Classifications

• • 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
  • C08G18/698—Mixtures with compounds of group C08G18/40
• • 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
  • C08G18/36—Hydroxylated esters of higher fatty acids
• • 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
  • C08G18/791—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups
• • 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
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
  • C08K3/20—Oxides; Hydroxides
  • C08K3/22—Oxides; Hydroxides of metals
• • 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
  • C08L75/08—Polyurethanes from polyethers
• • 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
  • H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
  • H01L23/293—Organic, e.g. plastic
• • 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
• • 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
  • C08G2190/00—Compositions for sealing or packing joints
• • 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
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
  • C08K3/20—Oxides; Hydroxides
  • C08K3/22—Oxides; Hydroxides of metals
  • C08K2003/2227—Oxides; Hydroxides of metals of aluminium

Definitions

• An embodiment of the present invention relates to a polyurethane resin composition.
• Patent Document 1 contains a hydroxyl group-containing compound, an isocyanate group-containing compound, a metal hydroxide and a plasticizer, the hydroxyl group-containing compound contains a polybutadiene polyol and a castor oil-based polyol, and the metal hydroxide contains water.
• a polyurethane resin composition is disclosed which is aluminum oxide 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 hydroxyl group-containing compound (A), an isocyanate group-containing compound (B), a metal hydroxide (C), and a plasticizer (D), wherein the hydroxyl group-containing compound (A) is , 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, and the butylene oxide polyol (A2) has a number average molecular weight of 400 or more and 3000 or less.
• a polyurethane resin composition comprising a hydroxyl group-containing compound (A), an isocyanate group-containing compound (B), a metal hydroxide (C), and a plasticizer (D), wherein the hydroxyl group-containing compound (A) is , a polybutadiene polyol (A1) and a butylene oxide polyol (A2) in which 50 mol% or more of the alkylene oxide units
• 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) is 1 part by mass with respect to 100 parts by mass of the polyurethane resin composition.
• [8] Contains a first liquid containing the hydroxyl group-containing compound (A), the metal hydroxide (C) and the plasticizer (D), and a second liquid containing the isocyanate group-containing compound (B)
• the polyurethane resin composition according to this embodiment contains a hydroxyl group-containing compound (A), an isocyanate group-containing compound (B), a metal hydroxide (C), and a plasticizer (D).
• 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 GPC (gel permeation chromatography) 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 JIS K1557 -1: A value measured according to 2007 A method, which is the number of mg of potassium hydroxide (KOH) that reacts with acetic acid that acetylates the hydroxyl group (OH group) in 1 g of polyol.
• 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, and may be 1 to 25 parts by mass, 2 to 20 parts by mass, or 3 to 15 parts by mass with respect to 100 parts by mass of the polyurethane resin composition.
• 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 mixed viscosity during production of the polyurethane resin composition can be lowered to improve workability.
• 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 1 to 15 parts by mass with respect to 100 parts by mass of the polyurethane resin composition.
• the content of the butylene oxide-based polyol (A2) is 1 part by mass or more, the wet heat resistance can be improved, and the mixed viscosity during production of the polyurethane resin composition can be lowered.
• the content is 15 parts by mass or less, bleeding from the surface of the resin after curing can be suppressed, and curability can be improved.
• the content of the butylene oxide-based polyol (A2) is more preferably 1 to 10 parts by mass, still more preferably 1.5 to 7 parts by mass, per 100 parts by mass of the polyurethane resin composition.
• 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 total content (A1+A2) of the polybutadiene polyol (A1) and the butylene oxide polyol (A2) is not particularly limited, and is preferably 4 to 26 parts by mass with respect to 100 parts by mass of the polyurethane resin composition. It is more preferably 5 to 21 parts by mass, still more preferably 6 to 16 parts by mass.
• the hydroxyl group-containing compound (A) is further a castor oil-based polyol (A3 ) may be included.
• 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.
• 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 (A3) is not particularly limited, and may be, for example, 50-250 mgKOH/g or 100-180 mgKOH/g.
• the hydroxyl value of the castor oil-based polyol (A3) is measured according to A method of JIS K1557-1:2007.
• the content of the castor oil-based polyol (A3) is not particularly limited, it is preferably a small amount from the viewpoint of moist heat resistance. , 0.1 to 1 part by mass.
• the hydroxyl group-containing compound (A) may be composed only of polybutadiene polyol (A1) and butylene oxide-based polyol (A2), and polybutadiene polyol (A1), butylene oxide-based polyol (A2) and castor oil-based although it may consist only of the polyol (A3), it may 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 compounds, and are not particularly limited. Examples thereof include polyester polyols other than castor oil-based polyols (A3), polyether polyols other than butylene oxide-based polyols (A2), polycarbonate polyols, dimer acid polyols, polycaprolactone polyols, acrylic polyols, and polyisoprene polyols. Furthermore, 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 may be used in combination with the above HDI and/or modified isocyanurate (preferably HDI isocyanurate).
• 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.
• Metal hydroxide (C) examples include aluminum hydroxide and/or magnesium hydroxide, preferably aluminum hydroxide.
• the content of the metal hydroxide (C) is not particularly limited, and may be 40 to 85 parts by mass or 50 to 75 parts by mass with respect to 100 parts by mass of the polyurethane resin composition. When the content of the metal hydroxide (C) is 40 parts by mass or more, flame retardancy can be improved. can be lowered.
• plasticizer (D) examples include phthalate esters such as dioctyl phthalate, diisononyl phthalate and diundecyl phthalate; adipate esters such as dioctyl adipate and diisononyl adipate; Triglycerides, castor oil-based esters such as acetylated polyricinoleic acid triglycerides, trimellitic acid esters such as trioctyl trimellitate, triisononyl trimellitate, pyromellitic acid such as tetraoctyl pyromellitate, tetraisononyl pyromellitate Esters, tricresyl phosphate, trisxylenyl phosphate, cresyl diphenyl phosphate, xylenyl phosphate, triphenyl phosphate and other phosphoric acid esters, etc., and these are
• the content of the plasticizer (D) is not particularly limited, and may be 5 to 30 parts by mass, 10 to 28 parts by mass, or 15 to 25 parts by mass with respect to 100 parts by mass of the polyurethane resin composition.
• the content of the plasticizer (D) is 5 parts by mass or more, the hardness of the cured polyurethane resin can be lowered.
• 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, and the like. 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 parts by mass or 0.001 to 0.01 parts by mass with respect to 100 parts by mass of the polyurethane resin composition.
• the polyurethane resin composition comprises a first liquid containing a hydroxyl group-containing compound (A), a metal hydroxide (C) and a plasticizer (D), and a second liquid containing an isocyanate group-containing compound (B). And may be configured as a two-part polyurethane resin composition containing. 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), the metal hydroxide (C) and the plasticizer (D).
• Various additives such as inhibitors, foam stabilizers, diluents, flame retardants, ultraviolet absorbers and colorants may be added.
• the first liquid contains a hydroxyl group-containing compound (A), a metal hydroxide (C), a plasticizer (D) and a catalyst.
• the second liquid may consist only of the isocyanate group-containing compound (B), or may contain the isocyanate group-containing compound (B) together with the metal hydroxide (C) and/or the plasticizer (D).
• various additives such as antioxidants, foam stabilizers, diluents, flame retardants, ultraviolet absorbers and colorants may be blended as needed.
• 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. [Other ingredients]
• ⁇ Plasticizer diundecyl phthalate
• Metal hydroxide aluminum hydroxide
• Catalyst dioctyl tin
• product name: Neostan U-810 manufactured by Nitto Kasei Co., Ltd.
• Examples 1 to 16 and Comparative Examples 1 to 6 Polyurethane resin compositions of each example and each comparative example were prepared according to the formulations (parts by mass) shown in Tables 1 to 3 below.
• a predetermined amount of the first liquid shown in Tables 1 to 3 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 this mixture as shown in Tables 1 to 3, and the mixture was stirred and mixed to degas.
• 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 oven at 80° C. for 48 hours to prepare resin pieces.
• the resin piece is 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, 750 hours, and 1000 hours, the hardness is measured with a type A durometer in accordance with JIS K6253-3. It was measured and evaluated according to the following criteria.
• Type A durometer hardness after 1000 hours is 5 or more
• B: Type A durometer hardness after 750 hours is 5 or more and Type A durometer hardness after 1000 hours is less than 5
• C After 500 hours The type A durometer hardness of 5 or more and the type A durometer hardness after 750 hours is less than 5 [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 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. Also, the mixed viscosity was high.
• Examples 1 to 16 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.

Landscapes

• Chemical & Material Sciences (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• General Physics & Mathematics (AREA)
• Condensed Matter Physics & Semiconductors (AREA)
• Physics & Mathematics (AREA)
• Engineering & Computer Science (AREA)
• Computer Hardware Design (AREA)
• Microelectronics & Electronic Packaging (AREA)
• Power Engineering (AREA)
• Polyurethanes Or Polyureas (AREA)
• Compositions Of Macromolecular Compounds (AREA)
• Structures Or Materials For Encapsulating Or Coating Semiconductor Devices Or Solid State Devices (AREA)

Priority Applications (2)

Applications Claiming Priority (2)

Publications (1)

Family

ID=82610389

Family Applications (1)

Country Status (5)

Citations (5)

Family Cites Families (1)

• 2021
  • 2021-07-13 JP JP2021115946A patent/JP7108757B1/ja active Active
• 2022
  • 2022-06-28 TW TW111123981A patent/TW202321334A/zh unknown
  • 2022-06-29 CN CN202280047512.6A patent/CN117597375A/zh active Pending
  • 2022-06-29 KR KR1020247002592A patent/KR20240032865A/ko unknown
  • 2022-06-29 WO PCT/JP2022/025876 patent/WO2023286596A1/ja active Application Filing

Patent Citations (5)

Also Published As

Similar Documents

Legal Events