WO2022244650A1 - Composition contenant un isocyanate et composition de résine de polyuréthane de type à réaction en deux parties - Google Patents

Composition contenant un isocyanate et composition de résine de polyuréthane de type à réaction en deux parties Download PDF

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Publication number
WO2022244650A1
WO2022244650A1 PCT/JP2022/019775 JP2022019775W WO2022244650A1 WO 2022244650 A1 WO2022244650 A1 WO 2022244650A1 JP 2022019775 W JP2022019775 W JP 2022019775W WO 2022244650 A1 WO2022244650 A1 WO 2022244650A1
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group
isocyanate
containing composition
general formula
polyol
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PCT/JP2022/019775
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English (en)
Japanese (ja)
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七大 田部
欣範 山田
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第一工業製薬株式会社
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Priority to CN202280034602.1A priority Critical patent/CN117295776A/zh
Publication of WO2022244650A1 publication Critical patent/WO2022244650A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—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
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • 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
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives
    • 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
    • C08K3/10—Metal compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/02—Polyalkylene oxides
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/20—Mountings; Secondary casings or frames; Racks, modules or packs; Suspension devices; Shock absorbers; Transport or carrying devices; Holders
    • H01M50/202—Casings or frames around the primary casing of a single cell or a single battery
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to a two-component reactive polyurethane resin composition and an isocyanate-containing composition used as a polyisocyanate component thereof.
  • Patent Document 1 discloses blending an inorganic filler, a plasticizer, and a phosphate ester into a polyurethane resin obtained by reacting a polyisocyanate and a polybutadiene polyol. Heat dissipation can be improved by containing it in a high compounding ratio.
  • the inorganic filler When blending an inorganic filler into a polyurethane resin composition, generally, the inorganic filler is blended with the polyol component, and the polyisocyanate component containing no inorganic filler is added and mixed to react the two components.
  • the polyol component containing an inorganic filler is difficult to mix with a polyisocyanate component containing no inorganic filler. If an inorganic filler is blended with the polyisocyanate component in order to improve the mixability of the two, the storage stability of the polyisocyanate component is lowered.
  • an embodiment of the present invention is a polyurethane resin composition containing an inorganic filler, while suppressing deterioration in storage stability of an isocyanate-containing composition used as a polyisocyanate component, polyol used as a polyol component
  • An object of the present invention is to provide an isocyanate-containing composition capable of improving miscibility with the containing composition.
  • R 1 represents OH or a group represented by the following general formula (2)
  • a compound in which R 1 is OH and R 1 is represented by general formula (2) It may be a mixture with a compound, and in general formula (3), k represents the number of 1 or 0, and X represents a linking group of —CH 2 —, —CO(CH 2 ) p — or —COCH ⁇ CH—.
  • R 2 and R 3 each independently represents a hydrocarbon group having 6 to 30 carbon atoms
  • a 1 O and A 3 O each independently represent an oxyalkylene group having 2 to 4 carbon atoms
  • m and n are the average addition of alkylene oxide.
  • the embodiment of the present invention it is possible to improve the miscibility with the polyol-containing composition while suppressing deterioration of the storage stability of the isocyanate-containing composition.
  • the two-liquid reactive polyurethane resin composition according to the present embodiment comprises a polyol-containing composition as a polyol component and an isocyanate-containing composition as a polyisocyanate component.
  • the isocyanate-containing composition contains a urethane prepolymer (a).
  • a urethane prepolymer
  • the average number of functional groups (average number of hydroxyl groups) of the polyol is 2.5 or less, the hardness of the polyurethane resin after curing can be kept low. When used as a gap filler to fill the gap, the reaction force generated against the external force can be reduced.
  • the average number of functional groups of the polyol is preferably 2.4 or less, more preferably 2.3 or less.
  • the lower limit of the average functional group number of the polyol is not particularly limited, and for example, the average functional group number may be 1.7 or more.
  • the above polyol preferably has hydroxyl groups at both ends, and therefore preferably has an average functional group number of 2.0 or more.
  • the storage stability of the isocyanate-containing composition can be improved.
  • the weight average molecular weight of the polyol is preferably 800 or more.
  • the upper limit of the weight average molecular weight of the polyol is not particularly limited. As used herein, the weight average molecular weight is a value calculated using a calibration curve based on standard polystyrene by GPC (gel permeation chromatography) measurement.
  • polyether polyols examples include polyether polyols, polyester polyols, polycarbonate polyols, polybutadiene polyols, polyisoprene polyols, etc., and these can be used singly or in combination of two or more.
  • polyether polyols include polyoxyalkylene polyols obtained by adding ethylene oxide or propylene oxide to polyhydric alcohols or polyamines.
  • Polyester polyols include those obtained by dehydration condensation of carboxylic acids such as adipic acid and phthalic acid and polyhydric alcohols such as ethylene glycol and 1,4-butanediol.
  • polybutadiene polyol those having hydroxyl groups at both ends of the polybutadiene structure are more preferable, and hydrogenated polybutadiene polyols may also be used. Among these, it is preferable to use polypropylene glycol and/or polybutadiene polyol.
  • the polyisocyanate is not particularly limited, and examples thereof include aliphatic diisocyanates, alicyclic diisocyanates, and aromatic diisocyanates.
  • aliphatic diisocyanates and alicyclic diisocyanates are used. They may be used together.
  • aliphatic diisocyanate examples 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. Moreover, you may use these in combination of 2 or more types.
  • 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
  • alicyclic diisocyanates examples include isophorone diisocyanate, hydrogenated xylylene diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, 1,4-cyclohexane diisocyanate, methylcyclohexylene diisocyanate, 1,3-bis(isocyanatomethyl)cyclohexane, and the like. is mentioned. Moreover, you may use these in combination of 2 or more types.
  • the urethane prepolymer (a) is obtained by reacting the above-mentioned polyol and polyisocyanate under the condition of excessive isocyanate groups.
  • the urethane prepolymer (a) is preferably a terminal isocyanate prepolymer having isocyanate groups at both ends.
  • the amount of the urethane prepolymer (a) is not particularly limited, but it is preferably 1.0 to 15% by mass, more preferably 1.5 to 10% by mass in 100% by mass of the isocyanate-containing composition. .
  • the isocyanate-containing composition contains an inorganic filler (b). By blending the inorganic filler (b), heat dissipation can be imparted to the cured polyurethane resin.
  • the inorganic filler (b) is not particularly limited, and examples thereof include metal oxides such as alumina and magnesium oxide, metal hydroxides such as aluminum hydroxide and magnesium hydroxide, and metal nitrides such as aluminum nitride and boron nitride. etc. These can be used either singly or in combination of two or more.
  • the content of the inorganic filler (b) is preferably 50 to 95% by mass in 100% by mass of the isocyanate-containing composition.
  • the compounding amount is 50% by mass or more, the heat dissipation property of the polyurethane resin can be improved.
  • the amount is 95% by mass or less, the storage stability of the isocyanate-containing composition can be improved.
  • the blending amount is more preferably 60% by mass or more, more preferably 70% by mass or more, still more preferably 80% by mass or more, and preferably 90% by mass or less.
  • the isocyanate-containing composition contains a plasticizer (c).
  • a plasticizer c
  • the storage stability of the isocyanate-containing composition can be improved, and the miscibility with the polyol-containing composition can be improved.
  • the plasticizer (c) is not particularly limited, and conventionally known ones blended in polyurethane resins can be used.
  • Adipic acid diesters such as diisononyl adipate, trimellitic acid esters such as trioctyl trimellitate and triisononyl trimellitate, pyromellitic acid esters such as tetraoctyl pyromellitate and tetraisononyl pyromellitate, tricresyl phosphate , trixylenyl phosphate, cresyl diphenyl phosphate, and the like, and phosphoric acid triesters and the like, and these can be used either singly or in combination of two or more.
  • phthalate diesters and/or adipate diesters are preferred as the plasticizer (c).
  • the amount of the plasticizer (c) is not particularly limited, and may be, for example, 1 to 40% by mass, 3 to 35% by mass, or 5 to 30% by mass in 100% by mass of the isocyanate-containing composition. It may be 10 to 20% by mass.
  • the isocyanate-containing composition contains at least one compound (hereinafter sometimes referred to as compound (d)) selected from the group consisting of compounds represented by general formula (1) and compounds represented by general formula (3). include.
  • compound (d) selected from the group consisting of compounds represented by general formula (1) and compounds represented by general formula (3).
  • the storage stability of the isocyanate-containing composition can be improved, and the miscibility with the polyol-containing composition can be improved.
  • compounds represented by the following general formula (1) are phosphate esters.
  • R 1 represents OH or a group represented by general formula (2) below.
  • the phosphate ester represented by formula (1) may be a compound (monoester) in which R 1 is OH, a compound (diester) in which R 1 is represented by general formula (2), or a mixture of both. good.
  • R 2 represents a hydrocarbon group having 6 to 30 carbon atoms, more preferably a hydrocarbon group having 8 to 20 carbon atoms.
  • the hydrocarbon group includes a linear or branched alkyl group, alkenyl group, aryl group, or aralkyl group, and these groups may have a substituent.
  • alkyl groups include hexyl, isohexyl, heptyl, isoheptyl, octyl, 2-ethylhexyl, isooctyl, nonyl, isononyl, decyl, isodecyl, undecyl, isoundecyl, and dodecyl.
  • alkenyl groups include hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tetradecenyl, and oleyl groups.
  • aryl groups include phenyl, tolyl, xylyl, cumenyl, mesityl, ethylphenyl, propylphenyl, butylphenyl, pentylphenyl, hexylphenyl, heptylphenyl, and octylphenyl groups.
  • nonylphenyl group decylphenyl group, undecylphenyl group, dodecylphenyl group, styrenated phenyl group, p-cumylphenyl group, phenylphenyl group, benzylphenyl group, ⁇ -naphthyl group, ⁇ -naphthyl group and the like.
  • aralkyl groups include benzyl, phenethyl, styryl, cinnamyl, benzhydryl, and trityl groups.
  • a 1 O represents an oxyalkylene group having 2 to 4 carbon atoms.
  • m represents the average number of added moles of alkylene oxide, and is a number of 1 to 100, preferably a number of 3 to 50, more preferably a number of 5 to 30, more preferably a number of 7 to 20 is.
  • the oxyalkylene chain represented by (A 1 O) m has an oxyethylene group content of 20 mol % or more. That is, when the oxyethylene group is EO and the oxyalkylene group other than the oxyethylene group is AO, EO/AO (molar ratio) is 100/0 to 20/80.
  • the content of oxyethylene groups is preferably 50 mol % or more, more preferably 70 mol % or more, even more preferably 80 mol % or more, and may be 100 mol %.
  • the oxyalkylene chain consists of a plurality of types of oxyalkylene groups, the oxyalkylene groups may be added randomly or by block addition.
  • the phosphate ester represented by formula (1) can be obtained, for example, by adding an alkylene oxide to a monoalcohol or phenol having 6 to 30 carbon atoms by a known method, and then adding the alkylene oxide terminal of the resulting polyether monool. It can be produced by reacting a hydroxyl group with a phosphorylating agent such as phosphoric anhydride, orthophosphoric acid, polyphosphoric acid, and phosphoric acid chloride. Depending on the manufacturing method, a monoester type compound and a diester type compound may be obtained as a mixture, and these may be separated or used as a mixture as they are. Moreover, it can also be used by reacting in the presence of water to increase the content of the monoester type compound.
  • a phosphorylating agent such as phosphoric anhydride, orthophosphoric acid, polyphosphoric acid, and phosphoric acid chloride.
  • a monoester type compound and a diester type compound may be obtained as a mixture, and these may be separated or used
  • the compound represented by the following general formula (3) is a sulfate ester, a sulfonic acid or a carboxylic acid, and these may be used alone or in combination of two or more.
  • k represents the number of 1 or 0.
  • Z in formula (3) represents a carboxy group (--COOH), a sulfo group (--SO 3 H), or a salt thereof, and may be in a mixture of acid and salt forms.
  • Salts include, for example, alkali metal salts, alkaline earth metal salts, ammonium salts, and alkanolamine salts.
  • alkali metal salts include sodium salts, potassium salts, lithium salts and the like.
  • alkaline earth metal salts include calcium salts and magnesium salts.
  • alkanolamine salts include monoethanolamine salts, diethanolamine salts, triethanolamine salts, triisopropanolamine salts, and the like.
  • R 3 in formula (3) represents a hydrocarbon group having 6 to 30 carbon atoms, more preferably a hydrocarbon group having 8 to 20 carbon atoms.
  • the hydrocarbon group includes a linear or branched alkyl group, alkenyl group, aryl group, or aralkyl group, and these groups may have a substituent. Specific examples of the alkyl group, alkenyl group, aryl group, and aralkyl group are the same as those for R 2 .
  • a 3 O represents an oxyalkylene group having 2 to 4 carbon atoms.
  • n represents the average number of added moles of alkylene oxide, and is a number of 1 to 100, preferably a number of 3 to 50, more preferably a number of 5 to 30, more preferably a number of 7 to 20 is.
  • the oxyalkylene chain represented by (A 3 O) m has an oxyethylene group content of 20 mol % or more. That is, when the oxyethylene group is EO and the oxyalkylene group other than the oxyethylene group is AO, EO/AO (molar ratio) is 100/0 to 20/80.
  • the content of oxyethylene groups is preferably 50 mol % or more, more preferably 70 mol % or more, even more preferably 80 mol % or more, and may be 100 mol %.
  • the oxyalkylene chain consists of a plurality of types of oxyalkylene groups, the oxyalkylene groups may be added randomly or by block addition.
  • the compound represented by formula (3) is a carboxylic acid.
  • the carboxylic acid of formula (3) can be obtained, for example, by adding an alkylene oxide to a monoalcohol or phenol having 6 to 30 carbon atoms by a known method, and then using a monohalogenated acetic acid or a salt thereof, in the presence of a base.
  • it can be produced by a ring-opening reaction with an alkylene oxide terminal hydroxyl group using an acid anhydride.
  • a sulfate ester can be produced by adding an alkylene oxide to a monoalcohol or phenol having 6 to 30 carbon atoms by a known method, and then reacting sulfamic acid with a hydroxyl group at the end of the alkylene oxide.
  • a sulfonic acid can be produced by adding the above alkylene oxide and then reacting it with a hydroxyl group at the end of the alkylene oxide using a monohalogenated sulfonic acid or a salt thereof.
  • the amount of the compound (d) is not particularly limited, and may be, for example, 0.01 to 5% by mass, 0.03 to 2% by mass, or 0.05 to 1% in 100% by mass of the isocyanate-containing composition. % by mass may be used.
  • the urethane prepolymer (a) may be used alone as the polyisocyanate compound, or the urethane prepolymer (a) may be used in combination with another polyisocyanate compound.
  • polyisocyanate compounds are not particularly limited, and various polyisocyanate compounds having two or more isocyanate groups in one molecule can be used, for example, aliphatic polyisocyanates, alicyclic polyisocyanates, and Aromatic polyisocyanates, and modified and polynuclear compounds thereof may be mentioned, and any one of them may be used alone or two or more of them may be used in combination.
  • Specific examples of aliphatic polyisocyanates and alicyclic polyisocyanates include the above-mentioned aliphatic diisocyanates and alicyclic diisocyanates.
  • aromatic polyisocyanates examples include tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), 4,4′-dibenzyl diisocyanate, 1,5-naphthylene diisocyanate, xylylene diisocyanate (XDI), 1,3- phenylene diisocyanate, 1,4-phenylene diisocyanate, and the like.
  • Modified products of these polyisocyanate compounds include, for example, isocyanurate modified products, allophanate modified products, buret modified products, adduct modified products, and carbodiimide modified products.
  • polyisocyanate compounds it is preferable to use isocyanurate-modified polyisocyanate compounds, more preferably isocyanurate-modified aliphatic polyisocyanates.
  • the amount of the modified isocyanurate compounded is not particularly limited. % by mass.
  • the polyisocyanate compound preferably contains the urethane prepolymer (a) as a main component, and even when used in combination with other polyisocyanate compounds, the total polyisocyanate compound exceeds 50% by mass, more preferably 60% by mass.
  • the above is preferably the urethane prepolymer (a).
  • the isocyanate-containing composition contains various additives such as moisture absorbers, antioxidants, foam stabilizers, diluents, flame retardants, ultraviolet absorbers, and colorants. It can be added as long as it does not damage it.
  • the isocyanate value (NCOV) of the isocyanate-containing composition is not particularly limited, and may be 1.0 to 10 mgKOH/g, 1.5 to 8.0 mgKOH/g, or 2.0 to 7.5 mgKOH/g. .
  • the polyol-containing composition contains polyol (e).
  • the polyol (e) is not particularly limited, and examples thereof include polyether polyol, polyester polyol, polycarbonate polyol, polybutadiene polyol, polyisoprene polyol, etc., and these can be used singly or in combination of two or more. .
  • polybutadiene polyol is preferably used.
  • the polybutadiene polyol those having hydroxyl groups at both ends of the polybutadiene structure are more preferable, and hydrogenated polybutadiene polyols may also be used.
  • the average functionality of polybutadiene polyol is preferably 2.0 to 2.5, more preferably 2.1 to 2.4.
  • the amount of the polyol (e) is not particularly limited, but it is preferably 2 to 30% by mass, more preferably 3 to 25% by mass, and still more preferably 5 to 30% by mass in 100% by mass of the polyol-containing composition. 20% by mass.
  • the polyol-containing composition contains an inorganic filler (f).
  • an inorganic filler (f) By blending the inorganic filler (f), heat dissipation can be imparted to the cured polyurethane resin.
  • the inorganic filler (f) is not particularly limited, and examples thereof include metal oxides such as alumina and magnesium oxide, metal hydroxides such as aluminum hydroxide and magnesium hydroxide, and metal nitrides such as aluminum nitride and boron nitride. etc. These can be used either singly or in combination of two or more.
  • the content of the inorganic filler (f) is preferably 50 to 95% by mass, more preferably 60% by mass or more, and more preferably 70% by mass or more in 100% by mass of the polyol-containing composition. , more preferably 80% by mass or more, and preferably 90% by mass or less.
  • the polyol-containing composition may contain a plasticizer (g). By containing the plasticizer (g), the hardness of the cured polyurethane resin can be lowered.
  • the plasticizer (g) is not particularly limited, and includes the above-mentioned phthalate diesters, adipate diesters, trimellitate esters, pyromellitic acid esters, and phosphate triesters. The above can be used in combination. Among these, phthalate diesters and/or adipate diesters are preferred as the plasticizer (g).
  • the amount of the plasticizer (g) is not particularly limited, and may be, for example, 1 to 30% by mass, 3 to 25% by mass, or 5 to 20% by mass in 100% by mass of the polyol-containing composition. It may be 5 to 15% by mass.
  • the polyol-containing composition may contain a phosphate ester (h). By containing the phosphate ester (h), the viscosity of the polyol-containing composition (h) can be reduced. A compound represented by the above formula (1) is used as the phosphate ester (h).
  • the amount of the phosphate ester (h) is not particularly limited, and may be, for example, 0.01 to 5% by mass, 0.03 to 2% by mass, or 0.05% by mass in 100% by mass of the polyol-containing composition. It may be up to 1% by mass.
  • additives such as a moisture absorbent, a catalyst, an antioxidant, a foam stabilizer, a diluent, a flame retardant, an ultraviolet absorber, and a colorant may be added according to the present embodiment. It can be added as long as it does not impair the purpose.
  • 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 hydroxyl value (OHV) of the polyol-containing composition is not particularly limited, and may be 1.0-15 mgKOH/g or 2.0-10 mgKOH/g.
  • the two-component reactive polyurethane resin composition according to the present embodiment is usually composed of a first component that is a polyol-containing composition and a second component that is an isocyanate-containing composition.
  • the third liquid may contain any of the above-mentioned other components as optional components.
  • the two-component reactive polyurethane resin composition can be produced by preparing a polyol-containing composition and an isocyanate-containing composition, respectively. Anything is fine.
  • the polyol-containing composition and the isocyanate-containing composition, which are filled in separate containers, may be mixed at the time of use so that the polyol and the polyisocyanate react to form a polyurethane resin and cure. At that time, it may be cured by heating.
  • the two-liquid reactive polyurethane resin composition according to the embodiment may be obtained by mixing a polyol-containing composition and an isocyanate-containing composition, may be in a liquid state before curing, or may be in a cured state. .
  • the mixing ratio of the polyol-containing composition and the isocyanate-containing composition is not particularly limited.
  • the molar ratio NCO/OH (index) of may be from 0.5 to 1.2, or from 0.6 to 0.9.
  • NCO/OH is calculated as NCOV/OHV from the above isocyanate value (NCOV) and hydroxyl value (OHV).
  • the hardness of the two-liquid reactive polyurethane resin composition after curing is not particularly limited, but the shore C hardness is preferably 60 or less, and may be 30-60.
  • the thermal conductivity (JIS R2618) of the two-liquid reactive polyurethane resin composition after curing is not particularly limited, and may be, for example, 1.0 W/m ⁇ K or more, or 2.0 W/m ⁇ K or more. 0 to 3.0 W/m ⁇ K.
  • Two-liquid reactive polyurethane resin composition is not particularly limited, and can be used for various applications such as electrical and electronic parts and vehicles. It is suitable for use as a heat-dissipating material because it has heat-dissipating properties when an inorganic filler is added. As one embodiment, it is preferably used as a heat dissipation gap filler for a heat source such as a battery.
  • the two-liquid reactive polyurethane resin composition will be described in detail below based on Examples and Comparative Examples, but the present invention is not limited thereto.
  • Polyol ⁇ Polybutadiene polyol: "POLYVEST HT" manufactured by Evonik, average functionality 2.3
  • Polybutadiene polyol "POLYVEST HT” manufactured by Evonik, average functionality 2.3
  • Plasticizer ⁇ DUP: diundecyl phthalate
  • DOA di-2-ethylhexyl adipate
  • Prepolymer 1 In a four-necked flask equipped with a stirrer, a reflux condenser, a thermometer and a nitrogen blowing tube, 33 parts by mass of hexamethylene diisocyanate (HDI) (manufactured by Asahi Kasei Corporation "Duranate 50M") and polypropylene glycol (average functional group number 2.0, weight average molecular weight 700, hydroxyl value 160) (“EXENOL 720” manufactured by AGC Co., Ltd.) and 67 parts by mass of the isocyanate group-terminated urethane prepolymer (prepolymer 1) by reacting at 90°C for 2 hours. Obtained.
  • HDI hexamethylene diisocyanate
  • EXENOL 720 manufactured by AGC Co., Ltd.
  • Prepolymer 2 In a four-necked flask equipped with a stirrer, a reflux condenser, a thermometer and a nitrogen blowing tube, 26 parts by mass of hexamethylene diisocyanate (HDI) ("Duranate 50M” manufactured by Asahi Kasei Corporation) and polypropylene glycol (average functional group number 2.0, weight average molecular weight 1000, hydroxyl value 112) ("EXENOL 1020" manufactured by AGC Co., Ltd.) and 74 parts by mass of the isocyanate group-terminated urethane prepolymer (prepolymer 2) by reacting at 90°C for 2 hours. Obtained.
  • HDI hexamethylene diisocyanate
  • EXENOL 1020 manufactured by AGC Co., Ltd.
  • Prepolymer 3 10 parts by mass of hexamethylene diisocyanate (HDI) ("Duranate 50M” manufactured by Asahi Kasei Corporation) and polypropylene glycol (average functional group number 2.0, weight average molecular weight 3000, hydroxyl value 35) (“EXENOL 3020” manufactured by AGC Co., Ltd.) and 90 parts by mass of the isocyanate group-terminated urethane prepolymer (prepolymer 3) by reacting it at 120°C for 6 hours. Obtained.
  • HDI hexamethylene diisocyanate
  • EXENOL 3020 manufactured by AGC Co., Ltd.
  • Prepolymer 4 In a four-necked flask equipped with a stirrer, a reflux condenser, a thermometer and a nitrogen blowing tube, 31 parts by mass of isophorone diisocyanate (IPDI) ("IPDI” manufactured by EVONIK) and polypropylene glycol (average functionality: 2.0 , weight average molecular weight: 1000, hydroxyl value: 112) ("EXENOL 1020" manufactured by AGC) was reacted with 69 parts by mass at 90°C for 2 hours to obtain an isocyanate group-terminated urethane prepolymer (prepolymer 4).
  • IPDI isophorone diisocyanate
  • EVONIK polypropylene glycol
  • EXENOL 1020 manufactured by AGC
  • Prepolymer 5 In a four-necked flask equipped with a stirrer, a reflux condenser, a thermometer and a nitrogen blowing tube, 46 parts by mass of hexamethylene diisocyanate (HDI) (manufactured by Asahi Kasei Corporation "Duranate 50M") and polypropylene glycol (average functional group number 2.0, weight average molecular weight 400, hydroxyl value 281) ("EXENOL 420" manufactured by AGC Co., Ltd.) and 54 parts by mass of the isocyanate group-terminated urethane prepolymer (Prepolymer 5) by reacting it at 90°C for 2 hours. Obtained.
  • HDI hexamethylene diisocyanate
  • Duranate 50M polypropylene glycol
  • Prepolymer 6 12 parts by mass of hexamethylene diisocyanate (HDI) ("Duranate 50M” manufactured by Asahi Kasei Corporation) and polybutadiene polyol (average functional group number 2.3, weight average molecular weight 3000, hydroxyl value 46) ("POLYVEST HT” manufactured by EVONIK) and 88 parts by mass of the mixture were reacted at 90°C for 2 hours to obtain an isocyanate group-terminated urethane prepolymer (prepolymer 6). rice field.
  • HDI hexamethylene diisocyanate
  • POLYVEST HT polybutadiene polyol
  • Prepolymer 7 In a four-necked flask equipped with a stirrer, a reflux condenser, a thermometer and a nitrogen blowing tube, 33 parts by mass of hexamethylene diisocyanate (HDI) (“Duranate 50M” manufactured by Asahi Kasei Corporation) and castor oil (average functional group number of 2 .7, weight average molecular weight 941, hydroxyl value 161) ("URIC H30" manufactured by Ito Seiyu Co., Ltd.) and 68 parts by mass of the isocyanate group-terminated urethane prepolymer (prepolymer 7) were reacted at 90°C for 2 hours. Obtained.
  • HDI hexamethylene diisocyanate
  • Carboxylic acid 1 200 g (1.0 mol) of tridecyl alcohol and 5 g of potassium hydroxide as a catalyst were placed in an autoclave equipped with a temperature controller equipped with a stirrer, a thermometer, a nitrogen inlet tube, a raw material inlet tube, and a decompression exhaust tube. After charging, the atmosphere in the autoclave was replaced with nitrogen, and 440 g (10 mol) of ethylene oxide was successively introduced under the conditions of a pressure of 0.15 MPa and a temperature of 130° C., followed by neutralization with acetic acid.
  • Carboxylic acid 2 200 g (1.0 mol) of tridecyl alcohol and 5 g of potassium hydroxide as a catalyst were placed in an autoclave equipped with a temperature controller equipped with a stirrer, a thermometer, a nitrogen inlet tube, a raw material inlet tube, and a decompression exhaust tube. After charging, the atmosphere in the autoclave was replaced with nitrogen, and 440 g (10 mol) of ethylene oxide was successively introduced under the conditions of a pressure of 0.15 MPa and a temperature of 130° C., followed by neutralization with acetic acid. Then, 156 g (1 mol) of suberic anhydride is reacted at 120° C.
  • carboxylic acid 2 of general formula (3) (wherein R 3 : tridecyl, A 3 O: EO, n: 10, k : 1, X: -CO-(CH 2 ) 6 -, Z: -COOH).
  • [Weight average molecular weight and number average molecular weight] It is a value calculated from the elution time of a measurement sample using a calibration curve prepared from the molecular weight of standard polystyrene and the elution time measured by the GPC method (gel permeation chromatography method).
  • TSKgel Hxl Tosoh Corporation
  • the mobile phase was THF (tetrahydrofuran)
  • the mobile phase flow rate was 1.0 mL/min
  • the column temperature was 40°C
  • the sample injection volume was 50 ⁇ L
  • the sample concentration was Measurement was performed under the condition of 0.2% by mass.
  • the isocyanate content is measured according to A method of JIS K1603-1:2007, and the isocyanate value is calculated by the following formula from the obtained isocyanate content.
  • 56.11 Molecular weight of potassium hydroxide 1000: Conversion factor from g to mg 42.02: Molecular weight of NCO 100: Conversion factor from percentage to /g
  • Polyol-containing compositions A1-7 were prepared according to the formulations (% by mass) shown in Table 1 below, and isocyanate-containing compositions B1-21 were prepared according to the formulations (% by mass) shown in Table 2 below.
  • the isocyanate-containing compositions B1-21 were evaluated for storage stability.
  • polyol-containing compositions A1 to 7 and isocyanate-containing compositions B1 to 21 were mixed in the combinations and volume mixing ratios shown in Table 3 below, and the miscibility of the two was evaluated.
  • the hardness of the cured product was measured.
  • the storage stability, mixability, and hardness measurement/evaluation methods are as follows.
  • Comparative Example 1 the hardness of the cured product was high because the polyol constituting the isocyanate group-containing urethane prepolymer had a large average number of functional groups.
  • Comparative Example 2 since the weight-average molecular weight of the polyol constituting the isocyanate group-containing urethane prepolymer was small, the isocyanate-containing composition solidified after being stored at 60°C for one month, resulting in low storage stability.
  • Comparative Example 3 since the isocyanate-containing composition did not contain a compound (d) such as a phosphate ester or an ammonium sulfate salt, the storage stability was lowered.
  • Comparative Example 4 since the isocyanate-containing composition did not contain an inorganic filler, the isocyanate-containing composition and the polyol-containing composition were poorly mixed. In Comparative Example 5, since the isocyanate-containing composition did not contain a plasticizer, the storage stability was poor, and the miscibility with the polyol-containing composition was also poor.
  • the isocyanate-containing composition has excellent storage stability, has good miscibility with the polyol-containing composition, and has a hardness of 60 or less after curing, which is good. good results were obtained.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

La présente invention améliore, dans une composition de résine de polyuréthane contenant une charge inorganique, la miscibilité d'une composition contenant un isocyanate par rapport à une composition contenant un polyol tout en supprimant la réduction de la stabilité au stockage de la composition contenant un isocyanate.　Une composition contenant un isocyanate selon un mode de réalisation de la présente invention est destinée à être utilisée en tant que composant polyisocyanate pour une composition de résine de polyuréthane de type à réaction en deux parties, et contient : un prépolymère d'uréthane contenant un groupe isocyanate obtenu en provoquant une réaction entre un polyisocyanate et un polyol ayant un nombre moyen de groupes fonctionnels de 2,5 ou moins et un poids moléculaire moyen en poids de 700 ou plus ; une charge inorganique ; un agent plastifiant ; et au moins un élément sélectionné dans le groupe constitué par des composés représentés par la formule générale (1) et/ou des composés représentés par la formule générale (3).
PCT/JP2022/019775 2021-05-17 2022-05-10 Composition contenant un isocyanate et composition de résine de polyuréthane de type à réaction en deux parties WO2022244650A1 (fr)

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JP2008222773A (ja) * 2007-03-09 2008-09-25 Auto Kagaku Kogyo Kk ポリウレタン系硬化性樹脂組成物及びこれからなる被覆材
JP2016008301A (ja) * 2014-06-26 2016-01-18 東ソー株式会社 産業機械部品部材に用いるポリウレタンエラストマー形成性組成物、およびそれを用いた産業機械部品

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008222773A (ja) * 2007-03-09 2008-09-25 Auto Kagaku Kogyo Kk ポリウレタン系硬化性樹脂組成物及びこれからなる被覆材
JP2016008301A (ja) * 2014-06-26 2016-01-18 東ソー株式会社 産業機械部品部材に用いるポリウレタンエラストマー形成性組成物、およびそれを用いた産業機械部品

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