Ｂ）と、を含有する。 The polyurethane resin composition according to this embodiment contains a hydroxyl group-containing compound (A) and an isocyanate group-containing compound (B).
　［水酸基含有化合物（Ａ）］
　水酸基含有化合物（Ａ）としては、１分子中に２つ以上の水酸基を有するポリオール化合物を用いることができ、本実施形態では、水酸基含有化合物（Ａ）は、ポリブタジエンポリオール（Ａ１）とブチレンオキシド系ポリオール（Ａ２）とを含む。 [Hydroxyl group-containing compound (A)]
As the hydroxyl group-containing compound (A), a polyol compound having two or more hydroxyl groups in one molecule can be used. In the present embodiment, the hydroxyl group-containing compound (A) is a polybutadiene polyol (A1) and a butylene oxide and a polyol (A2).
　ポリブタジエンポリオール（Ａ１）としては、特に限定されず、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つの水酸基を有するものが好ましい。より好ましくは、ポリブタジエン構造の両末端にそれぞれ水酸基を有するものである。ポリブタジエンポリオール（Ａ１）としては、その不飽和二重結合の一部または全てが水添された水添ポリブタジエンポリオールでもよく、未水添のものと水添されたものを併用してもよい。また、分子量や官能基数の異なるポリブタジエンポリオールを２種以上併用してもよい。 The polybutadiene polyol (A1) is not particularly limited, and preferably has a 1,4-bonded type, 1,2-bonded type, or a mixture of these polybutadiene structures and at least two hydroxyl groups in the molecule. More preferably, both ends of the polybutadiene structure have hydroxyl groups. The polybutadiene polyol (A1) may be a hydrogenated polybutadiene polyol in which some or all of its unsaturated double bonds are hydrogenated, or a combination of non-hydrogenated and hydrogenated polybutadiene polyols. Moreover, two or more polybutadiene polyols having different molecular weights and functional group numbers may be used in combination.
　ポリブタジエンポリオール（Ａ１）の分子量は特に限定されず、例えば、数平均分子量（Ｍｎ）が６００～１５０００でもよく、８００～９０００でもよく、１０００～７０００でもよく、１３００～５０００でもよく、１４００～３０００でもよい。 The molecular weight of the polybutadiene polyol (A1) is not particularly limited. good.
　ポリブタジエンポリオール（Ａ１）の官能基数は特に限定されず、例えば２．０～４．０でもよく、２．０～２．５でもよい。 The number of functional groups of polybutadiene polyol (A1) is not particularly limited, and may be, for example, 2.0 to 4.0 or 2.0 to 2.5.
　ポリブタジエンポリオール（Ａ１）の水酸基価は特に限定されず、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 polybutadiene polyol (A1) is not particularly limited, and 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.
　本明細書において、ポリブタジエンポリオール（Ａ１）の数平均分子量（Ｍｎ）は、ＧＰＣ法（ゲルパーミエーションクロマトグラフィー法）により測定し、標準ポリスチレンによる検量線を用いて算出した値である。ＧＰＣの条件は、例えば、カラム：東ソー（株）製「ＴＳＫｇｅｌ　ＧＭＨＨＲ－Ｈ」、溶媒：ＴＨＦ、流速：０．６ｍＬ／分、測定温度：４０℃である。ポリブタジエンポリオール（Ａ１）の水酸基価はＪＩＳ　Ｋ１５５７－１：２００７のＡ法に準じて測定される値であり、ポリオール１ｇ中の水酸基（ＯＨ基）をアセチル化する酢酸と反応する、水酸化カリウム（ＫＯＨ）のｍｇ数である。ポリブタジエンポリオール（Ａ１）の官能基数は、下記式により算出される値である。 In this specification, the number average molecular weight (Mn) of polybutadiene polyol (A1) is a value measured by the GPC method (gel permeation chromatography method) and calculated using a standard polystyrene calibration curve. GPC conditions are, for example, column: "TSKgel GMHHR-H" manufactured by Tosoh Corporation, solvent: THF, flow rate: 0.6 mL/min, measurement temperature: 40°C. The hydroxyl value of polybutadiene polyol (A1) is a value measured according to A method of JIS K1557-1:2007. Potassium hydroxide ( KOH) in mg. The number of functional groups of polybutadiene polyol (A1) is a value calculated by the following formula.
　官能基数＝｛（水酸基価）×（Ｍｎ）｝／（５６．１×１０００）
　ポリブタジエンポリオール（Ａ１）の含有量は特に限定されないが、水酸基含有化合物（Ａ）１００質量％に対して、２０～９０質量％であることが好ましく、より好ましくは４０～８０質量％であり、さらに好ましくは５０～８０質量％である。 Number of functional groups = {(hydroxyl value) x (Mn)}/(56.1 x 1000)
The content of the polybutadiene polyol (A1) is not particularly limited, but is preferably 20 to 90% by mass, more preferably 40 to 80% by mass, based on 100% by mass of the hydroxyl group-containing compound (A). It is preferably 50 to 80% by mass.
　ブチレンオキシド系ポリオール（Ａ２）は、アルキレンオキシド単位の５０モル％以上
がブチレンオキシド単位であるポリオールである。より詳細には、ブチレンオキシド系ポリオール（Ａ２）は、当該ポリオールを形成するのに使用される全アルキレンオキシドの５０モル％以上がブチレンオキシドであるポリアルキレングリコールであり、広義のポリブチレングリコールである。水酸基含有化合物（Ａ）として、かかるブチレンオキシド系ポリオール（Ａ２）を上記ポリブタジエンポリオール（Ａ１）とともに併用することにより、ポリウレタン樹脂組成物の耐湿熱性を向上することができる。また、ひまし油系ポリオールを用いた場合に比べて、ポリウレタン樹脂組成物の製造時の混合粘度を低くして作業性を向上することができる。 The butylene oxide-based polyol (A2) is a polyol in which 50 mol % or more of the alkylene oxide units are butylene oxide units. More specifically, the butylene oxide-based polyol (A2) is a polyalkylene glycol in which 50 mol% or more of the total alkylene oxide used to form the polyol is butylene oxide, and is a broadly defined polybutylene glycol. . By using the butylene oxide polyol (A2) together with the polybutadiene polyol (A1) as the hydroxyl group-containing compound (A), the moist heat resistance of the polyurethane resin composition can be improved. In addition, compared to the case of using a castor oil-based polyol, it is possible to lower the mixed viscosity during the production of the polyurethane resin composition, thereby improving the workability.
　ブチレンオキシド系ポリオール（Ａ２）において、全アルキレンオキシド単位に対するブチレンオキシド単位の量は、耐湿熱性およびポリブタジエンポリオール（Ａ１）との相溶性の観点から、６０モル％以上であることが好ましく、より好ましくは７０モル％以上であり、８０モル％以上でもよく、９０モル％以上でもよく、１００モル％でもよい。ブチレンオキシド単位以外のアルキレンオキシド単位を有する場合、当該他のアルキレンオキシド単位としては、特に限定されず、例えばエチレンオキシド単位および／またはプロピレンオキシド単位が挙げられる。 In the butylene oxide-based polyol (A2), the amount of butylene oxide units relative to all alkylene oxide units is preferably 60 mol% or more, more preferably 60 mol% or more, from the viewpoint of wet heat resistance and compatibility with the polybutadiene polyol (A1). It may be 70 mol % or more, may be 80 mol % or more, may be 90 mol % or more, or may be 100 mol %. When having alkylene oxide units other than butylene oxide units, the other alkylene oxide units are not particularly limited, and examples include ethylene oxide units and/or propylene oxide units.
　好ましい一実施形態において、ブチレンオキシド系ポリオール（Ａ２）は、アルキレンオキシド単位が１００モル％のブチレンオキシド単位からなるポリブチレングリコールでもよい。 In a preferred embodiment, the butylene oxide-based polyol (A2) may be a polybutylene glycol composed of 100 mol% of alkylene oxide units and of butylene oxide units.
　本実施形態では、ブチレンオキシド系ポリオール（Ａ２）として、数平均分子量（Ｍｎ）が４００～３０００のものを用いる。ブチレンオキシド系ポリオール（Ａ２）の数平均分子量が４００以上であることにより、ポリブタジエンポリオール（Ａ１）との相溶性を向上することができる。また、３０００以下であることにより、ポリウレタン樹脂組成物の硬化性を向上することができる。ブチレンオキシド系ポリオール（Ａ２）の数平均分子量は６００以上であることが好ましく、より好ましくは８００以上である。該数平均分子量は、２０００以下であることが好ましく、より好ましくは１６００以下であり、１３００以下でもよい。 In this embodiment, a butylene oxide-based polyol (A2) having a number average molecular weight (Mn) of 400 to 3000 is used. When the butylene oxide polyol (A2) has a number average molecular weight of 400 or more, compatibility with the polybutadiene polyol (A1) can be improved. Moreover, when it is 3000 or less, the curability of the polyurethane resin composition can be improved. The butylene oxide polyol (A2) preferably has a number average molecular weight of 600 or more, more preferably 800 or more. The number average molecular weight is preferably 2000 or less, more preferably 1600 or less, and may be 1300 or less.
　ブチレンオキシド系ポリオール（Ａ２）の水酸基価は特に限定されず、例えば３７～５００ｍｇＫＯＨ／ｇでもよく、５０～３００ｍｇＫＯＨ／ｇでもよく、６０～２００ｍｇＫＯＨ／ｇでもよい。 The hydroxyl value of the butylene oxide-based polyol (A2) is not particularly limited, and may be, for example, 37-500 mgKOH/g, 50-300 mgKOH/g, or 60-200 mgKOH/g.
　本明細書において、ブチレンオキシド系ポリオール（Ａ２）の数平均分子量（Ｍｎ）は、下記式により、水酸基価と官能基数から換算される値である。 In this specification, the number average molecular weight (Mn) of the butylene oxide-based polyol (A2) is a value converted from the hydroxyl value and the number of functional groups according to the following formula.
　数平均分子量＝５６．１×１０００×官能基数／水酸基価
　ブチレンオキシド系ポリオール（Ａ２）の水酸基価は、ＪＩＳ　Ｋ１５５７－１：２００７のＡ法に準じて測定される値（ｍｇＫＯＨ／ｇ）である。ブチレンオキシド系ポリオール（Ａ２）の官能基数は、下記のように開始剤としての活性水素原子含有化合物における活性水素の数から求められる。 Number average molecular weight = 56.1 × 1000 × number of functional groups / hydroxyl value The hydroxyl value of the butylene oxide polyol (A2) is a value (mgKOH/g) measured according to A method of JIS K1557-1:2007. . The number of functional groups of the butylene oxide-based polyol (A2) is obtained from the number of active hydrogen atoms in the active hydrogen atom-containing compound as an initiator as described below.
　ブチレンオキシド系ポリオール（Ａ２）の構造は特に限定されず、例えば、２～８個の活性水素原子を有する化合物を開始剤として、これにブチレンオキシドを含むアルキレンオキシドを付加重合させた構造を有してもよい。ブチレンオキシドとしては、１，２－ブチレンオキシドおよび／または２，３－ブチレンオキシドが用いられるが、好ましくは１，２－ブチレンオキシドである。 The structure of the butylene oxide-based polyol (A2) is not particularly limited. For example, it has a structure obtained by addition polymerization of an alkylene oxide containing butylene oxide to a compound having 2 to 8 active hydrogen atoms as an initiator. may As the butylene oxide, 1,2-butylene oxide and/or 2,3-butylene oxide are used, preferably 1,2-butylene oxide.
　上記開始剤として、例えばエチレングリコールやプロピレングリコールなどの２個の活
性水素原子を持つ化合物（ジオール）を用いれば、２官能のブチレンオキシド系ポリオール（Ａ２）が得られる。また、開始剤として、例えばグリセリンやトリメチロールプロパンなどの３個の活性水素原子を持つ化合物（トリオール）を用いれば、３官能のブチレンオキシド系ポリオール（Ａ２）が得られる。３官能の方が２官能よりも硬化が速くなると考えられるため、より速い硬化が求められる場合、３官能のブチレンオキシド系ポリオール（Ａ２）を使用してもよい。ブチレンオキシド系ポリオール（Ａ２）の官能基数は特に限定されず、２～８でもよく、２～４でもよい。好ましくは、ブチレンオキシド系ポリオール（Ａ２）は、２官能または３官能であり、２官能のものと３官能のものを併用してもよい。 If a compound (diol) having two active hydrogen atoms such as ethylene glycol or propylene glycol is used as the initiator, a bifunctional butylene oxide polyol (A2) can be obtained. If a compound (triol) having three active hydrogen atoms such as glycerin or trimethylolpropane is used as the initiator, a trifunctional butylene oxide polyol (A2) can be obtained. Since it is believed that tri-functionality cures faster than di-functionality, a tri-functional butylene oxide polyol (A2) may be used when faster curing is desired. The number of functional groups of the butylene oxide-based polyol (A2) is not particularly limited, and may be 2-8 or 2-4. Preferably, the butylene oxide-based polyol (A2) is bifunctional or trifunctional, and a combination of bifunctional and trifunctional may be used.
　また、上記付加重合の形態として、ブチレンオキシドとともに他のアルキレンオキシドを共重合させる場合、ランダム共重合でもよく、ブロック共重合でもよい。一実施形態において、開始剤にブチレンオキシドを付加重合させた後、当該ポリブチレンオキシド鎖の末端にエチレンオキシドを付加させた構造を持つ、末端エチレンオキシド付加ポリブチレングリコールを用いてもよい。末端にエチレンオキシドを付加させることにより、硬化性を高めることができる。 In addition, as the form of the addition polymerization, when butylene oxide is copolymerized with other alkylene oxide, random copolymerization or block copolymerization may be used. In one embodiment, a terminal ethylene oxide-added polybutylene glycol having a structure in which butylene oxide is added to an initiator and then ethylene oxide is added to the end of the polybutylene oxide chain may be used. Curability can be enhanced by adding ethylene oxide to the terminal.
　なお、ブチレンオキシド系ポリオール（Ａ２）としては、上記の構成を持つものをいずれか１種用いてもよく、また、数平均分子量や構造等が異なる２種以上のものを併用してもよい。 As the butylene oxide-based polyol (A2), any one of those having the above structure may be used, or two or more of those having different number average molecular weights, structures, etc. may be used in combination.
　ブチレンオキシド系ポリオール（Ａ２）の含有量は特に限定されないが、水酸基含有化合物（Ａ）１００質量％に対して、１０～８０質量％であることが好ましい。ブチレンオキシド系ポリオール（Ａ２）の含有量が１０質量％以上であることにより、ポリウレタン樹脂組成物の製造時の混合粘度を低くすることができる。また該含有量が８０質量％以下であることにより、硬化性を向上することができる。ブチレンオキシド系ポリオール（Ａ２）の含有量は、より好ましくは２０～６０質量％であり、さらに好ましくは２０～５０質量％である。 Although the content of the butylene oxide-based polyol (A2) is not particularly limited, it is preferably 10 to 80% by mass with respect to 100% by mass of the hydroxyl group-containing compound (A). When the content of the butylene oxide-based polyol (A2) is 10% by mass or more, the mixed viscosity during production of the polyurethane resin composition can be lowered. Further, when the content is 80% by mass or less, the curability can be improved. The content of the butylene oxide-based polyol (A2) is more preferably 20 to 60% by mass, still more preferably 20 to 50% by mass.
　ポリブタジエンポリオール（Ａ１）とブチレンオキシド系ポリオール（Ａ２）との質量比は特に限定されないが、（Ａ２）／（Ａ１）が０．１～３．５であることが好ましく、より好ましくは０．２～１．０である。 The mass ratio of the polybutadiene polyol (A1) and the butylene oxide polyol (A2) is not particularly limited, but (A2)/(A1) is preferably 0.1 to 3.5, more preferably 0.2. ~1.0.
　本実施形態において、水酸基含有化合物（Ａ）は、ポリブタジエンポリオール（Ａ１）とブチレンオキシド系ポリオール（Ａ２）のみで構成されてもよいが、他の水酸基含有化合物を含んでもよい。水酸基含有化合物（Ａ）１００質量％に対するポリブタジエンポリオール（Ａ１）とブチレンオキシド系ポリオール（Ａ２）との合計量（Ａ１＋Ａ２）は特に限定されないが、７０質量％以上であることが好ましく、より好ましくは８０質量％以上であり、さらに好ましくは９０質量％以上であり、１００質量％でもよい。 In the present embodiment, the hydroxyl group-containing compound (A) may consist only of the polybutadiene polyol (A1) and the butylene oxide-based polyol (A2), but may also contain other hydroxyl group-containing compounds. Although the total amount (A1+A2) of the polybutadiene polyol (A1) and the butylene oxide polyol (A2) relative to 100% by mass of the hydroxyl group-containing compound (A) is not particularly limited, it is preferably 70% by mass or more, more preferably 80% by mass. It is at least 90% by mass, more preferably at least 90% by mass, and may be 100% by mass.
　上記他の水酸基含有化合物としては、各種ポリオールが用いられ、特に限定されない。例えば、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ヒマシ油系ポリオールが挙げられる。また、その他のポリエステルポリオール、ポリエーテルポリオール、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などが挙げられる。さらに、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でもよく、具体的には、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、エチレングリコール、１，４－ブタンジオール、オクタンジオール、トリメチロールプロパン、トリイソプロパノールアミン等の脂肪
族アルコールが挙げられる。 Various polyols are used as the other hydroxyl group-containing compound, and there is no particular limitation. Examples thereof include castor oil, castor oil fatty acids, hydrogenated castor oils obtained by hydrogenating these, and castor oil-based polyols produced using hydrogenated castor oil fatty acids. Further, other polyester polyols, polyether polyols, polycarbonate polyols, dimer acid polyols, polycaprolactone polyols, acrylic polyols, polyisoprene polyols, and the like are included. Furthermore, low-molecular-weight polyols that are commonly used as cross-linking agents may be used. Specifically, N,N-bis(2-hydroxypropyl)aniline, hydroquinone-bis(β-hydroxyethyl)ether, resorcinol-bis(β -hydroxyethyl) ether, and aliphatic alcohols such as ethylene glycol, 1,4-butanediol, octanediol, trimethylolpropane, and triisopropanolamine.
　［イソシアネート基含有化合物（Ｂ）］
　イソシアネート基含有化合物（Ｂ）としては、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。イソシアネート基含有化合物（Ｂ）としては、例えば、脂肪族ポリイソシアネート化合物（Ｂ１）、脂環式ポリイソシアネート化合物（Ｂ２）、および芳香族ポリイソシアネート化合物（Ｂ３）、ならびにこれらの変性体および多核体が挙げられ、いずれか１種用いても２種以上併用してもよい。 [Isocyanate group-containing compound (B)]
Various polyisocyanate compounds having two or more isocyanate groups in one molecule can be used as the isocyanate group-containing compound (B). Examples of the isocyanate group-containing compound (B) include an aliphatic polyisocyanate compound (B1), an alicyclic polyisocyanate compound (B2), an aromatic polyisocyanate compound (B3), and modified and polynuclear compounds thereof. Any one of them may be used, or two or more may be used in combination.
　脂肪族ポリイソシアネート化合物（Ｂ１）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－ジイソシアネートなどが挙げられる。 Examples of the aliphatic polyisocyanate compound (B1) include tetramethylene diisocyanate, dodecamethylene diisocyanate, hexamethylene diisocyanate (HDI), 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, 2-methylpentane-1,5-diisocyanate, 3-methylpentane-1,5-diisocyanate and the like.
　脂環式ポリイソシアネート化合物（Ｂ２）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）シクロヘキサンなどが挙げられる。 Examples of the alicyclic polyisocyanate compound (B2) include isophorone diisocyanate (IPDI), hydrogenated xylylene diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, 1,4-cyclohexane diisocyanate, methylcyclohexylene diisocyanate, 1,3 -Bis(isocyanatomethyl)cyclohexane and the like.
　芳香族ポリイソシアネート化合物（Ｂ３）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などが挙げられる。 Examples of the aromatic polyisocyanate compound (B3) 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, etc. mentioned.
　これらのポリイソシアネート化合物（Ｂ１）～（Ｂ３）の変性体としては、例えば、イソシアヌレート変性体、アロファネート変性体、ビウレット変性体、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。 Modified products of these polyisocyanate compounds (B1) to (B3) include, for example, isocyanurate modified products, allophanate modified products, biuret modified products, adduct modified products, and carbodiimide modified products.
　一実施形態において、イソシアネート基含有化合物（Ｂ）は、イソシアヌレート変性体を含むことが好ましい。イソシアヌレート変性体を用いることにより、上記水酸基含有化合物（Ａ）との混合性に優れ、ポリウレタン樹脂組成物の硬化後における硬度の均一性を向上することができる。イソシアヌレート変性体としては、脂肪族ポリイソシアネート化合物（Ｂ１）のイソシアヌレート変性体、脂環式ポリイソシアネート化合物（Ｂ２）のイソシアヌレート変性体、芳香族ポリイソシアネート化合物（Ｂ３）のイソシアヌレート変性体が挙げられる。好ましくは脂肪族ポリイソシアネート化合物（Ｂ１）のイソシアヌレート変性体であり、より好ましくはＨＤＩイソシアヌレートである。 In one embodiment, the isocyanate group-containing compound (B) preferably contains an isocyanurate modified product. By using the modified isocyanurate, it has excellent miscibility with the hydroxyl group-containing compound (A), and can improve uniformity of hardness of the cured polyurethane resin composition. Examples of the isocyanurate modified product include an isocyanurate modified product of the aliphatic polyisocyanate compound (B1), an isocyanurate modified product of the alicyclic polyisocyanate compound (B2), and an isocyanurate modified product of the aromatic polyisocyanate compound (B3). mentioned. Preferred is the isocyanurate modified form of the aliphatic polyisocyanate compound (B1), and more preferred is HDI isocyanurate.
　他の一実施形態において、イソシアネート基含有化合物（Ｂ）は、ＨＤＩを含むことが好ましい。イソシアネート基含有化合物（Ｂ）としては、ＨＤＩと上記イソシアヌレート変性体を併用してもよく、ＨＤＩとＨＤＩイソシアヌレートを併用してもよい。 In another embodiment, the isocyanate group-containing compound (B) preferably contains HDI. As the isocyanate group-containing compound (B), HDI and the modified isocyanurate may be used in combination, or HDI and HDI isocyanurate may be used in combination.
　さらに他の一実施形態において、イソシアネート基含有化合物（Ｂ）は、ＭＤＩを含んでもよい。ＭＤＩとしてはモノメリックＭＤＩでもよく、ポリメリックＭＤＩ（クルードＭＤＩ）でもよい。イソシアネート基含有化合物（Ｂ）としては、ＭＤＩと、上記のＨＤ
Ｉおよび／またはイソシアヌレート変性体（好ましくはＨＤＩイソシアヌレート）を併用してもよい。 In yet another embodiment, the isocyanate group-containing compound (B) may contain MDI. MDI may be monomeric MDI or polymeric MDI (crude MDI). As the isocyanate group-containing compound (B), MDI and the above HD
I and/or modified isocyanurate (preferably HDI isocyanurate) may be used in combination.
　ポリウレタン樹脂組成物における、イソシアネート基含有化合物（Ｂ）の含有量は、特に限定されず、例えば、水酸基含有化合物（Ａ）１００質量部に対して、５～６０質量部でもよく、８～５０質量部でもよく、１０～４０質量部でもよく、１５～３０質量部でもよい。 The content of the isocyanate group-containing compound (B) in the polyurethane resin composition is not particularly limited. parts, 10 to 40 parts by mass, or 15 to 30 parts by mass.
　水酸基含有化合物（Ａ）とイソシアネート基含有化合物（Ｂ）との比は、特に限定されず、例えば、イソシアネート基含有化合物（Ｂ）の持つイソシアネート基と水酸基含有化合物（Ａ）の持つ水酸基とのモル比ＮＣＯ／ＯＨ（インデックス）が、０．６～１．５でもよく、０．７～１．３でもよく、０．８～１．２でもよい。 The ratio of the hydroxyl group-containing compound (A) and the isocyanate group-containing compound (B) is not particularly limited. The ratio NCO/OH (index) may be from 0.6 to 1.5, from 0.7 to 1.3, or from 0.8 to 1.2.
　［その他の成分］
　本実施形態に係るポリウレタン樹脂組成物には、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 polyurethane resin composition according to the present embodiment may optionally contain, for example, a catalyst, an antioxidant, a foam stabilizer, a diluent, a flame retardant, an ultraviolet absorber, a colorant, Various additives such as fillers and plasticizers 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。触媒の含有量は、特に限定されず、例えば、ポリウレタン樹脂組成物１００質量％に対して０．０００１～０．１質量％でよく、０．００１～０．０１質量％でもよい。 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. The content of the catalyst is not particularly limited, and may be, for example, 0.0001 to 0.1% by mass or 0.001 to 0.01% by mass with respect to 100% by mass of the polyurethane resin composition.
　［ポリウレタン樹脂組成物］
　本実施形態に係るポリウレタン樹脂組成物は、水酸基含有化合物（Ａ）を含む第１液と、イソシアネート基含有化合物（Ｂ）を含む第２液と、を含む二液型ポリウレタン樹脂組成物として構成されてもよい。かかる二液型ポリウレタン樹脂組成物は、第１液および第２液とともに、上記その他の成分を含む第３液をさらに備えてもよい。 [Polyurethane resin composition]
The polyurethane resin composition according to the present embodiment is configured as a two-component polyurethane resin composition containing a first liquid containing a hydroxyl group-containing compound (A) and a second liquid containing an isocyanate group-containing compound (B). may Such a two-pack type polyurethane resin composition may further comprise a third liquid containing the other components as well as the first and second liquids.
　該二液型ポリウレタン樹脂組成物は、第１液と第２液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液と第２液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液と第２液は、使用時に混合されることにより水酸基含有化合物（Ａ）とイソシアネート基含有化合物（Ｂ）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。本実施形態に係るポリウレタン樹脂組成物は、第１液と第２液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、硬化したものであってもよい。 The two-component polyurethane resin composition can be produced by preparing a first liquid and a second liquid, respectively, that is, the first liquid and the second liquid may be filled in separate containers. . The first liquid and the second liquid filled in separate containers are mixed at the time of use, whereby the hydroxyl group-containing compound (A) and the isocyanate group-containing compound (B) react to form a polyurethane resin, which is cured. good too. At that time, it may be cured by heating. The polyurethane resin composition according to this embodiment may be obtained by mixing the first liquid and the second liquid, may be in a liquid state before curing, or may be in a cured state.
　第１液は、水酸基含有化合物（Ａ）のみで構成されてもよく、また、水酸基含有化合物（Ａ）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が配合されてもよい。好ましくは、第１液は水酸基含有化合物（Ａ）および触媒を含むことである。 The first liquid may be composed only of the hydroxyl group-containing compound (A), and in addition to the hydroxyl group-containing compound (A), if necessary, for example, a catalyst, an antioxidant, a foam stabilizer, a diluent , flame retardants, ultraviolet absorbers, colorants, fillers, plasticizers, and other additives. Preferably, the first liquid contains a hydroxyl group-containing compound (A) and a catalyst.
　第２液は、イソシアネート基含有化合物（Ｂ）のみで構成されてもよく、また、イソシアネート基含有化合物（Ｂ）の他に、必要に応じて、例えば、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が配合されてもよい。 The second liquid may be composed only of the isocyanate group-containing compound (B), and in addition to the isocyanate group-containing compound (B), if necessary, for example, an antioxidant, a foam stabilizer, a diluent , flame retardants, ultraviolet absorbers, colorants, fillers, plasticizers, and other additives.
　［ポリウレタン樹脂組成物の用途］
　本実施形態に係る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
品における電気絶縁用封止剤として用いることが好ましい。電気電子部品としては、特に限定されないが、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。 [Applications of Polyurethane Resin Composition]
The use of the polyurethane resin composition according to the present embodiment is not particularly limited, but it is preferably used as an electrical insulating sealant in electrical and electronic parts. Examples of electric/electronic components include, but are not limited to, transformers such as transformer coils, choke coils and reactor coils, equipment control boards, sensors, and wireless communication components.
　本実施形態に係る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 polyurethane resin composition according to the present embodiment include, for example, electric washing machines, toilet seats, water heaters, water purifiers, baths, dishwashers, solar panels, power tools, and automobiles. , can be used for motorcycles, etc.
　以下、実施例及び比較例に基づいて、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 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する各成分の詳細を以下に示す。 Details of each component used in Examples and Comparative Examples are shown below.
　［水酸基含有化合物（Ａ）］
・ポリブタジエンポリオール１：数平均分子量２８００、水酸基価４７ｍｇＫＯＨ／ｇ、官能基数２．３、製品名：Ｐｏｌｙ　ｂｄ　Ｒ－４５ＨＴＬＯ、クレイバレー社製
・ポリブタジエンポリオール２：数平均分子量１６００、水酸基価８０ｍｇＫＯＨ／ｇ、官能基数２．３、下記製法による調製品
　窒素で系内を置換した攪拌反応器に１５０質量部の１，３－ブタジエン、イソプロパノール８８質量％と水１２質量％とを含有する共沸混合物１０５質量部、および６０％過酸化水素水溶液３０質量部を仕込んだ。その反応器の内容物を連続的に攪拌しながら１２０℃になるまで加熱し、攪拌しながら１２０℃から１３０℃に保ち２時間重合反応を行った。所定時間完了後、その反応器の内容物を冷却し、その反応生成物を反応器から取り出し、未反応モノマーを反応生成物から取り除き、その生成物を水洗して残留イソプロパノール及び未反応過酸化水素を除去した。この生成物を真空乾燥して、粘度が２５℃で５０００ｍＰａ・ｓのポリブタジエンポリオールを得た。
・ＢＯ系ポリオール１：下記合成例１に従い、プロピレングリコールを開始剤としてブチレンオキシドを付加重合して得られたポリブチレングリコール（数平均分子量３０００、官能基数２、全アルキレンオキシド単位中のブチレンオキシド単位の量１００モル％）
　合成例１：プロピレングリコール２．５３質量部に４８％ＫＯＨ０．５５質量部と１，２－ブチレンオキシド（ＢＯ）１０．８質量部をステンレス製オートクレーブに仕込み、窒素置換した後、釜内を減圧し、昇温した。そして、１２０℃±５℃および最高圧０．２ＭＰａにてＢＯ導入反応を行った後、１２０±５℃で２４０分間、ＢＯ熟成反応を行った。次いで、８０℃まで冷却後、９０～１１０℃で１０ｍｍＨｇ以下に減圧した。その後、ＢＯを８６．６７質量部追加し、１２０℃±５℃および最高圧０．４ＭＰａにてＢＯ導入反応を行った後、１２０±５℃で３６０分間、ＢＯ熟成反応を行った。冷却後、１００±５℃にて２０ｍｍＨｇ（２．７ｋＰａ）到達まで減圧し、次いで、精製・ろ過して、２官能のポリブチレングリコールを得た。
・ＢＯ系ポリオール２：上記合成例１において１段目のＢＯ熟成反応後に追加するＢＯの量を４０質量部とし、その他は合成例１と同様の方法に従い、プロピレングリコールを開始剤としてブチレンオキシドを付加重合して得られたポリブチレングリコール（数平均分子量１６００、官能基数２、全アルキレンオキシド単位中のブチレンオキシド単位の量１００モル％）
・ＢＯ系ポリオール３：上記合成例１において１段目のＢＯ熟成反応後に追加するＢＯの量を１３．３質量部とし、その他は合成例１と同様の方法に従い、プロピレングリコールを開始剤としてブチレンオキシドを付加重合して得られたポリブチレングリコール（数平均分子量８００、官能基数２、全アルキレンオキシド単位中のブチレンオキシド単位の量１００モル％）
・ＢＯ系ポリオール４：下記合成例２に従い、プロピレングリコールを開始剤としてブチ
レンオキシドを付加重合して得られたポリブチレングリコール（数平均分子量４００、官能基数２、全アルキレンオキシド単位中のブチレンオキシド単位の量１００モル％）
　合成例２：プロピレングリコール１９質量部に４８％ＫＯＨ０．８３質量部と１，２－ブチレンオキシド（ＢＯ）８１質量部をステンレス製オートクレーブに仕込み、窒素置換した後、釜内を減圧し、昇温した。そして、１２０℃±５℃および最高圧０．２ＭＰａにてＢＯ導入反応を行った後、１２０±５℃で２４０分間、ＢＯ熟成反応を行った。脱ＢＯ冷却後、１００±５℃にて２０ｍｍＨｇ（２．７ｋＰａ）到達まで減圧し、次いで、精製・ろ過して、２官能のポリブチレングリコールを得た。
・ＢＯ系ポリオール５：下記合成例３に従い、プロピレングリコールを開始剤としてブチレンオキシドを付加重合し、さらにその末端にエチレンオキシドを付加して得られた末端ＥＯ付加ポリブチレングリコール（数平均分子量１２５０、官能基数２、全アルキレンオキシド単位中のブチレンオキシド単位の量５７モル％、エチレンオキシド単位の量４３モル％）
　合成例３：プロピレングリコール６．０８質量部に４８％ＫＯＨ０．５５質量部と１，２－ブチレンオキシド（ＢＯ）２５．９質量部をステンレス製オートクレーブに仕込み、窒素置換した後、釜内を減圧し、昇温した。そして、１２０℃±５℃および最高圧０．２ＭＰａにてＢＯ導入反応を行った後、１２０±５℃で２４０分間、ＢＯ熟成反応を行った。次いで、８０℃まで冷却後、抜き取り、９０～１１０℃で１０ｍｍＨｇ以下に減圧した。その後、ＢＯを３８．０質量部追加し、１２０℃±５℃および最高圧０．４ＭＰａにてＢＯ導入反応を行った後、１２０±５℃で３６０分間、ＢＯ熟成反応を行った。その後、エチレンオキシド（ＥＯ）を３０．０質量部追加し、１２０℃±５℃および最高圧０．４ＭＰａにてＥＯ導入反応を行った後、１２０±５℃で３６０分間、ＥＯ熟成反応を行った。脱ＥＯ冷却後、１００±５℃にて２０ｍｍＨｇ（２．７ｋＰａ）到達まで減圧し、次いで、精製・ろ過して、ＥＯ末端付加ポリブチレングリコールを得た。
・ＢＯ系ポリオール６：下記合成例４に従い、グリセリンを開始剤としてブチレンオキシドを付加重合して得られたポリブチレングリコール（数平均分子量１１００、官能基数３、全アルキレンオキシド単位中のブチレンオキシド単位の量１００モル％）
　合成例４：グリセリン８．３７質量部に４８％ＫＯＨ０．５質量部と１，２－ブチレンオキシド（ＢＯ）２８．１質量部をステンレス製オートクレーブに仕込み、窒素置換した後、釜内を減圧し、昇温した。そして、１２０℃±５℃および最高圧０．２ＭＰａにてＢＯ導入反応を行った後、１２０±５℃で２４０分間、ＢＯ熟成反応を行った。次いで、８０℃まで冷却後、９０～１１０℃で１０ｍｍＨｇ以下に減圧した。その後、ＢＯを６３．６２質量部追加し、１２０℃±５℃および最高圧０．４ＭＰａにてＢＯ導入反応を行った後、１２０±５℃で３６０分間、ＢＯ熟成反応を行った。冷却後、１００±５℃にて２０ｍｍＨｇ（２．７ｋＰａ）到達まで減圧し、次いで、精製・ろ過して、３官能のポリブチレングリコールを得た。
・ＢＯ系ポリオール７：下記合成例５に従い、グリセリンを開始剤としてブチレンオキシドを付加重合し、さらにその末端にエチレンオキシドを付加して得られた末端ＥＯ付加ポリブチレングリコール（数平均分子量１１２０、官能基数３、全アルキレンオキシド単位中のブチレンオキシド単位の量８４モル％、エチレンオキシド単位の量１６モル％）
　合成例５：上記合成例４において、２段目のＢＯ熟成反応でＢＯを５５．２４質量部追加し、エチレンオキシド（ＥＯ）を１０．２質量部追加し、１２０℃±５℃および最高圧０．４ＭＰａにてＥＯ導入反応を行った後、１２０±５℃で３６０分間、ＥＯ熟成反応を行った。脱ＥＯ冷却後、１００±５℃にて２０ｍｍＨｇ（２．７ｋＰａ）到達まで減圧し、次いで、精製・ろ過して、３官能のＥＯ末端付加ポリブチレングリコールを得た。
・ＰＯ系ポリオール１：数平均分子量７００、官能基数２のポリプロピレングリコール、製品名：ハイフレックスＤ－７００、第一工業製薬（株）製
・ＰＯ系ポリオール２：数平均分子量１０００、官能基数２のポリプロピレングリコール、製品名：ハイフレックスＤ－１０００、第一工業製薬（株）製
・ＰＯ系ポリオール３：数平均分子量１３００、官能基数２のポリオキシエチレンポリオ
キシプロピレングリコール、製品名：エパン４１０、第一工業製薬（株）製
・ＰＯ系ポリオール４：数平均分子量１０００、官能基数３のポリプロピレングリコール、製品名：Ｘ－２１１６、第一工業製薬（株）製
・ＰＯ系ポリオール５：数平均分子量３０００、官能基数３のポリプロピレングリコール、製品名：ハイフレックスＧ－３０００、第一工業製薬（株）製
・ひまし油系ポリオール：数平均分子量９３８、官能基数２．７、製品名：ひまし油Ｄ、伊藤製油（株）製
　［触媒］
・触媒：ジオクチル錫、製品名：ネオスタンＵ－８１０、日東化成（株）製
　［イソシアネート基含有化合物（Ｂ）］
・ポリイソシアネート１：ＨＤＩイソシアヌレート、製品名：デュラネートＴＰＡ－１００、旭化成（株）製
・ポリイソシアネート２：ＨＤＩ、製品名：デュラネートＤ－２０１、旭化成（株）製
・ポリイソシアネート３：クルードＭＤＩ、製品名：ルプラネートＭ５Ｓ、ＢＡＳＦ　ＩＮＯＡＣ　ポリウレタン（株）製
　［実施例１～１０及び比較例１～６］
　下記表１および表２に示す配合（質量部）により、各実施例および各比較例の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液を所定量秤量し、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液（イソシアネート基含有化合物（Ｂ））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。 [Hydroxyl group-containing compound (A)]
· Polybutadiene polyol 1: number average molecular weight 2800, hydroxyl value 47 mgKOH / g, functional group number 2.3, product name: Poly bd R-45HTLO, manufactured by Clay Valley · Polybutadiene polyol 2: number average molecular weight 1600, hydroxyl value 80 mgKOH / g Azeotropic mixture 105 containing 150 parts by mass of 1,3-butadiene, 88% by mass of isopropanol and 12% by mass of water in a stirred reactor in which the system is purged with nitrogen, with a functional group number of 2.3. Parts by mass and 30 parts by mass of a 60% aqueous hydrogen peroxide solution were charged. The contents of the reactor were heated to 120° C. with continuous stirring and maintained at 120° C. to 130° C. with stirring for 2 hours to carry out the polymerization reaction. After the predetermined time period is complete, the reactor contents are cooled, the reaction product is removed from the reactor, unreacted monomer is removed from the reaction product, and the product is washed with water to remove residual isopropanol and unreacted hydrogen peroxide. removed. This product was vacuum dried to obtain a polybutadiene polyol having a viscosity of 5000 mPa·s at 25°C.
BO-based polyol 1: Polybutylene glycol obtained by addition polymerization of butylene oxide using propylene glycol as an initiator according to Synthesis Example 1 below (number average molecular weight: 3000, number of functional groups: 2, butylene oxide units among all alkylene oxide units amount of 100 mol%)
Synthesis Example 1: 2.53 parts by mass of propylene glycol, 0.55 parts by mass of 48% KOH and 10.8 parts by mass of 1,2-butylene oxide (BO) were charged into a stainless steel autoclave, and after replacing with nitrogen, the pressure in the autoclave was reduced. and heated. After the BO introduction reaction was carried out at 120±5° C. and the maximum pressure of 0.2 MPa, the BO aging reaction was carried out at 120±5° C. for 240 minutes. After cooling to 80°C, the pressure was reduced to 10 mmHg or less at 90 to 110°C. After that, 86.67 parts by mass of BO was added, and after performing BO introduction reaction at 120±5° C. and maximum pressure of 0.4 MPa, BO aging reaction was performed at 120±5° C. for 360 minutes. After cooling, the pressure was reduced to 20 mmHg (2.7 kPa) at 100±5° C., followed by purification and filtration to obtain bifunctional polybutylene glycol.
BO-based polyol 2: In Synthesis Example 1 above, the amount of BO added after the BO aging reaction in the first stage was set to 40 parts by mass, and the others were the same as in Synthesis Example 1, butylene oxide was added using propylene glycol as an initiator. Polybutylene glycol obtained by addition polymerization (number average molecular weight: 1600, number of functional groups: 2, amount of butylene oxide units in all alkylene oxide units: 100 mol%)
BO-based polyol 3: In Synthesis Example 1 above, the amount of BO added after the BO ripening reaction in the first stage was set to 13.3 parts by mass, and the other methods were the same as in Synthesis Example 1, butylene glycol was used as an initiator. Polybutylene glycol obtained by addition polymerization of oxide (number average molecular weight 800, number of functional groups 2, amount of butylene oxide units in all alkylene oxide units 100 mol%)
BO-based polyol 4: Polybutylene glycol obtained by addition polymerization of butylene oxide using propylene glycol as an initiator according to Synthesis Example 2 below (number average molecular weight: 400, number of functional groups: 2, butylene oxide units among all alkylene oxide units amount of 100 mol%)
Synthesis Example 2: 19 parts by mass of propylene glycol, 0.83 parts by mass of 48% KOH and 81 parts by mass of 1,2-butylene oxide (BO) were charged into a stainless steel autoclave and replaced with nitrogen. bottom. After the BO introduction reaction was carried out at 120±5° C. and the maximum pressure of 0.2 MPa, the BO aging reaction was carried out at 120±5° C. for 240 minutes. After cooling to remove BO, the pressure was reduced to 20 mmHg (2.7 kPa) at 100±5° C., followed by purification and filtration to obtain bifunctional polybutylene glycol.
BO-based polyol 5: According to Synthesis Example 3 below, butylene oxide was addition-polymerized using propylene glycol as an initiator, and ethylene oxide was added to the end of the polybutylene glycol with EO added (number average molecular weight: 1250, functional radix 2, amount of butylene oxide units in all alkylene oxide units: 57 mol%, amount of ethylene oxide units: 43 mol%)
Synthesis Example 3: 6.08 parts by mass of propylene glycol, 0.55 parts by mass of 48% KOH, and 25.9 parts by mass of 1,2-butylene oxide (BO) were charged into a stainless steel autoclave, and after purging with nitrogen, the pressure in the autoclave was reduced. and heated. After the BO introduction reaction was carried out at 120±5° C. and the maximum pressure of 0.2 MPa, the BO aging reaction was carried out at 120±5° C. for 240 minutes. Then, after cooling to 80°C, it was withdrawn, and the pressure was reduced to 10 mmHg or less at 90 to 110°C. After that, 38.0 parts by mass of BO was added, and after performing BO introduction reaction at 120±5° C. and maximum pressure of 0.4 MPa, BO aging reaction was performed at 120±5° C. for 360 minutes. After that, 30.0 parts by mass of ethylene oxide (EO) was added, and an EO introduction reaction was performed at 120 ± 5°C and a maximum pressure of 0.4 MPa, and then an EO aging reaction was performed at 120 ± 5°C for 360 minutes. . After cooling without EO, the pressure was reduced to 20 mmHg (2.7 kPa) at 100±5° C., followed by purification and filtration to obtain EO-terminated polybutylene glycol.
BO-based polyol 6: Polybutylene glycol obtained by addition polymerization of butylene oxide using glycerin as an initiator according to Synthesis Example 4 below (number average molecular weight of 1100, number of functional groups of 3, number of butylene oxide units in all alkylene oxide units amount 100 mol%)
Synthesis Example 4: To 8.37 parts by mass of glycerin, 0.5 parts by mass of 48% KOH and 28.1 parts by mass of 1,2-butylene oxide (BO) were charged into a stainless steel autoclave, and after purging with nitrogen, the pressure in the autoclave was reduced. , raised the temperature. After the BO introduction reaction was carried out at 120±5° C. and the maximum pressure of 0.2 MPa, the BO aging reaction was carried out at 120±5° C. for 240 minutes. After cooling to 80°C, the pressure was reduced to 10 mmHg or less at 90 to 110°C. After that, 63.62 parts by mass of BO was added, and after performing BO introduction reaction at 120±5° C. and maximum pressure of 0.4 MPa, BO aging reaction was performed at 120±5° C. for 360 minutes. After cooling, the pressure was reduced to 20 mmHg (2.7 kPa) at 100±5° C., followed by purification and filtration to obtain trifunctional polybutylene glycol.
- BO-based polyol 7: According to Synthesis Example 5 below, butylene oxide is addition-polymerized using glycerin as an initiator, and ethylene oxide is added to the end of the polybutylene glycol (number average molecular weight: 1,120, number of functional groups 3, the amount of butylene oxide units in all alkylene oxide units is 84 mol%, and the amount of ethylene oxide units is 16 mol%)
Synthesis Example 5: In Synthesis Example 4 above, 55.24 parts by mass of BO was added in the second-stage BO aging reaction, 10.2 parts by mass of ethylene oxide (EO) was added, and the temperature was adjusted to 120°C ± 5°C and the maximum pressure of 0. After performing the EO introduction reaction at 4 MPa, the EO aging reaction was performed at 120±5° C. for 360 minutes. After cooling without EO, the pressure was reduced to 20 mmHg (2.7 kPa) at 100±5° C., followed by purification and filtration to obtain trifunctional EO-terminated polybutylene glycol.
・ PO polyol 1: number average molecular weight 700, functional group 2 polypropylene glycol, product name: Hiflex D-700, manufactured by Daiichi Kogyo Seiyaku Co., Ltd. ・ PO polyol 2: number average molecular weight 1000, functional group 2 Polypropylene glycol, product name: Hiflex D-1000, manufactured by Daiichi Kogyo Seiyaku Co., Ltd. PO-based polyol 3: polyoxyethylene polyoxypropylene glycol with a number average molecular weight of 1,300 and a number of functional groups of 2, product name: Epan 410, No. Ichi Kogyo Seiyaku Co., Ltd. PO polyol 4: number average molecular weight 1000, functional group 3 polypropylene glycol, product name: X-2116, Daiichi Kogyo Seiyaku Co., Ltd. PO polyol 5: number average molecular weight 3000 , Polypropylene glycol with a functional number of 3, Product name: Hiflex G-3000, Daiichi Kogyo Seiyaku Co., Ltd. Castor oil-based polyol: Number average molecular weight 938, Functional group number 2.7, Product name: Castor oil D, Ito oil ( Co., Ltd. [catalyst]
・ Catalyst: dioctyl tin, product name: Neostan U-810, manufactured by Nitto Kasei Co., Ltd. [Isocyanate group-containing compound (B)]
・Polyisocyanate 1: HDI isocyanurate, product name: Duranate TPA-100, manufactured by Asahi Kasei Co., Ltd. ・Polyisocyanate 2: HDI, product name: Duranate D-201, manufactured by Asahi Kasei Co., Ltd. ・Polyisocyanate 3: Crude MDI, Product name: Luplanate M5S, manufactured by BASF INOAC Polyurethane Co., Ltd. [Examples 1 to 10 and Comparative Examples 1 to 6]
Polyurethane resin compositions of Examples and Comparative Examples 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 liquid 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 liquid (isocyanate group-containing compound (B)) 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.
　各実施例および各比較例について、相溶性、硬化性、耐久性、体積固有抵抗およびマイグレーション特性を測定・評価した。測定・評価方法は以下のとおりである。 Compatibility, curability, durability, volume resistivity and migration properties were measured and evaluated for each example and each comparative example. The measurement and evaluation methods are as follows.
　［相溶性］
　水酸基含有化合物である、ポリブタジエンポリオールと、ＢＯ系ポリオール、ＰＯ系ポリオールまたはひまし油系ポリオールとを混合した後、室温で７日間放置し、放置後の液の状態を下記基準により評価した。 [Compatibility]
After mixing polybutadiene polyol, which is a hydroxyl group-containing compound, with BO-based polyol, PO-based polyol or castor oil-based polyol, the mixture was allowed to stand at room temperature for 7 days, and the state of the liquid after standing was evaluated according to the following criteria.
　Ａ：透明
　Ｂ：濁りあり
　Ｃ：分離
　［硬化性］
　上記脱泡後のポリウレタン樹脂組成物を、縦５ｃｍ×横５ｃｍ×高さ３ｃｍの容器に流し込み、８０℃の硬化炉で１時間放置後、樹脂の硬度を測定した。硬度は、ＪＩＳ　Ｋ６２５３－３に準拠したタイプＡデュロメータおよびＪＩＳ　Ｋ７３１２に準拠したタイプＣ硬さ試験機で測定し、下記基準により評価した。なお、硬化性は速く硬化するか否かの評価である。 A: Transparent B: Turbidity C: Separation [Curability]
The polyurethane resin composition after defoaming was poured into a container of 5 cm long×5 cm wide×3 cm high, left in a curing oven at 80° C. for 1 hour, and then the hardness of the resin was measured. The hardness was measured with a type A durometer conforming to JIS K6253-3 and a type C hardness tester conforming to JIS K7312, and evaluated according to the following criteria. The curability is an evaluation of whether or not the composition cures quickly.
　Ａ：タイプＡデュロメータ硬さが０以上、
　Ｂ：タイプＡデュロメータ硬さが０未満（タイプＡデュロメータでは測定不可）かつタイプＣ硬さが０以上
　Ｃ：硬化発現なし、または液状
　［耐久性］
　上記脱泡後のポリウレタン樹脂組成物を、縦５ｃｍ×横５ｃｍ×高さ１ｃｍの型に流し込み、８０℃の硬化炉で４８時間硬化させて樹脂片を作製した。該樹脂片を温度１２１℃、湿度１００％、２ａｔｍの高温高湿槽で処理し、５００時間経過後、１０００時間経過後に硬度をＪＩＳ　Ｋ６２５３－３に準拠したタイプＡデュロメータにより測定し、初期の硬度からの変化を確認し、下記基準により評価した。 A: type A durometer hardness of 0 or more,
B: Type A durometer hardness is less than 0 (cannot be measured with type A durometer) and type C hardness is 0 or more C: No curing or liquid [Durability]
The defoamed polyurethane resin composition was poured into a mold of 5 cm long×5 cm wide×1 cm high and cured in a curing furnace at 80° C. for 48 hours to prepare resin pieces. The resin piece was treated in a high temperature and high humidity bath at a temperature of 121 ° C., a humidity of 100%, and a humidity of 2 atm, and after 500 hours and 1000 hours, the hardness was measured with a type A durometer in accordance with JIS K6253-3. The change from 0.01 to 0.000 was confirmed and evaluated according to the following criteria.
　Ａ：１０００時間経過後の硬度変化が１０％未満
　Ｂ：５００時間経過後の硬度変化が１０％未満かつ１０００時間経過後の硬度変化が１０％以上
　Ｃ：５００時間経過後の硬度変化が１０％以上
　［体積固有抵抗］
　上記の耐久性と同様の樹脂片を作製し、該樹脂片を温度１２１℃、湿度１００％、２ａｔｍの高温高湿槽で処理し、５００時間経過後、７５０時間経過後、１０００時間経過後に体積固有抵抗をＪＩＳ　Ｋ６９１１により測定し（測定電圧：５００Ｖ）、下記基準により評価した。 A: Less than 10% change in hardness after 1000 hours B: Less than 10% change in hardness after 500 hours and 10% or more change in hardness after 1000 hours C: 10% change in hardness after 500 hours [Volume specific resistance]
A resin piece having the same durability as described above was prepared, and the resin piece was treated in a high-temperature and high-humidity bath at a temperature of 121 ° C., a humidity of 100%, and 2 atm. The specific resistance was measured according to JIS K6911 (measured voltage: 500 V) and evaluated according to the following criteria.
　Ａ：１０００時間経過後の体積固有抵抗が１０９Ω・ｃｍ以上
　Ｂ：１０００時間経過後の体積固有抵抗が１０９Ω・ｃｍ未満かつ７５０時間経過後の体積固有抵抗が１０９Ω・ｃｍ以上
　Ｃ：７５０時間経過後の体積固有抵抗が１０９Ω・ｃｍ未満かつ５００時間経過後の体積固有抵抗が１０９Ω・ｃｍ以上
　［マイグレーション特性］
　ガラスシャーレにＪＩＳ２型くし形電極基板を配置し、陽極および陰極を配線した。その上に、上記脱泡後のポリウレタン樹脂組成物を注型し、８０℃の硬化炉で４８時間硬化させて試験片を作製した。該試験片を温度８５℃、湿度８５％の湿熱槽にて、１００Ｖの電圧を印加してマイグレーション試験を実施し、１０００時間経過までに通電するか否かを、下記基準により評価した。電極周囲の水分が多いほど、陽極から銅イオンが溶出し、陰極へ移動、陰極側で析出する。析出分が成長すると絶縁不良となり、最終的には配線パターン間がショートする。かかるショートが発生するか否かの試験である。 A: Volume resistivity after 1000 hours is 10 9 Ω·cm or more B: Volume resistivity is less than 10 9 Ω·cm after 1000 hours and volume resistivity is 10 9 Ω·cm or more after 750 hours C: The volume resistivity after 750 hours is less than 10 9 Ω·cm and the volume resistivity after 500 hours is 10 9 Ω·cm or more [migration property]
A JIS type 2 comb-shaped electrode substrate was placed on a glass petri dish, and an anode and a cathode were wired. The defoamed polyurethane resin composition was poured onto the mold and cured in a curing oven at 80° C. for 48 hours to prepare a test piece. The test piece was subjected to a migration test by applying a voltage of 100 V in a moist heat bath at a temperature of 85° C. and a humidity of 85%, and whether or not the current was applied within 1000 hours was evaluated according to the following criteria. As the amount of water around the electrode increases, copper ions are eluted from the anode, migrate to the cathode, and deposit on the cathode side. If the deposit grows, it causes insulation failure, and finally short-circuits between wiring patterns. This is a test of whether or not such a short circuit occurs.
　Ａ：通電なし
　Ｃ：通電あり A: Not energized C: Energized
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000002
 　結果は表１および表２に示すとおりである。ポリブタジエンポリオールと併用するポリオールとしてＰＯ系ポリオール１～５を用いた比較例１～５であると、湿熱処理後の耐久性（硬度変化）には優れていたものの、湿熱処理後の体積固有抵抗の低下が大きく、またマイグレーション特性にも劣っており、耐湿熱性に劣っていた。
Figure JPOXMLDOC01-appb-T000002
 The results are shown in Tables 1 and 2. Comparative Examples 1 to 5 using PO-based polyols 1 to 5 as polyols used in combination with polybutadiene polyol were excellent in durability (hardness change) after wet heat treatment, but the volume resistivity after wet heat treatment was excellent. The deterioration was large, the migration property was poor, and the wet heat resistance was poor.
　ポリブタジエンポリオールと併用するポリオールとしてひまし油系ポリオールを用いた比較例６では、湿熱処理後のマイグレーション特性には優れていたものの、湿熱処理後の耐久性（硬度変化）が劣っており、体積固有抵抗についても低下傾向が見られた。また、ひまし油系ポリオールを用いた場合、硬化性にも劣っていた。 In Comparative Example 6, in which a castor oil-based polyol was used as the polyol used in combination with the polybutadiene polyol, the migration properties after the wet heat treatment were excellent, but the durability (hardness change) after the wet heat treatment was poor, and the volume resistivity was poor. also showed a downward trend. Moreover, when a castor oil-based polyol was used, curability was also inferior.
　これに対し、ポリブタジエンポリオールとＢＯ系ポリオールを併用した実施例１～１０であると、湿熱処理後の耐久性（硬度変化）、体積固有抵抗およびマイグレーション特性に優れており、比較例１～６に対して耐湿熱性に優れていた。 On the other hand, Examples 1 to 10 in which polybutadiene polyol and BO-based polyol were used in combination were excellent in durability (hardness change), volume resistivity and migration properties after wet heat treatment, and were superior to Comparative Examples 1 to 6. It was excellent in heat and humidity resistance.
　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 invention have been described above, these embodiments are presented by way of example 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 (6)

  1. 　水酸基含有化合物（Ａ）およびイソシアネート基含有化合物（Ｂ）を含むポリウレタン樹脂組成物であって、
    　前記水酸基含有化合物（Ａ）が、ポリブタジエンポリオール（Ａ１）と、アルキレンオキシド単位の５０モル％以上がブチレンオキシド単位であるブチレンオキシド系ポリオール（Ａ２）とを含み、
    　前記ブチレンオキシド系ポリオール（Ａ２）の数平均分子量が４００以上３０００以下である、ポリウレタン樹脂組成物。     A polyurethane resin composition containing a hydroxyl group-containing compound (A) and an isocyanate group-containing compound (B),
    The hydroxyl group-containing compound (A) contains a polybutadiene polyol (A1) and a butylene oxide polyol (A2) in which 50 mol% or more of the alkylene oxide units are butylene oxide units,
    A polyurethane resin composition, wherein the butylene oxide-based polyol (A2) has a number average molecular weight of 400 or more and 3,000 or less.
  2. 　前記水酸基含有化合物（Ａ）１００質量％における前記ブチレンオキシド系ポリオール（Ａ２）の含有量が１０質量％以上８０質量％以下である、請求項１記載のポリウレタン樹脂組成物。 The polyurethane resin composition according to claim 1, wherein the content of the butylene oxide-based polyol (A2) in 100% by mass of the hydroxyl group-containing compound (A) is 10% by mass or more and 80% by mass or less.
  3. 　前記ブチレンオキシド系ポリオール（Ａ２）の数平均分子量が６００以上１６００以下であり、前記水酸基含有化合物（Ａ）１００質量％における前記ブチレンオキシド系ポリオール（Ａ２）の含有量が２０質量％以上６０質量％以下である、請求項１または２に記載のポリウレタン樹脂組成物。 The number average molecular weight of the butylene oxide-based polyol (A2) is 600 or more and 1600 or less, and the content of the butylene oxide-based polyol (A2) in 100% by mass of the hydroxyl group-containing compound (A) is 20% by mass or more and 60% by mass. The polyurethane resin composition according to claim 1 or 2, wherein:
  4. 　前記イソシアネート基含有化合物（Ｂ）がイソシアヌレート変性体を含む、請求項１～３のいずれか１項に記載のポリウレタン樹脂組成物。 The polyurethane resin composition according to any one of claims 1 to 3, wherein the isocyanate group-containing compound (B) contains an isocyanurate modified product.
  5. 　前記水酸基含有化合物（Ａ）を含む第１液と、前記イソシアネート基含有化合物（Ｂ）を含む第２液と、を含む二液型である、請求項１～４のいずれか１項に記載のポリウレタン樹脂組成物。 The first liquid containing the hydroxyl group-containing compound (A) and the second liquid containing the isocyanate group-containing compound (B), which is a two-component type according to any one of claims 1 to 4. Polyurethane resin composition.
  6. 　電気絶縁用封止剤として用いられる請求項１～５のいずれか１項に記載のポリウレタン樹脂組成物。
          The polyurethane resin composition according to any one of claims 1 to 5, which is used as an electrical insulating sealant.
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JP2015131883A (en) * 2014-01-10 2015-07-23 第一工業製薬株式会社 polyurethane resin composition
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