WO2024004813A1 - Composition de matériau de revêtement à base d'uréthane - Google Patents

Composition de matériau de revêtement à base d'uréthane Download PDF

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WO2024004813A1
WO2024004813A1 PCT/JP2023/023074 JP2023023074W WO2024004813A1 WO 2024004813 A1 WO2024004813 A1 WO 2024004813A1 JP 2023023074 W JP2023023074 W JP 2023023074W WO 2024004813 A1 WO2024004813 A1 WO 2024004813A1
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polyol
glycerol ester
hydrogen
group
ester polyol
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PCT/JP2023/023074
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English (en)
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
    • C08G18/28—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
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes

Definitions

  • the present invention relates to a urethane coating composition using a glycerol ester polyol as a polyol.
  • Urethane paints are widely used because of their high hardness and good gloss.
  • urethane paints have low flexibility and elasticity, insufficient water and chemical resistance, slow curing speed at low temperatures, and skin irritation due to the amine hardener used as a hardener. There are problems such as:
  • 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.
  • Japanese Patent Publication 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 the reaction with polyisocyanate creates an ideal crosslinked structure. 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.
  • PCT International Publication No. 2021-536501 discloses a polyol having a primary hydroxyl group (methylol group) obtained by hydroformylating and hydrogenating triacylglycerol derived from algae. However, this document does not specifically disclose a urethane coating composition using a polyol having a methylol group.
  • Patent No. 5398715 Special Publication No. 2008-504287 Special Publication No. 2021-536501
  • the present inventors found that by using a specific glycerol ester polyol, the physical properties of the coating film were significantly improved without using reaction accelerators such as amines. They have discovered that this is the case and have completed the present invention.
  • a urethane coating composition containing a glycerol ester polyol and a polyisocyanate The glycerol ester polyol includes a compound represented by the following formula (1), A urethane coating composition, 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
  • 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.
  • 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.
  • the urethane-based coating composition according to [1], comprising at least one member selected from the group consisting of allophanate-type polyisocyanates obtained from [4]
  • a urethane coating composition comprising a glycerol ester polyol, a polyol other than the glycerol ester polyol, and a polyisocyanate
  • the glycerol ester polyol includes a compound represented by the following formula (1),
  • 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,
  • the content of the glycerol ester polyol is 5 to 50% by mass based on the mass of polyols other than the glycerol ester polyol.
  • Urethane paint composition Urethane paint composition.
  • 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.
  • the polyol other than the glycerol ester polyol is selected from the group consisting of polyether polyol, polyester polyol, polyacrylic polyol, polyepoxy polyol, polyolefin polyol, polycarbonate polyol, partially modified products thereof, and combinations thereof.
  • the polyisocyanate is diphenylmethane diisocyanate, tolylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, and a nurate obtained by polymerizing one or more of the above diisocyanates (i.e., diphenylmethane diisocyanate, tolylene diisocyanate, hexamethylene diisocyanate, and isophorone diisocyanate).
  • uretdione type polyisocyanate obtained by polymerizing one or more of the above diisocyanates, adduct type polyisocyanate obtained from one or more of the above diisocyanates and a polyhydric alcohol, and obtained from one or more of the above diisocyanates and water and/or an amine.
  • [5] comprising at least one selected from the group consisting of buret type polyisocyanate, allophanate type polyisocyanate obtained from one or more of the above diisocyanates and alcohol, polymeric diphenylmethane diisocyanate, and modified diphenylmethane diisocyanate.
  • Urethane paint composition comprising at least one selected from the group consisting of buret type polyisocyanate, allophanate type polyisocyanate obtained from one or more of the above diisocyanates and alcohol, polymeric diphenylmethane diisocyanate, and modified diphenylmethane diisocyanate.
  • the equivalent ratio (isocyanate group/hydroxyl group) of the isocyanate group in the polyisocyanate to the hydroxyl group in the glycerol ester polyol and the polyol other than the glycerol ester polyol is 0.5 to 2.0.
  • the glycerol ester polyol used in the present invention contains a primary hydroxyl group (methylol group), it has high reactivity with isocyanate groups. Furthermore, the proportion of fatty acid residues derived from oleic acid is high, and the molecular structure is highly regular. As a result, the physical properties of the coating composition of the present invention such as drying properties, hardness, adhesion, elastic modulus, and solvent resistance are significantly improved. Furthermore, since the coating composition of the present invention has high reactivity, the amount of reaction accelerators such as highly toxic amines can be reduced, and when bio-derived glycerol ester is used, 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 coating composition of the present invention contains a glycerol ester polyol and a polyisocyanate.
  • the coating composition of the present invention may further contain polyols other than glycerol ester polyols.
  • the coating composition of the present invention may be a one-component coating composition or a two-component coating composition.
  • the coating composition may be composed of a base agent containing a glycerol ester polyol and a curing agent containing a polyisocyanate, and may include a glycerol ester polyol and a polyol other than the glycerol ester polyol.
  • the coating composition may be composed of a main agent containing polyisocyanate and a curing agent containing polyisocyanate.
  • the glycerol ester polyol used in the present invention has a methylol group in the molecule. That is, the glycerol ester polyol used in the present invention is represented by the following formula (1).
  • 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 is preferably 80 mol% or more, more preferably 90 mol% or more, based on the total amount of glycerol ester polyol.
  • the glycerol ester used as a raw material for the main ingredient contains at least one carbon-carbon double bond in an unsaturated fatty acid residue.
  • the fatty acid residue is an oleic acid residue.
  • the glycerol ester used in the present invention may contain triacylglycerol and/or diacylglycerol derived from a diolein compound in addition to triolein, depending on the type of raw material used.
  • 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 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.
  • catalysts such as Raney nickel (sponge nickel), Urushihara nickel, nickel, palladium, platinum, rhodium, and ruthenium can be used.
  • the urethane coating composition of the present invention contains a glycerol ester polyol represented by the above formula (1) and the above formula (2-1) and/or formula (2-2) in a polyol other than the glycerol ester polyol. It may also be included as a reactive diluent. Reactive diluents have functions such as increasing reactivity and adjusting the balance between elasticity and hardness of the paint.
  • polyols other than glycerol ester polyols include polyether polyols, polyester polyols, polyacrylic polyols, polyepoxy polyols, polyolefin polyols, polycarbonate polyols, partially modified products thereof, and combinations thereof.
  • 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.
  • polyester polyol examples include condensed polyester polyols, lactone polyester polyols, and the like.
  • Condensed polyester polyols include, for example, low-molecular polyhydric alcohols (ethylene glycol (EG), diethylene glycol, propylene glycol (PG), dipropylene glycol, (1,3- or 1,4-)butanediol, pentanediol, neo low molecular weight polyols such as pentyl glycol, hexanediol, cyclohexanedimethanol, glycerin, 1,1,1-trimethylolpropane (TMP), 1,2,5-hexanetriol, pentaerythritol, sugars such as sorbitol, etc.), Polybasic carboxylic acids (glutaric acid, adipic acid, azelaic acid, fumaric acid, maleic acid, pimelic acid, suberic
  • 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.
  • Polyacrylic polyols include, 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 having one or more hydroxyl groups in one molecule and vinyl monomers, 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.
  • polyepoxy polyols include diglycidyl compounds (bisphenol A type epoxy resin, bisphenol F type 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, etc.
  • polyolefin polyol examples include polyethylene polyol, polypropylene polyol, polybutadiene polyol, hydrogenated polybutadiene polyol, polyisoprene polyol, hydrogenated polyisoprene polyol, and the like.
  • Preferred polyisocyanates for use in the present invention include aromatic polyisocyanates, aliphatic polyisocyanates, alicyclic polyisocyanates, and one of the above polyisocyanates (i.e., aromatic polyisocyanates, aliphatic polyisocyanates, and alicyclic polyisocyanates).
  • isocyanurate type polyisocyanate obtained by polymerizing one or more of the above polyisocyanates uretdione type polyisocyanate obtained by polymerizing one or more of the above polyisocyanates, an adduct type polyisocyanate obtained from one or more of the above polyisocyanates and a polyhydric alcohol, and one of the above polyisocyanates.
  • uretdione type polyisocyanate obtained by polymerizing one or more of the above polyisocyanates
  • an adduct type polyisocyanate obtained from one or more of the above polyisocyanates and a polyhydric alcohol and one of the above polyisocyanates.
  • 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), and the like.
  • the polyisocyanate used in the present invention is more preferably MDI, polymeric MDI, modified MDI, or a combination thereof.
  • the preferred polyisocyanate used in the present invention may be a blocked isocyanate obtained by blocking the polyisocyanate listed above with a blocking agent.
  • Blocking agents are not particularly limited, and include, for example, phenolics (phenol, cresol, xylenol, chlorophenol, ethylphenol, etc.), lactams ( ⁇ -caprolactam, ⁇ -valerolactam, ⁇ -butyrolactam, ⁇ -propiolactam, etc.) ), activated methylene (ethyl acetoacetate, acetylacetone, etc.), alcohol (methanol, ethanol, propanol, isopropanol, n-butanol, isobutanol, t-butanol, amyl alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, Ethylene glycol monomethyl ether, ethylene glycol mono-2-ethylhexyl ether,
  • the blending ratio (% by mass) (glycerol ester polyol/other polyol) to the polyol other than the glycerol ester polyol is preferably 5 to 5. It is 50% by mass, more preferably 10 to 40% by mass. If the mass ratio decreases beyond the above-mentioned preferred range, the curability, solvent resistance, chemical resistance, etc. of the coating film tends to decrease, and if it increases beyond the above-mentioned preferred range, the viscosity increases in a short time due to reaction with isocyanate. However, the pot life tends to be shortened.
  • the equivalent ratio of the isocyanate groups of the polyisocyanate to the hydroxyl groups of the polyol (isocyanate groups/hydroxyl groups) is preferably 0.3 to 3.0, more preferably 0.5 to 2.5.
  • the hydroxyl group of the polyol is a hydroxyl group of a glycerol ester polyol.
  • the equivalent ratio of the isocyanate groups of the polyisocyanate to the hydroxyl groups of the polyol (isocyanate groups/hydroxyl groups) is preferably 0.5 to 2.0, more preferably 0. 7 to 1.5.
  • the hydroxyl group of the polyol is a hydroxyl group of a glycerol ester polyol and a polyol other than the glycerol ester polyol.
  • the resulting cured product can have high adhesiveness and high elastic modulus.
  • the equivalent ratio becomes smaller than the above-mentioned preferred range, unreacted hydroxyl groups increase and curability, solvent resistance, chemical resistance, etc. tend to decrease. Furthermore, if the equivalent ratio exceeds the above-mentioned preferred range, the number of unreacted isocyanate groups increases, which tends to reduce the curing speed and appearance of the coating film.
  • the coating composition of the present invention may contain components that are generally added to coating compositions within a range that does not impair the object of the present invention.
  • various additives pigments, dyes, ultraviolet absorbers, light stabilizers, surface conditioners, etc.
  • various solvents aromatic solvents such as toluene, xylene, and their hydrogenated substances, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.
  • Ketone solvents such as ethyl acetate, butyl acetate, isobutyl acetate, ethylene glycol ethyl ether acetate, propylene glycol methyl ether acetate, 3-methyl-3-methoxybutyl acetate, ethyl-3-ethoxypropionate, etc.
  • glycol ether ester solvents such as tetrahydrofuran, dioxane, etc.
  • ether solvents such as tetrahydrofuran, dioxane, etc.
  • a solvent-free coating composition may be obtained by blending a polyol such as a polyether polyol.
  • One embodiment of the coating composition of the present invention is a two-component coating composition composed of a base agent containing a glycerol ester polyol and a curing agent containing a polyisocyanate.
  • Another embodiment of the coating composition of the present invention is a two-component coating composition composed of a main agent containing a glycerol ester polyol and a polyol other than the glycerol ester polyol, and a curing agent containing a polyisocyanate.
  • two-component coating compositions tend to react quickly by mixing the two components, and have higher durability than one-component coating compositions.
  • the above-mentioned additives can be added, for example, to the base resin or when mixing the base resin and the curing agent.
  • the solvent can be added to either the base agent or the curing agent, or both.
  • the above two components are mixed immediately before use and applied.
  • the coating method is not limited, and can be carried out by conventional methods such as spray coating, brush coating, and roller coating. After painting, it may be cured by heating to about 40 to 100°C.
  • One-component coating composition is a one-component coating composition comprising a glycerol ester polyol and a blocked isocyanate. Yet another embodiment of the present invention is a one-component coating composition containing a glycerol ester polyol, a polyol other than the glycerol ester polyol, and a blocked polyisocyanate.
  • One-component coating compositions have advantages such as being able to be stored for a long time and having a long pot life when applied.
  • the coating method is not limited, and the coating can be carried out by a conventional coating method such as spray coating, brush coating, or roll coating.
  • curing and drying can be performed at room temperature, it is possible to improve the performance of the cured coating film by heating and curing preferably at 50 to 210°C, more preferably at 110 to 180°C for 30 minutes to 2 hours.
  • the triglycerol ester used in the present invention has a highly regular content of oleic acid residues of 70 mol% or more.
  • the high regularity of the molecular structure improves the hardness, chemical resistance, drying properties, and other properties of the urethane resin obtained by reacting with polyisocyanate.
  • the resulting urethane resin is flexible and strong.
  • resin polyols polyols such as acrylic resins, epoxy resins, polyester resins, polyether resins, and polycarbonate resins
  • the system After starting stirring and raising the temperature to 90° C., the system was pressurized to 1000 psi with synthesis gas and reacted for 6 hours. After cooling down to room temperature, the synthesis gas was discharged. Next, 50 ml of isopropanol and 10 g of Raney nickel were added, and the inside of the system was replaced with hydrogen gas. After starting stirring and raising the temperature to 110° C., the inside of the system was pressurized to 1000 psi with hydrogen gas and reacted for 5 hours. After the temperature was lowered to room temperature and the gas in the system was discharged, 22 ml of isopropanol was added, mixed with stirring, and purified by filtration.
  • 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.
  • Example 1 Preparation of cured coating film 1 Polyol 1 (100 parts by mass), Burnock D-750-45 as curing agent (tolylene diisocyanate adduct type polyisocyanate manufactured by DIC Corporation, NCO%: 7.9%) (160 parts by mass) was mixed (the amount of curing agent D-750-45 was blended so that the equivalent ratio of isocyanate groups/hydroxyl groups was 1.1), and a 6 mil application was applied on a glass plate and a PP plate. After coating, it was dried for two weeks at 25° C. to obtain a cured coating film with a thickness of 70 ⁇ m. Table 4 shows the evaluation results of the obtained coating films.
  • Examples 2 to 7 Preparation of cured coating films 2 to 7
  • the blending amounts of polyol 1 and curing agent (D-750-45) of Example 1 are shown in Table 4.
  • Cured coating films 2 to 6 were obtained in the same manner as in Example 1, except that the amount of the curing agent was blended so that the equivalent ratio of isocyanate group/hydroxyl group was 1.1.
  • the blending amounts of polyol 1 and curing agent (D-750-45) of Example 1 are shown in Table 4. Co., Ltd.) (the curing agent was blended in such a way that the equivalent ratio of isocyanate groups/hydroxyl groups was 1.1), and ethyl acetate was added.
  • a cured coating film 7 was obtained.
  • the evaluation results are shown in Table 4.
  • ⁇ Evaluation method of cured coating film> The cured coating films prepared in Examples and Comparative Examples were evaluated according to the following evaluation method.
  • ⁇ Paint film adhesion test>> In accordance with the 100-square grid test (JIS K-5400-8.5), the gap between the cuts is 1 mm, 100 grid grids are made, and cellophane adhesive tape is adhered to the surface of the grid. The number of grid lines remaining on the painted surface was investigated.
  • ⁇ Chemical resistance test>> The felt on which the coating film was formed was immersed in xylene by a method in accordance with JIS A-5209, and the coating film was subjected to a rubbing test 50 times under a load of 500 g.
  • the evaluation was as follows: 1: The coating film peeled off and the base material was exposed, 2: Whitening due to scratches on the coating film, 3: Slight scratches on the coating film, and 4: No change.
  • Comparative Examples 1 to 5 Preparation of comparative cured coating films 1 to 5 The blending amounts of polyol 1 of Example 1 and curing agent (D-750-45) are shown in Table 5. ) Comparative cured coating film 1 was prepared in the same manner as in Example 1 except that the amount of curing agent D-750-45 was blended so that the equivalent ratio of isocyanate groups/hydroxyl groups was 1.1. I got ⁇ 5. The evaluation results are shown in Table 5.
  • T-1000 Actocol T-1000 (polypropylene glycol manufactured by Mitsui Chemicals, Inc., hydroxyl value: 164 mgKOH/g)
  • PTMG-650 Polytetramethylene glycol manufactured by Mitsubishi Chemical Corporation, hydroxyl value: 172mgKOH/g)
  • Castor oil Castor oil HS2G-160R (manufactured by Toyokuni Oil Co., Ltd., hydroxyl value: 158mgKOH/g)
  • Example 8 Preparation of cured coating film 8 Acrydic A-801 (acrylic resin polyol manufactured by DIC Corporation, hydroxyl value: 50 mgKOH/g) (100 parts by mass) and polyol 1 (12.5 parts by mass) were mixed. Then, Burnock D-750-45 (67.5 parts by mass) as a hardening agent was added into the polyol mixture, stirred well, and coated on SPCC-SB water-sanded board and PP board with a 6 mil applicator at 25°C. After drying for two weeks, a cured coating film with a thickness of 70 ⁇ m was obtained (the amount of curing agent D-750-45 was blended such that the equivalent ratio of isocyanate groups/hydroxyl groups was 1.1). Table 6 shows the evaluation results of the obtained coating film.
  • Example 9 to 15 Preparation of cured coating films 9 to 15
  • the blending amounts of polyol 1 of Example 8, Acridic A-801, and curing agent (D-750-45) are shown in Table 6.
  • Polyol and curing agent Cured coating films 9 to 15 were obtained in the same manner as in Example 8, except that the curing agent was blended in an amount such that the equivalent ratio of isocyanate group/hydroxyl group was 1.1.
  • the evaluation results are shown in Table 6.
  • A-801 Acrydic A-801 (acrylic resin polyol manufactured by DIC Corporation, hydroxyl value: 50 mgKOH/g) H-202: EPICLON H-202-60MT (epoxy resin polyol manufactured by DIC Corporation, hydroxyl value: 120 mgKOH/g, non-volatile content: 60%)
  • D-210 Burnock D-210-80 (polyester polyol manufactured by DIC Corporation, hydroxyl value: 175 mgKOH/g, non-volatile content: 80%)
  • D-750-45 Burnock D-750-45 (tolylene diisocyanate adduct type polyisocyanate manufactured by DIC Corporation, NCO%: 7.9%)
  • DN-902S Burnock DN-902S (isocyanurate type polyisocyanate of hexamethylene diisocyanate manufactured by DIC Corporation, NCO%: 23.3%)
  • T1890E VASTANAT T1890E (isocyanurate type polyisocyanate of

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Paints Or Removers (AREA)

Abstract

La présente invention a pour but de procurer un matériau de revêtement à base d'uréthane obtenu à l'aide d'un polyol à base d'ester de glycérol et qui permet d'obtenir un film de revêtement présentant d'excellentes propriétés physiques. La présente invention concerne une composition de matériau de revêtement à base d'uréthane contenant un polyol à base d'ester de glycérol et un polyisocyanate. La teneur d'un résidu d'acide gras issu de l'acide oléique dans le polyol à base d'ester de glycérol est de 70 % molaire ou plus par rapport à la quantité totale de résidus d'acide gras dans le polyol à base d'ester de glycérol. Cette composition de matériau de revêtement à base d'uréthane peut en outre contenir un polyol autre que le polyol à base d'ester de glycérol.　
PCT/JP2023/023074 2022-06-30 2023-06-22 Composition de matériau de revêtement à base d'uréthane WO2024004813A1 (fr)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20140096754A (ko) * 2013-01-29 2014-08-06 에이치플러스에코 주식회사 속건경화형 폴리우레탄 도료 조성물
US20180030196A1 (en) * 2016-07-28 2018-02-01 Soprema Method for manufacturing a polyurethane-modified foam, foam obtained, and uses
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

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20140096754A (ko) * 2013-01-29 2014-08-06 에이치플러스에코 주식회사 속건경화형 폴리우레탄 도료 조성물
US20180030196A1 (en) * 2016-07-28 2018-02-01 Soprema Method for manufacturing a polyurethane-modified foam, foam obtained, and uses
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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