WO2024004715A1 - Adhésif de durcissement à deux composants à base d'uréthane - Google Patents

Adhésif de durcissement à deux composants à base d'uréthane Download PDF

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WO2024004715A1
WO2024004715A1 PCT/JP2023/022420 JP2023022420W WO2024004715A1 WO 2024004715 A1 WO2024004715 A1 WO 2024004715A1 JP 2023022420 W JP2023022420 W JP 2023022420W WO 2024004715 A1 WO2024004715 A1 WO 2024004715A1
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polyol
tolylene diisocyanate
group
polyisocyanate
glycerol ester
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PCT/JP2023/022420
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Japanese (ja)
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肇 菅沼
岳 渡辺
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Dic株式会社
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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
    • 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
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—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
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/44—Polycarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—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
    • C08G18/58—Epoxy resins
    • 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
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes

Definitions

  • the present invention relates to a urethane-based two-part curable adhesive using a glycerol ester polyol having a methylol group.
  • Urethane adhesives exhibit high strength and, due to the unique flexibility of urethane, can be used to bond dissimilar materials such as metals and plastics, so they are widely used in a variety of fields.
  • resin materials such as fiber-reinforced plastics (FRP) have been used in place of steel plates in order to reduce weight, and this has led to a demand for urethane adhesives with higher performance. It is being
  • the plant-derived polyol disclosed in Patent No. 5398715 is a polyol having secondary hydroxyl groups derived from castor oil, and the polyols having secondary hydroxyl groups are less likely to be polyisocyanate than the polyols having primary hydroxyl groups.
  • 2008-504287 discloses a polyol obtained from hydroformylated soybean oil, but soybean oil has a low oleic acid content of 25% and has an ideal crosslinked structure due to reaction with polyisocyanate. There was a problem that a cured urethane product having the following properties could not be obtained, and the hardness and physical properties were poor.
  • Japanese Patent Publication No. 2021-536501 discloses a polyol having a primary hydroxyl group obtained by hydroformylating and hydrogenating triacylglycerol derived from algae. However, this document does not disclose a polyurethane adhesive that satisfies the requirements at a practical level.
  • Patent No. 5398715 Special Publication No. 2008-504287 Special Publication No. 2021-536501
  • An object of the present invention is to provide a urethane-based two-component curing adhesive consisting of a glycerol ester polyol and a polyisocyanate, which reduces the amount of highly reactive and highly toxic amine reaction accelerators and is also considerate to the health of workers. That's true.
  • the present inventors have found that by using a specific glycerol ester polyol as a curing agent, it is possible to improve curability and adhesiveness without using reaction accelerators such as amines.
  • the present invention was completed based on the discovery that adhesive performance such as strength was significantly improved.
  • Two-component curable adhesive comprising a base agent containing an isocyanate group-containing urethane prepolymer obtained from the reaction of polyisocyanate and polyol A and/or tolylene diisocyanate-based polyisocyanate, and a curing agent containing a glycerol ester-based polyol.
  • the tolylene diisocyanate-based polyisocyanate includes tolylene diisocyanate, an adduct type polyisocyanate consisting of tolylene diisocyanate and a polyhydric alcohol, a nurate type polyisocyanate obtained by polymerizing tolylene diisocyanate, and an allophanate type polyisocyanate obtained from tolylene diisocyanate and alcohol.
  • the glycerol ester polyol includes a compound represented by the following formula (1), A two-part curable adhesive, wherein the content of fatty acid residues derived from oleic acid in the glycerol ester polyol is 70 mol% or more based on the total amount of fatty acid residues in the glycerol ester polyol.
  • One of X 1 and X 2 is hydrogen, and the other is a methylol group
  • One of X 3 and X 4 is hydrogen, and the other is a methylol group
  • One of X 5 and X 6 is hydrogen, and the other is a methylol group.
  • the polyol A is at least one selected from the group consisting of polyether polyols, polyester polyols, polyacrylic polyols, polyolefin polyols, polycarbonate polyols, epoxy resin polyols, low-molecular polyhydric alcohols, and partially modified products thereof.
  • the polyisocyanate is diphenylmethane diisocyanate, polymeric diphenylmethane diisocyanate, modified diphenylmethane diisocyanate, tolylene diisocyanate, an adduct type polyisocyanate consisting of tolylene diisocyanate and a polyhydric alcohol, a nurate type polyisocyanate of tolylene diisocyanate, and tolylene diisocyanate. and alcohol.
  • the glycerol ester polyol is obtained from at least one member selected from the group consisting of triolein, olive oil, high oleic acid safflower oil, high oleic camellia oil, and algae-derived high oleic oil and fat, [1] A two-component curing adhesive described in .
  • the shear strength of the completely cured adhesive is 15 MPa or more when measured according to JIS K6859, and the shear strength 7 days after the curing reaction is taken as 100%.
  • the two-component curing adhesive is made of a base material containing a urethane prepolymer and/or tolylene diisocyanate-based polyisocyanate produced by the reaction of polyisocyanate and polyol A, and a curing agent containing a glycerol ester-based polyol. Adhesive performance such as fast curing properties and adhesive strength can be further improved. Furthermore, since the adhesive of the present invention has high curability, the amount of reaction accelerators such as highly toxic amines can be reduced, and by using bio-derived triacylglycerol, the amount of petroleum raw materials can be reduced. Can be done.
  • FIG. 1 shows the measurement results of polyol 5 by LC/CAD (liquid chromatography/charged particle detector).
  • the adhesive of the present invention is a two-component curing adhesive containing a base agent and a curing agent. By appropriately combining the base resin and the curing agent, it is possible to further accelerate curing and improve adhesive performance.
  • the main ingredient used in the two-component curable adhesive of the present invention is an isocyanate group-containing urethane prepolymer obtained from the reaction of polyisocyanate and polyol A, and/or tolylene diisocyanate (TDI)-based polyisocyanate (hereinafter referred to as TDI-based polyisocyanate). ). That is, the main agent contains either a urethane prepolymer and a TDI polyisocyanate, a urethane prepolymer, or a TDI polyisocyanate.
  • TDI-based polyisocyanate tolylene diisocyanate
  • TDI polyisocyanate consists of tolylene diisocyanate, adduct type polyisocyanate made of tolylene diisocyanate and polyhydric alcohol, nurate type polyisocyanate obtained by polymerizing tolylene diisocyanate, and allophanate type polyisocyanate obtained from tolylene diisocyanate and alcohol. at least one selected from the group.
  • a urethane prepolymer obtained by the reaction of polyisocyanate and polyol A is included as the main ingredient, the reaction of the polyisocyanate and polyol A yields a urethane prepolymer containing a plurality of isocyanate groups at the molecular ends.
  • the number average molecular weight of the urethane prepolymer is preferably 500 to 10,000, more preferably 1,000 to 5,000.
  • Preferred polyisocyanates used in the urethane prepolymer of the present invention include aromatic polyisocyanates, aliphatic polyisocyanates, and alicyclic polyisocyanates, and two or more of these can be used in combination.
  • aromatic polyisocyanates include tolylene diisocyanate (TDI) [for example, 2,4-tolylene diisocyanate (2,4-TDI), 2,6-tolylene diisocyanate (2,6-TDI), etc.], diphenylmethane diisocyanate (MDI) [for example, 4,4'-diphenylmethane diisocyanate (4,4'-MDI), 2,4'-diphenylmethane diisocyanate (2,4'-MDI), etc.], 1,4-phenylene diisocyanate, polymethylene polyphenylene Polyisocyanate, xylylene diisocyanate (XDI), tetramethylxylylene diisocyanate (TMXDI), tolidine diisocyanate (TODI), 1,5-naphthalene diisocyanate (NDI), triphenylmethane triisocyanate, polymeric diphenylmethane diisocyanate (polymeric
  • aliphatic or alicyclic polyisocyanates examples include hexamethylene diisocyanate (HDI), trimethylhexamethylene diisocyanate (TMHDI), lysine diisocyanate, norbornane diisocyanate (NBDI), transcyclohexane-1,4-diisocyanate, and isophorone diisocyanate (IPDI). , bis(isocyanatomethyl)cyclohexane (H6XDI), dicyclohexylmethane diisocyanate (H12MDI), carbodiimide-modified products, isocyanurate-modified products of these, and the like.
  • HDI hexamethylene diisocyanate
  • TMHDI trimethylhexamethylene diisocyanate
  • NBDI norbornane diisocyanate
  • IPDI isophorone diisocyanate
  • H6XDI bis(isocyanatomethyl)cyclohexan
  • the polyisocyanate used in the present invention is more preferably MDI, polymeric MDI, modified MDI, TDI, adduct type polyisocyanate obtained from TDI and polyhydric alcohol, nurate type polyisocyanate of TDI, allophanate type polyisocyanate obtained from TDI and alcohol. , or a combination thereof.
  • the polyol A used in the present invention is, for example, a polyether polyol, a polyester polyol, a polycarbonate polyol, a polyacrylic polyol, an alkylene polyol, an epoxy resin polyol, a polyolefin polyol, a low-molecular polyhydric alcohol, or a partially modified product thereof. It's a combination.
  • Polyol A used in the present invention preferably contains a polyether polyol.
  • polyether polyol examples include polymers or copolymers formed by combining ethylene oxide, propylene oxide, butylene oxide, alkylene oxide such as tetrahydrofuran, styrene oxide, and the like. Specific examples include polyoxyethylene diol (polyethylene glycol: PEG), polyoxypropylene diol (polypropylene glycol: PPG), polytetramethylene ether polyol (PTMEG), polyoxypropylene triol, and ethylene oxide/propylene oxide copolymer ( diol), ethylene oxide/propylene oxide copolymer (triol), and the like.
  • Low-molecular polyhydric alcohols include ethylene glycol (EG), diethylene glycol, propylene glycol (PG), dipropylene glycol, (1,3- or 1,4-)butanediol, pentanediol, neopentyl glycol, hexanediol. , cyclohexanedimethanol, glycerin, 1,1,1-trimethylolpropane (TMP), 1,2,5-hexanetriol, low molecular weight polyols such as pentaerythritol, and saccharides such as sorbitol.
  • polyester polyol examples include condensed polyester polyols, lactone polyester polyols, and the like.
  • the condensed polyester polyol is, for example, a combination of the above-mentioned low-molecular-weight polyhydric alcohol and a polybasic carboxylic acid (glutaric acid, adipic acid, azelaic acid, fumaric acid, maleic acid, pimelic acid, suberic acid, sebacic acid, phthalic acid, It is a reaction product with terephthalic acid, isophthalic acid, dimer acid, pyromellitic acid, oligomer acid, etc.).
  • the lactone-based polyester polyol is, for example, a polycaprolactone polyol obtained by ring-opening polymerization of a lactone such as ⁇ -caprolactone, ⁇ -methyl- ⁇ -caprolactone, and ⁇ -methyl- ⁇ -caprolactone.
  • Polycarbonate polyols include, for example, polyols (1,6-hexanediol, diethylene glycol, triethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, pentanediol, 3-methyl-1 , 5-pentanediol, octanediol, 1,4-butynediol, dipropylene glycol, tripropylene glycol, various saturated or unsaturated glycols such as polytetramethylene ether glycol, 1,4-cyclohexane diglycol, 1, It is a polyol obtained by reacting an alicyclic glycol such as 4-cyclohexanedimethanol with a dialkyl carbonate (dimethyl carbonate, diethyl carbonate, etc.), ethylene carbonate, diphenyl carbonate, etc.
  • a polyacrylic polyol is, for example, a polymerizable acrylic monomer having one or more hydroxyl groups in one molecule and other monomers copolymerizable therewith (for example, other (meth)acrylic acid monomers and/or other monomers). unsaturated monomers).
  • Specific examples of polyacrylic polyols include copolymers of polymerizable acrylic monomers and vinyl monomers having one or more hydroxyl groups in one molecule, polymerizable acrylic monomers and lactones such as ⁇ -caprolacrone and ⁇ -valerolactone. Examples include ring-opening polymerization adducts with.
  • polymerizable acrylic monomers examples include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, and (meth)acrylate.
  • Examples include chloropropyl.
  • vinyl monomers include monoesters of (meth)acrylic acid and glycols having 2 to 10 carbon atoms (hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, etc.), carboxyl group-containing vinyl monomers, and amide.
  • vinyl monomers glycidyl group-containing vinyl monomers, styrene and its derivatives, acrylonitrile, vinyltoluene, vinyl chloride, vinyl acetate, and the like.
  • alkylene polyol examples include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, and 1,5-pentanediol.
  • polyolefin polyol examples include polyethylene polyol, polypropylene polyol, polybutadiene polyol, hydrogenated polybutadiene polyol, polyisoprene polyol, hydrogenated polyisoprene polyol, and the like.
  • epoxy resin polyols include diglycidyl compounds (bisphenol A epoxy resin, bisphenol F epoxy resin, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, hexahydrophthalic acid diglycidyl ether, glycidyl ester, etc.), bisphenol compounds (bisphenol A, bisphenol F, biphenol, etc.), and/or polybasic carboxylic acids (glutaric acid, adipic acid, azelaic acid, fumaric acid, maleic acid, pimelic acid, suberic acid, sebacic acid, phthalic acid, terephthalic acid, isophthalic acid, dimer acid, pyromellitic acid, oligomer acid, etc.), and/or polyamines (monomethylamine, monoethylamine, monopropylamine, monobutylamine, mono
  • the main ingredient may contain a polyamine compound as a compound having an active hydrogen group as a component of the urethane prepolymer, and may also contain additives within a range that does not impair the purpose of the present invention.
  • polyamine compounds include aliphatic polyamines (ethylene diamine, propylene diamine, butylene diamine, diethylene triamine, diethylaminopropylamine, triethylene tetramine, etc.), aromatic polyamines (diaminodiphenylmethane, diaminodiphenyl sulfone, benzidine, etc.), polyether polyamines (polyoxy propylene diamine, etc.). Since amines are highly toxic, in the present invention, the polyamine compound is preferably 0.1 mol% or less, more preferably 0.01 mol% or less, and even more preferably contains no polyamine compound at all. do not have.
  • additives include additives commonly used in urethane adhesives, such as fillers (silica such as fumed silica and calcined silica, diatomaceous earth, talc, magnesium oxide, calcium carbonate, heavy calcium carbonate, calcined clay, carbon black, etc.), plasticizers (diisononyl phthalate, dioctyl adipate, isodecyl succinate, diethylene glycol dibenzoate, pentaerythritol ester, etc.), anti-aging agents (hindered phenol compounds, etc.), antioxidants (butylated hydroxytoluene, butylhydroxyanisole, etc.), UV absorbers, flame retardants, surfactants, dispersants, dehydrating agents, adhesion promoters (phenolic resins, rosin resins, etc.), antistatic agents (quaternary ammonium salts; polyglycols, ethylene oxides) derivatives, etc.).
  • fillers such as fumed silica
  • the amounts of polyisocyanate and polyol A in the base urethane prepolymer are preferably such that the isocyanate groups in the polyisocyanate are in excess of the hydroxyl groups in polyol A.
  • the equivalent ratio of isocyanate groups in the polyisocyanate to the hydroxyl groups in polyol A (isocyanate groups/hydroxyl groups) is preferably 1.5 to 5.0, more preferably 2.5 to 4.0.
  • Polyisocyanate is blended and reacted preferably at 50 to 110°C for 4 to 20 hours, more preferably at 70 to 100°C for 6 to 12 hours.
  • the reaction of the polyisocyanate and polyol A preferably reacts all of the polyol A to form the urethane prepolymer.
  • the obtained base resin preferably unreacted polyisocyanate exists as residual polyisocyanate.
  • the base material may contain residual polyisocyanate in addition to the urethane prepolymer.
  • the content of isocyanate groups (NCO%: weight %) in the main resin obtained by reacting polyisocyanate and polyol A is preferably 2 when measured by a method based on JIS K-1603-1:2007. 0 to 15.0%, more preferably 4.0 to 12.0%.
  • the curing agent contains a glycerol ester polyol having a methylol group.
  • the glycerol ester polyol having a methylol group quickly reacts with the urethane prepolymer and unreacted residual polyisocyanate in the base material to form a cured product.
  • the glycerol ester polyol used in the present invention contains a methylol group in the molecule. That is, the glycerol ester polyol used in the present invention contains a compound represented by the following formula (1), and the content of fatty acid residues derived from oleic acid in the glycerol ester polyol is as follows: It is 70 mol% or more based on the total amount of fatty acid residues.
  • One of X 1 and X 2 is hydrogen, and the other is a methylol group
  • One of X 3 and X 4 is hydrogen, and the other is a methylol group
  • One of X 5 and X 6 is hydrogen, and the other is a methylol group.
  • the glycerol ester polyol used in the present invention may further contain a compound represented by the following formula (2-1) and/or formula (2-2).
  • One of X 1 and X 2 is hydrogen, and the other is a methylol group
  • One of X 3 and X 4 is hydrogen, and the other is a methylol group
  • One of X 5 and X 6 is hydrogen, and the other is a methylol group
  • R and R' are each independently a residue of an unsaturated fatty acid or a saturated fatty acid other than the group represented by the following formula (3), or hydrogen.
  • R and R' in formula (3) include unsaturated fatty acids (for example, myristoleic acid, palmitoleic acid, sapienoic acid, elaidic acid, vaccenic acid, petroselic acid, eicosenoic (gondoic) acid, paulic acid, gadoleic acid, Erucic acid, brassic acid, nervonic acid, hexadecatrienoic acid, linoleic acid, linolelaidic acid, ⁇ -linolenic acid, pinolenic acid, stearidonic acid, eicosadienoic acid, mead acid, eicosatrienoic acid, ⁇ -linolenic acid, ⁇ - Linolenic acid, dihomo-gamma-linolenic acid, podocarpic acid, arachidonic acid, eicosatetraenoic acid, eicosapentaenoic acid, heneicosapentaen
  • the content of fatty acid residues derived from oleic acid in the glycerol ester polyol is based on the total amount of fatty acid residues in the glycerol ester polyol (i.e., the total amount of fatty acid residues in the glycerol ester polyol is 100 mol). %), preferably 70 mol% or more, more preferably 80 mol% or more, still more preferably 90 mol% or more.
  • the amount of triacylglycerol represented by the above formula (1) and triacylglycerol and/or diacylglycerol represented by the above formulas (2-1) and (2-2) in the glycerol ester polyol is , preferably 80 mol% or more, more preferably 90 mol% or more, based on the total amount of glycerol ester polyol.
  • the glycerol ester polyol used in the present invention has a high content of oleic acid residues and high regularity. Furthermore, since it has a primary hydroxyl group (methylol group) in its molecule, it has high reactivity (curability) with isocyanate groups. Therefore, rapid adhesion (curing) can be achieved without using a reaction accelerator (such as a tertiary amine) or a curing catalyst (such as a metal catalyst or an amine catalyst).
  • a reaction accelerator such as a tertiary amine
  • a curing catalyst such as a metal catalyst or an amine catalyst
  • the curing agent may contain polyols other than the glycerol ester polyols represented by formula (1), formula (2-1), and formula (2-2), polyamine compounds, additives, etc. that do not impair the purpose of the present invention. It may be contained within a range.
  • the other polyols include polyols that can be used in the polyol A above.
  • the polyamine compound include compounds similar to the polyamine compound that can be used as the main agent, but since amines are highly toxic, the polyamine compound in the curing agent preferably has a ratio of 0.1 to the glycerol ester polyol. It is less than mol %, more preferably less than 0.01 mol %, and even more preferably the curing agent does not contain any polyamine compound.
  • the same additives as those that can be used in the main ingredient can be added.
  • the glycerol ester polyol in the curing agent has an equivalent ratio of isocyanate groups in the base agent to hydroxyl groups in the glycerol ester polyol in the curing agent (isocyanate group/hydroxyl group) of preferably 0.3 to 3.0, more preferably 0. Blend so that the ratio is .5 to 2.0. If the amount of isocyanate groups exceeds the above range relative to the amount of hydroxyl groups in the glycerol ester polyol, the elastic modulus of the adhesive tends to decrease. When it decreases beyond this range, the adhesive strength of the adhesive tends to decrease.
  • the equivalent ratio of the isocyanate group in the base resin to the hydroxyl group in the curing agent is preferably 0.3 to 3.0, more preferably 0.5 to 2.0. If the amount of isocyanate groups exceeds the above range relative to the amount of hydroxyl groups in the curing agent, the elastic modulus of the adhesive tends to decrease. When the adhesive strength of the adhesive decreases beyond this value, the adhesive strength of the adhesive tends to decrease.
  • the glycerol ester used as a raw material for the curing agent contains at least one carbon-carbon double bond in the fatty acid residue.
  • preferably two fatty acid residues are oleic acid residues, more preferably three fatty acid residues are oleic acid residues.
  • the glycerol ester used in the present invention may contain triacylglycerol and/or diacylglycerol derived from a diolein compound other than triolein.
  • the content of fatty acid residues derived from oleic acid in the glycerol ester used in the present invention is preferably 70 mol% or more, more preferably 80 mol% or more, and even more preferably It is 90 mol% or more.
  • the glycerol ester used in the present invention can be obtained from, for example, triolein, olive oil, high oleic safflower oil, high oleic camellia oil, algae-derived high oleic fat or oil, or a combination of one or more of these, but is not limited thereto.
  • the glycerol ester used as a raw material is preferably derived from non-petroleum.
  • Non-petroleum-derived raw materials include bio-derived raw materials.
  • bio refers to biological resources such as animals, plants, and microorganisms.
  • Microorganisms are a general term for microscopic microorganisms.
  • microorganisms include eukaryotes such as unicellular algae (including microalgae) and eukaryotic fungi (molds and yeast), and prokaryotes such as blue-green algae and bacteria.
  • eukaryotes such as unicellular algae (including microalgae) and eukaryotic fungi (molds and yeast), and prokaryotes such as blue-green algae and bacteria.
  • microalgae one or more of the following genera and species are preferably used to produce glycerol esters: Examples of microalgae include Chlorella species, Pseudochlorella species, Heterochlorella species, Prototheca species, Arthrospira species, Euglena species, Nanochloropsis species, and Phaeoda.
  • Species of the genus ctylum species of the genus Chlamydomonas, Scenedesmus species, Ostreococcus species, Selenastrum species, Haematococcus species, Nitzschia, Dunaliella, Navicula species, Trebouxia species, Pseudotrebou xia species, Vavicula species, Bracteococcus species, Gomphonema species of the genus Watanabea, species of the genus Botryococcus, species of the genus Tetraselmis and species of the genus Isochrysis.
  • yeasts one or more of the following genera and species are preferably used to produce glycerol esters:
  • yeast include Candida species, Cryptococcus species, Debaromyces species, Endomycopsis species, Geotrichum species, Hyphopicia species, Lipomyces species, Pichia species, Rhodospori Rhodotorula, a species of the genus Dium Species of the genus Sporobolomyces, spp. Starmerella, spp. Torulaspora, spp. Trichosporon, spp. Wickerhamomyces, spp. Yarrowia, and spp. Zygoascus.
  • bacteria one or more of the following genera and species are preferably used to produce glycerol esters:
  • bacteria include Flavimonas oryzihabitans, Pseudomonas aeruginosa, species of the genus Morococcus, Rhodobacter sphaeroides, Rhodococcus opacus, Rhodococcus erythropolis, Streptomyces jeddahensis, species of the genus Ochrobactrum, species of the genus Arthrobacter, species of the genus Nocardia, species of the genus Mycobacteria, species of the genus Gordonia. species of the genus Catenisphaera and species of the genus Dietzia.
  • Hydroformylation is, for example, the reaction of glycerol esters with unsaturated fatty acid residues with carbon monoxide and hydrogen, resulting in the addition of formyl (CHO) groups and hydrogen to the carbon-carbon double bonds of unsaturated fatty acid residues.
  • Hydroformylation can be carried out, for example, by pressurizing a reaction vessel containing the glycerol ester and catalyst to about 500 psi to about 1,500 psi with a synthesis gas of carbon monoxide and hydrogen at a temperature of about 40° C. to about 200° C. for about 1 hour to about 100 psi. This can be done by time reaction.
  • Catalysts used for hydroformylation include cobalt-based catalysts (such as cobalt hydridetetracarbonyl catalysts, cobalt phosphine catalysts, cobalt catalysts supplemented with noble metals (e.g. palladium, ruthenium, or platinum)), rhodium-based catalysts (e.g. rhodium phosphine catalyst, acetylacetonato-dicarbonylrhodium(I) (Rh(CO) 2 acac) catalyst, rhodium/cyclohexyldiphenylphosphine (Rh/CHDPP) catalyst, etc.), or any other transition metal-based suitable for hydroformylation.
  • a catalyst etc. can be used.
  • the formyl (CHO) group of the hydroformylated triacylglycerol is reduced to a primary alcohol (methylol group) using hydrogen in the presence of a hydrogenation catalyst.
  • Hydrogenation can be carried out, for example, by reacting at a pressure of about 500 psi to about 1500 psi and a temperature of about 40° C. to about 250° C. for about 1 hour to about 10 hours.
  • the hydrogenation catalyst may be a general hydrogenation catalyst, and for example, a catalyst such as Raney nickel (sponge nickel), urushihara nickel, nickel, palladium, platinum, rhodium, or ruthenium can be used.
  • a catalyst such as Raney nickel (sponge nickel), urushihara nickel, nickel, palladium, platinum, rhodium, or ruthenium can be used.
  • the adhesive of the present invention is a two-component curing adhesive
  • the main ingredient and the curing agent are mixed at the time of use to cause a curing reaction and bond the adhesive.
  • the glycerol ester polyol used as the curing agent has a primary hydroxyl group (methylol group), and the reaction with the isocyanate group proceeds quickly, so a reaction accelerator or curing catalyst is not required for the curing reaction.
  • the curing performance of the two-part curable adhesive of the present invention is based on the appropriate combination of the base agent and the curing agent.
  • polyol A and polyisocyanate as the main ingredients
  • the glycerol ester polyol as the curing agent
  • the appropriate blending ratio of polyisocyanate and polyol A, and polyisocyanate and glycerol ester polyol are based on the appropriate selection of polyol A and polyisocyanate as the main ingredients, the glycerol ester polyol as the curing agent, and the appropriate blending ratio of polyisocyanate and polyol A, and polyisocyanate and glycerol ester polyol.
  • Synthesis of Polyol 1 100 g of olive oil (oleic acid content: 75 mol%, iodine value: 80) was placed in a stainless steel high-pressure reaction vessel equipped with a temperature controller, a gas-filled terminal, and a stirrer. After adding 0.1 g of dicarbonium rhodium (I) (manufactured by Sigma-Aldrich) and 0.5 g of triphenylphosphine (manufactured by Tokyo Kasei Co., Ltd.) as a ligand, the system was flushed with synthesis gas (manufactured by Tokyo Kasei Co., Ltd.).
  • I dicarbonium rhodium
  • triphenylphosphine manufactured by Tokyo Kasei Co., Ltd.
  • the obtained polyol 1 had a hydroxyl value of 154 mgKOH/g and a viscosity of 1700 mPa ⁇ s.
  • Comparative Synthesis Examples 1 and 2 Synthesis of Comparative Polyols 1 and 2 Comparative polyols 1 and 2 were synthesized in the same manner as Synthesis Example 1, except that the oils and fats listed in Table 3 were used in place of the olive oil in Synthesis Example 1. The results are shown in Table 3.
  • Preparation Example 1 Preparation of polyol curing agent (1) Polyol 1 (667 parts by mass), fumed silica (AEROSIL (registered trademark) 200 manufactured by EVONIC) (10 parts by mass), calcium carbonate (CaCO 3 ) (Omi Chemical Light calcium carbonate (manufactured by Kogyo Co., Ltd.) (323 parts by mass) was added to a container and thoroughly stirred and mixed with a disper until the solid content disappeared.Then, the mixture was defoamed under vacuum and a white polyol curing agent (1 ) was obtained.
  • AEROSIL registered trademark
  • CaCO 3 Omi Chemical Light calcium carbonate
  • Comparative Preparation Examples 1 to 5 Preparation of Comparative Curing Agents (1) to (5) Comparative Polyol 1 to Comparative Polyol 2 in place of Polyol 1, and Actol (registered trademark) T-1000 (manufactured by Mitsui Chemicals, Inc.) Polypropylene glycol, hydroxyl value: 164 mgKOH/g), PTMG-650 (polytetramethylene glycol, manufactured by Mitsubishi Chemical Corporation, hydroxyl value: 172 mgKOH/g), and castor oil (castor oil HS2G-160R, manufactured by Toyokuni Oil Co., Ltd.), Comparative curing agents (1) to (5) were prepared in the same manner as in Preparation Example 1, except that hydroxyl value: 158 mgKOH/g) was used. The composition is shown in Table 5.
  • T-2000, Mw: 2000, number of functional groups: 3 (637 parts by mass) was added in portions over 2 hours.
  • the inside of the system was heated to 80°C and reacted for 6 hours to obtain urethane prepolymer (1).
  • the NCO% of the obtained urethane prepolymer (1) was 8.0%.
  • Actol T-1000 Actol (registered trademark) T-1000 (Mw: 1000, number of functional groups: 3) (PP polyol manufactured by Mitsui Chemicals, Inc.)
  • Actol T-2000 Actol (registered trademark) T-2000 (Mw: 2000, number of functional groups: 3)
  • Actol ED-56 Actol (registered trademark) ED-56 (Mw: 2000, number of functional groups: 2)
  • Millionate MT MDI: diphenylmethane diisocyanate, NCO%: 33.2) (manufactured by Tosoh Corporation) Coronate 1391 (MDI polyisocyanate, NCO%: 33.2) (manufactured by Tosoh Corporation)
  • ⁇ Evaluation method> ⁇ Tensile shear test>> The tensile shear strength was measured at 25° C. using AUTOGRAPH AG-XPlus 100 kN (manufactured by Shimadzu Corporation) according to a method based on JIS K6859 (creep rupture test for adhesives).
  • Adhesive 1 was prepared and applied using a two-liquid micro-quantity metering, mixing and discharging device having a temperature raising device and a static mixer nozzle.
  • the above adhesive 1 is obtained from a vacuum defoamed urethane prepolymer (1) and a polyol curing agent (1), the mixing mass ratio of which is 1/1 (isocyanate group/hydroxyl group equivalent ratio: 1/1), The mixing temperature was 50°C.
  • the adhesive strength was evaluated by tensile shear strength, and the drying time (curing rate) was determined by the ratio of the tensile shear strength after 1 day when the tensile shear strength after 7 days of curing was taken as 100%. evaluated. Table 7 shows the results.
  • the adhesive of the present invention using polyols 1 to 6 has a tensile shear strength of 19 to 25 MPa after 7 days after being completely cured, and a ratio of the tensile shear strength after 1 day when the tensile shear strength after 7 days is taken as 100%.
  • soybean-derived comparative polyol 1 (comparative curing agent 1)
  • rapeseed oil-derived comparative polyol 2 (comparative curing agent 2)
  • polypropylene glycol (comparative curing agent 3)
  • Adhesives of comparative examples using polytetramethylene glycol (comparative curing agent 4) or castor oil (comparative curing agent 5) (tensile shear strength after 7 days: 5 to 11 MPa, tensile shear strength after 7 days as 100%) (Tensile shear strength ratio after 1 day: 57-73%), the adhesive strength and curing speed were significantly improved.

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  • Medicinal Chemistry (AREA)
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Abstract

La présente invention concerne un adhésif de durcissement à deux composants à base d'uréthane présentant une capacité de durcissement et un pouvoir adhésif élevés et utilisant, comme agent de durcissement, un polyol à base d'ester de glycérol.　L'adhésif de durcissement à deux composants de la présente invention comprend : un agent principal comprenant un prépolymère d'uréthane contenant un groupe isocyanate obtenu à partir d'une réaction entre un polyisocyanate et un polyol a, et/ou un polyisocyanate à base de diisocyanate de tolylène ; et un agent de durcissement comprenant un polyol à base d'ester de glycérol spécifique. Le polyisocyanate à base de diisocyanate de tolylène comprend au moins un type choisi dans le groupe constitué du diisocyanate de tolylène, d'un polyisocyanate de type adduit comprenant du diisocyanate de tolylène et un alcool polyhydrique, d'un polyisocyanate de type nurate obtenu par polymérisation du diisocyanate de tolylène et d'un polyisocyanate de type allophanate obtenu à partir du diisocyanate de tolylène et d'un alcool.
PCT/JP2023/022420 2022-06-30 2023-06-16 Adhésif de durcissement à deux composants à base d'uréthane WO2024004715A1 (fr)

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JP2021536501A (ja) * 2018-08-30 2021-12-27 チェッカースポット， インコーポレイテッド ヒドロホルミル化されたトリグリセリドおよびその使用

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JP2021536501A (ja) * 2018-08-30 2021-12-27 チェッカースポット， インコーポレイテッド ヒドロホルミル化されたトリグリセリドおよびその使用

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"Polymeric Materials", 1 December 2009, TRANSWORLD RESEARCH NETWORK, TRIVANDRUM, ISBN: 978-81-7895-398-4, article ZLATANIC, ALISA: "Poly(urethane)s from model triglycerides.", pages: 103 - 129, XP009551964 *
PETROVIC Z S, ZHANG W, JAVNI I: "STRUCTURE AND PROPERTIES OF POLYURETHANES FROM TRIACYLGLYCERIDE POLYOLS BY OZONOLYSIS", BIOMACROMOLECULES, AMERICAN CHEMICAL SOCIETY, US, vol. 6, no. 2, 1 January 2005 (2005-01-01), US , pages 713 - 719, XP003015363, ISSN: 1525-7797, DOI: 10.1021/bm049451s *

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