Polyurethane resin-forming composition, molded body, and coating material

Abstract

To provide a polyurethane resin forming composition that contributes to forming a polyurethane resin having a great ability to scavenge aldehyde, and a molding having a great ability to scavenge aldehyde, and a coating material.SOLUTION: A polyurethane resin forming composition comprises a polyol (A), a polyisocyanate (B), a chain extender (C), and an aldehyde scavenger (D), an organic solvent as an optional component, and water as an optional component, the aldehyde scavenger (D) being an amino oxy alkyl group-supporting carrier in which a compound having a specific structure is chemically bonded to a carrier, the amino oxy alkyl group-supporting carrier having one or more structures represented by formula (2).SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a polyurethane resin-forming composition, a molded article, and a coating material. [Background technology]

[0002] Polyurethane resins are widely used in a variety of applications, including as coating materials for clothing, furniture, home appliances, daily necessities, construction and civil engineering, and automotive parts, as resin components for inks, adhesives, and paints, as well as in various molded products such as films and sheets.

[0003] On the other hand, aldehydes such as acetaldehyde and formaldehyde are typical odorants in the living environment, and because their odor threshold is extremely low, they cause unpleasant odors even at low concentrations. However, because lower aldehydes such as acetaldehyde and formaldehyde have low boiling points, the capture efficiency of inorganic porous materials such as silica gel and activated carbon, which are commonly used as deodorizers, is low. Therefore, Patent Document 1 discloses a method of capturing aldehydes by chemically reacting an aldehyde scavenger made of an amine or the like with the aldehydes. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Laid-Open No. 2018-108360 Summary of the Invention [Problem to be solved by the invention]

[0005] However, the method disclosed in Patent Document 1 has problems such as insufficient capture efficiency, low capture ability of the capture agent applied to the substrate, and reduced performance due to loss of reactive groups.

[0006] One aspect of the present invention is directed to providing a polyurethane resin-forming composition that contributes to the formation of a polyurethane resin having excellent aldehyde scavenging ability. Another aspect of the present invention is directed to providing a molded article and a coating material having excellent aldehyde scavenging ability. [Means for solving the problem]

[0007] According to one aspect of the present invention, a polyol (A); a polyisocyanate (B); a chain extender (C); an aldehyde scavenger (D); an optional organic solvent; and water as an optional component, the aldehyde scavenger (D) is an aminooxyalkyl group-carrying carrier in which the compound represented by formula (1) and the carrier are chemically bonded, There is provided a polyurethane resin-forming composition, wherein the aminooxyalkyl group-supported carrier has one or more structures represented by formula (2):

[0008] [ka]

[0009] [ka]

[0010] During the ceremony, R represents an alkyl group having 1 to 4 carbon atoms; When m is 2, two R's may be the same or different; X represents an alkoxy group having 1 to 4 carbon atoms; When m is 0 or 1, multiple Xs may be the same or different; m represents an integer of 0 to 2; m' represents an integer of 0 to 1; n represents an integer of 1 to 12.

[0011] According to another aspect of the present invention, there is provided a molded article that is a cured product of the polyurethane resin-forming composition. According to yet another aspect of the present invention, there is provided a coating material which is a cured product of the polyurethane resin-forming composition described above. [Effects of the Invention]

[0012] According to one aspect of the present invention, a polyurethane resin-forming composition that contributes to the formation of a polyurethane resin having excellent aldehyde scavenging ability can be provided. Also, according to another aspect of the present invention, a molded article and a coating material having excellent aldehyde scavenging ability can be provided. DETAILED DESCRIPTION OF THE INVENTION

[0013] Exemplary embodiments for carrying out each aspect of the present invention will be described in further detail below, although the present invention is not limited to the following embodiments.

[0014] The polyurethane resin-forming composition according to one embodiment of the present invention comprises: a polyol (A); a polyisocyanate (B); a chain extender (C); an aldehyde scavenger (D); an optional organic solvent; and water as an optional component, the aldehyde scavenger (D) is an aminooxyalkyl group-carrying carrier in which the compound represented by formula (1) and the carrier are chemically bonded, The aminooxyalkyl group-supported carrier has one or more structures represented by formula (2):

[0015] [ka]

[0016] [ka]

[0017] During the ceremony, R represents an alkyl group having 1 to 4 carbon atoms; When m is 2, two R's may be the same or different; X represents an alkoxy group having 1 to 4 carbon atoms; When m is 0 or 1, multiple Xs may be the same or different; m represents an integer of 0 to 2; m' represents an integer of 0 to 1; n represents an integer of 1 to 12.

[0018] [Polyol (A)] The polyol (A) is not particularly limited, and examples thereof include one or more selected from the group consisting of polycarbonate polyols, polycaprolactone polyols, polyester polyols, polyether polyols, polyolefin polyols, acrylic polyols, silicone polyols, castor oil-based polyols, and fluorine-based polyols.

[0019] <Polycarbonate polyol> Specific examples of polycarbonate polyols include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 3-methyl-1,5-pentanediol, 3,3-dimethylolheptane, diethylene glycol, dipropylene glycol, neopentyl glycol, diethylene glycol, dipropylene glycol, cyclohexane-1,4-diol, cyclohexane-1,4-dimethanol, dimer diol, and ethylene oxide of bisphenol A. and propylene oxide adducts, bis(β-hydroxyethyl)benzene, xylylene glycol, glycerin, trimethylolpropane, pentaerythritol, and other low-molecular-weight polyols; and one or more carbonates, such as dialkyl carbonates (dimethyl carbonate, diethyl carbonate, and other), alkylene carbonates (ethylene carbonate, propylene carbonate, and other), and diaryl carbonates (diphenyl carbonate, dinaphthyl carbonate, dianthryl carbonate, diphenanthryl carbonate, diindanyl carbonate, tetrahydronaphthyl carbonate, and other diaryl carbonates. Among these, polycarbonate polyols obtained by dealcoholization reaction of 1,6-hexanediol and diethyl carbonate are preferred, from the viewpoint of imparting abrasion resistance, scratch resistance, and oleic acid resistance.

[0020] <Polycaprolactone polyol> Specific examples of polycaprolactone polyols include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 3-methyl-1,5-pentanediol, 3,3-dimethylolheptane, diethylene glycol, dipropylene glycol, neopentyl glycol, diethylene glycol, dipropylene ... Examples include those obtained by ring-opening addition of either or both of ε-caprolactone and alkyl-substituted ε-caprolactone to one or more low-molecular-weight polyols such as propylene glycol, cyclohexane-1,4-diol, cyclohexane-1,4-dimethanol, dimer acid diol, ethylene oxide or propylene oxide adduct of bisphenol A, bis(β-hydroxyethyl)benzene, xylylene glycol, glycerin, trimethylolpropane, and pentaerythritol as an initiator.

[0021] <Polyester polyol> Specific examples of polyester polyols include phthalic acid, isophthalic acid, terephthalic acid, naphthalenedicarboxylic acid, succinic acid, tartaric acid, oxalic acid, malonic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, glutaconic acid, azelaic acid, sebacic acid, 1,4-cyclohexyldicarboxylic acid, α-hydromuconic acid, β-hydromuconic acid, α-butyl-α-ethylglutaric acid, α,β-diethylsuccinic acid, maleic acid, and fumaric acid, and one or more dicarboxylic acids or anhydrides thereof; and ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, and the like. Examples of polyester polyols include those obtained by a condensation polymerization reaction with one or more low-molecular-weight polyols having a molecular weight of 500 or less, such as hexanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 3-methyl-1,5-pentanediol, 3,3-dimethylolheptane, diethylene glycol, dipropylene glycol, neopentyl glycol, cyclohexane-1,4-diol, cyclohexane-1,4-dimethanol, diol dimer acid, ethylene oxide or propylene oxide adducts of bisphenol A, bis(β-hydroxyethyl)benzene, xylylene glycol, glycerin, trimethylolpropane, and pentaerythritol. The polyester polyol may also be a polyester-amide polyol obtained by replacing a portion of the low-molecular-weight polyol with a low-molecular-weight polyamine or low-molecular-weight amino alcohol, such as hexamethylenediamine, isophoronediamine, or monoethanolamine.

[0022] <Polyether polyol> Specific examples of polyether polyols include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 3-methyl-1,5-pentanediol, 3,3-dimethylolheptane, diethylene glycol, dipropylene glycol, neopentyl glycol, cyclohexane-1,4-diol, cyclohexane-1,4-dimethanol, dimer acid diol, bisphenol A, bis(β-hydroxyethyl)benzene, xylylene glycol, glycerin, trimethylolpropane, and pentaerythritol. Examples of the polyether polyol include polyether polyols obtained by addition polymerization of alkylene oxides such as ethylene oxide, propylene oxide, butylene oxide, etc., using as an initiator a compound having two or more, preferably two to three, active hydrogen groups, such as low molecular weight polyols such as toluenediamine, or low molecular weight polyamines such as ethylenediamine, propylenediamine, toluenediamine, metaphenylenediamine, diphenylmethanediamine, xylylenediamine, etc.; and polyether polyols obtained by ring-opening polymerization of cyclic ether monomers such as alkyl glycidyl ethers such as methyl glycidyl ether, aryl glycidyl ethers such as phenyl glycidyl ether, and tetrahydrofuran.

[0023] <Polyolefin polyol> Polyolefin polyol is a polyolefin having two or more hydroxyl groups. Specific examples of polyolefin include polybutadiene, hydrogenated polybutadiene, polyisoprene, and hydrogenated polyisoprene.

[0024] <Acrylic polyol> Examples of acrylic polyols include those obtained by copolymerizing an acrylic monomer with an acrylic acid ester and / or a methacrylic acid ester (hereinafter referred to as a (meth)acrylic acid ester), an acrylic acid hydroxy compound and / or a methacrylic acid hydroxy compound (hereinafter referred to as a (meth)acrylic acid hydroxy compound) having at least one hydroxyl group in the molecule that can serve as a reaction site (hereinafter referred to as a (meth)acrylic acid hydroxy compound), and a polymerization initiator using thermal energy or light energy such as ultraviolet light or electron beams.

[0025] (Meth)acrylic acid esters Specific examples of (meth)acrylic acid esters include alkyl esters having 1 to 20 carbon atoms. Specific examples of such (meth)acrylic acid esters include (meth)acrylic acid alkyl esters such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, octyl (meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate, dodecyl (meth)acrylate, and benzyl (meth)acrylate; esters of (meth)acrylic acid with alicyclic alcohols such as cyclohexyl (meth)acrylate; and aryl (meth)acrylic acid esters such as phenyl (meth)acrylate. These (meth)acrylic acid esters may be used alone or in combination of two or more.

[0026] (Meth)acrylic acid hydroxy compounds The (meth)acrylic acid hydroxy compound has at least one hydroxyl group in the molecule that can serve as a reaction site with the polyisocyanate (B). Specific examples of the (meth)acrylic acid hydroxy compound include acrylic acid hydroxy compounds such as 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 3-hydroxy-2,2-dimethylpropyl acrylate, and pentaerythritol triacrylate; and methacrylic acid hydroxy compounds such as 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, 3-hydroxy-2,2-dimethylpropyl methacrylate, and pentaerythritol trimethacrylate. These acrylic acid hydroxy compounds and methacrylic acid hydroxy compounds may be used alone or in combination of two or more.

[0027] <Silicone polyol> Specific examples of silicone polyols include vinyl group-containing silicone compounds obtained by polymerizing γ-methacryloxypropyltrimethoxysilane, and polysiloxanes having at least one terminal hydroxyl group in the molecule, such as α,ω-dihydroxypolydimethylsiloxane and α,ω-dihydroxypolydiphenylsiloxane.

[0028] <Castor oil polyol> Specific examples of castor oil-based polyols include linear or branched polyester polyols obtained by reacting castor oil fatty acids with polyols, as well as dehydrated castor oil, partially dehydrated castor oil, and hydrogenated castor oil.

[0029] <Fluorine-based polyol> Specific examples of fluorine-based polyols include linear or branched polyols obtained by copolymerization of a fluorine-containing monomer and a monomer having a hydroxyl group as essential components.Here, the fluorine-containing monomer is preferably a fluoroolefin, such as tetrafluoroethylene, chlorotrifluoroethylene, trichlorofluoroethylene, hexafluoropropylene, vinylidene fluoride, vinyl fluoride, and trifluoromethyltrifluoroethylene.In addition, examples of monomers having a hydroxyl group include hydroxyalkyl vinyl ethers such as hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, and cyclohexanediol monovinyl ether, hydroxyalkyl allyl ethers such as 2-hydroxyethyl allyl ether, and hydroxyl group-containing vinyl carboxylates or allyl esters such as hydroxyalkyl vinyl crotonates.

[0030] <Copolymer polyol> From the viewpoints of durability, weather resistance, flexibility, etc., the polyol (A) may also include copolymer polyols obtained by transesterification of the above-mentioned polycarbonate polyol, the above-mentioned polycaprolactone polyol, and an aliphatic glycol. The optimal ratio of polycarbonate polyol and aliphatic glycol to polycaprolactone polyol [(polycarbonate polyol + aliphatic glycol) / polycaprolactone polyol] is preferably 99 / 1 to 60 / 40 by mass. The copolymer polyol obtained in this manner can have improved performance such as durability, weather resistance, flexibility, etc., compared to when each is used alone or as a mixture.

[0031] Aliphatic glycols Examples of aliphatic glycols include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 3-methyl-1,5-pentanediol, dimethylolheptane, diethylene glycol, dipropylene glycol, and neopentyl glycol.

[0032] ·Method of manufacturing copolymer polyol Known techniques can be used to produce copolymer polyols. For example, polycarbonate polyol, polycaprolactone polyol, and aliphatic glycol are blended and dissolved at 60°C while bubbling nitrogen gas through the mixture until the mixture becomes homogeneous. The copolymer polyol is then obtained by a transesterification reaction at 190°C until the desired molecular weight is achieved.

[0033] The number average molecular weight of the polyol (A) is preferably 500 or more and 50,000 or less, and more preferably 1,000 to 4,000. When the number average molecular weight is within this range, the mechanical properties and heat resistance are further improved.

[0034] The polyol (A) preferably has an active hydrogen group number (average functional group number) per molecule of 1.9 to 4.0, which further improves abrasion resistance, flexibility, and mechanical properties.

[0035] [Polyisocyanate (B)] Examples of the polyisocyanate (B) include alicyclic diisocyanates, aromatic diisocyanates, aliphatic diisocyanates, araliphatic diisocyanates, isocyanurate group-containing polyisocyanates obtained using these polyisocyanates as raw materials, uretdione group-containing polyisocyanates, uretdione group- and isocyanurate group-containing polyisocyanates, urethane group-containing polyisocyanates, allophanate group-containing polyisocyanates, biuret group-containing polyisocyanates, and uretoimine group-containing polyisocyanates.

[0036] <Alicyclic diisocyanate> Specific examples of alicyclic diisocyanates include isophorone diisocyanate, cyclohexane diisocyanate, hydrogenated diphenylmethane diisocyanate, norbornane diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated xylene diisocyanate, and hydrogenated tetramethylxylene diisocyanate.

[0037] <Aromatic diisocyanate> Specific examples of aromatic diisocyanates include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, a 2,4-tolylene diisocyanate / 2,6-tolylene diisocyanate mixture, m-xylylene diisocyanate, p-xylylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, a 2,4'-diphenylmethane diisocyanate / 4,4'-diphenylmethane diisocyanate mixture, 4,4'-diphenylamine diisocyanate, Examples of suitable diisocyanates include terdiisocyanate, 2-nitrodiphenyl-4,4'-diisocyanate, 2,2'-diphenylpropane-4,4'-diisocyanate, 3,3'-dimethyldiphenylmethane-4,4'-diisocyanate, 4,4'-diphenylpropane diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, naphthylene-1,4-diisocyanate, naphthylene-1,5-diisocyanate, and 3,3'-dimethoxydiphenyl-4,4'-diisocyanate.

[0038] <Aliphatic diisocyanate> Specific examples of aliphatic diisocyanates include hexamethylene diisocyanate, tetramethylene diisocyanate, 2-methyl-pentane-1,5-diisocyanate, 3-methyl-pentane-1,5-diisocyanate, lysine diisocyanate, and trioxyethylene diisocyanate.

[0039] <Aromatic aliphatic diisocyanate> Specific examples of aromatic aliphatic diisocyanates include 1,3- or 1,4-xylylene diisocyanate or a mixture thereof, 1,3- or 1,4-bis(1-isocyanato-1-methylethyl)benzene or a mixture thereof, ω,ω'-diisocyanato-1,4-diethylbenzene, and the like.

[0040] [Chain extender (C)] The chain extender (C) is not particularly limited, but examples thereof include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,3-butanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 1,4-bis(β-hydroxyethoxy)benzene, neopentyl glycol, methyloctanediol, 1,9-nonanediol, bisphenol, cyclohexanedimethanol, dimethylolheptane, polypropylene glycol, isophoronediamine, cyclohexanediamine, norbornanediamine, hydrogenated tolylenediamine, hydrogenated xylenediamine, hydrogenated tetramethylxylenediamine, etc. Among these, 1,4-butanediol and isophoronediamine are preferred in terms of the balance between flexibility and durability.

[0041] [Aldehyde Scavenger (D)] The aldehyde scavenger (D) is an aminooxyalkyl group-supported carrier in which the compound represented by formula (1) and the carrier are chemically bonded, and the aminooxyalkyl group-supported carrier has one or more structures represented by formula (2).

[0042] [ka]

[0043] [ka]

[0044] During the ceremony, R represents an alkyl group having 1 to 4 carbon atoms; When m is 2, two R's may be the same or different; X represents an alkoxy group having 1 to 4 carbon atoms; When m is 0 or 1, multiple Xs may be the same or different; m represents an integer of 0 to 2; m' represents an integer of 0 to 1; n represents an integer of 1 to 12.

[0045] An example of the aldehyde scavenger (D) is one obtained by chemically modifying a support with a compound represented by formula (1) (hereinafter also referred to as a "silane coupling agent") (hereinafter also referred to as a "silane coupling reaction").

[0046] In the silane coupling agent, R represents an alkyl group having 1 to 4 carbon atoms, and X represents an alkoxy group having 1 to 4 carbon atoms. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a 2-methylpropyl group, a 1-methylpropyl group, and a tert-butyl group. Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, a 2-methylpropyloxy group, a 1-methylpropyloxy group, and a tert-butoxy group. In terms of efficiency of the silane coupling reaction, R is preferably a methyl group, and each X is preferably a methoxy group, an ethoxy group, or an isopropoxy group, while m is preferably an integer of 0 to 1, m' is preferably 0, and n is preferably an integer of 3 to 9.

[0047] The silane coupling agent represented by formula (1) may be a commercially available product and used, or may be synthesized in accordance with the methods described in Organic Preparations and Procedures International, 1994, Vol. 26, pp. 111-113, JP-A-7-233132, and Tetrahedron Letters, 2005, Vol. 46, pp. 7973-7975.

[0048] In the aminooxyalkyl group-carrying carrier, a part or all of the aminooxyalkyl group may be a chemically acceptable salt with an inorganic acid or an organic acid. The type of salt is not particularly limited, but examples thereof include inorganic acid salts such as hydrochloride, hydrobromide, perchlorate, silicate, tetrafluoroborate, hexafluorophosphate, sulfate, nitrate, phosphate, and organic acid salts such as acetate, citrate, fumarate, maleate, trifluoromethanesulfonate, trifluoroacetate, benzoate, p-toluenesulfonate, and inorganic acid salts are preferred in terms of low cost, and hydrochloride is more preferred.

[0049] The amount of aminooxyalkyl group supported on the carrier can be adjusted as desired depending on the purpose and is not particularly limited, but it is preferable that the amount of aminooxyalkyl group is in the range of 0.01 mmol / g or more and 10 mmol / g or less relative to the mass of the carrier.

[0050] The carrier is not particularly limited as long as it is insoluble in water. Examples include polymer carriers such as styrene-based polymers such as polystyrene and cross-linked polystyrene, polyolefins such as polyethylene and polypropylene, poly(halogenated olefins) such as polyvinyl chloride and polytetrafluoroethylene, nitrile-based polymers such as polyacrylonitrile, (meth)acrylic polymers such as polymethyl methacrylate and polyethyl acrylate, and high-molecular-weight polysaccharides such as cellulose, agarose, and dextran; and inorganic carriers such as silica gel, alumina, zeolite, magnesia, titania, zirconia, ceria, diatomaceous earth, activated carbon, cellulose, and hydroxyapatite. As the carrier to be mixed with the silane coupling agent, inorganic carriers are preferred, and silica gel is more preferred, because the silane coupling reaction is efficient.

[0051] The shape of the carrier is not particularly limited, but examples include shapes commonly used as separation substrates, such as spherical (e.g., spherical particles), granular, fibrous, granular, monolithic column, hollow fiber, and membrane (e.g., flat membrane). Of these, spherical, membranous, granular, and fibrous carriers are preferred. Spherical, granular, and granular carriers are particularly preferred because their usage volume can be freely set when used in column and batch methods. The particle size of spherical, granular, or granular carriers is usually in the range of 0.1 μm to 10 mm on average, but is preferably 0.1 μm to 100 μm in terms of good dispersibility in liquid.

[0052] The carrier may be porous or non-porous. The average pore size of the porous carrier is usually 1 nm to 1 μm, but is preferably in the range of 1 nm to 300 nm in terms of the aldehyde capture rate.

[0053] <Monoamine> Specific examples of monoamines include ethylamine, morpholine, propylamine, dibutylamine, diethylamine, monoethanolamine, dibutylamine monoethanolamine, diethanolamine, N-methylethanolamine, N-ethylethanolamine, Nn-butylethanolamine, Nt-butylethanolamine, hydroxyethylpiperazine, N-(3-aminopropyl)diethanolamine, and N-cyclohexylethanolamine, and these may be used alone or in combination of two or more.

[0054] <Organic solvents> Specific examples of organic solvents include aliphatic hydrocarbons such as octane; alicyclic hydrocarbons such as cyclohexane and methylcyclohexane; ketones such as methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; esters such as butyl acetate and isobutyl acetate; glycol ether esters such as ethylene glycol ethyl ether acetate, propylene glycol monomethyl ether acetate, 3-methyl-3-methoxybutyl acetate, and ethyl-3-ethoxypropionate; ethers such as dioxane; halogenated hydrocarbons such as methylene iodide and monochlorobenzene; and polar aprotic solvents such as N-methylpyrrolidone, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, and hexamethylphosphonylamide. These solvents may be used alone or in combination of two or more.

[0055] The content of the organic solvent in the polyurethane resin-forming composition is from 0% to 90% by mass, more preferably from 10% to 85% by mass, even more preferably from 20% to 80% by mass, and particularly preferably from 30% to 75% by mass.

[0056] <Water> The water content in the polyurethane resin-forming composition is from 0% to 10% by mass, more preferably from 0% to 7% by mass, even more preferably from 0% to 3% by mass, and particularly preferably from 0% to 1% by mass.

[0057] <Other ingredients> The polyurethane resin-forming composition may contain other well-known and commonly used components.

[0058] [Molded bodies, coating materials] A molded article according to another embodiment of the present invention is a cured product of the polyurethane resin-forming composition described above. A coating material according to yet another embodiment of the present invention is a cured product of the polyurethane resin-forming composition described above. The molded body and coating material may contain other well-known and commonly used materials. [Example]

[0059] The present invention will be described in more detail below based on examples and comparative examples, but the present invention is not limited to the following examples. Unless otherwise specified, "parts" and "%" are by mass.

[0060] <Synthesis example> After mixing 19.94 g of silica gel (NIPGEL BY-400, manufactured by Tosoh Silica) and 173.4 g of toluene, a mixture of 8.08 g of the silane coupling agent represented by chemical formula (1') and 43.35 g of toluene was added dropwise under a nitrogen atmosphere and stirred at 25°C for 120 hours. The resulting reaction solution was filtered, and the residue was dried at 120°C for 4 hours to obtain a support with aminooxyalkyl groups supported by chemical bonding (hereinafter referred to as "aminooxy group-supported support"). Elemental analysis of the resulting aminooxy group-supported support revealed that the aminooxyalkyl group content was 1.4 mmol / g relative to the support mass.

[0061] [ka]

[0062] <Synthesis of Polyurethane Resin-Forming Composition>

[0063] Example 1 A 2-liter four-neck flask equipped with a stirrer, a thermometer, a heating device, and a distillation column was charged with 232.2 g of a polyol (1,6-hexanediol-based polycarbonate polyol, number average molecular weight 2,000), 6.3 g of 1,4-butanediol, and 350 g of N,N-dimethylformamide (hereinafter referred to as DMF). These were stirred uniformly at 45 °C while nitrogen gas was bubbled through to prepare a solution of the high molecular weight polyol. 46.5 g of 4,4'-diphenylmethane diisocyanate (hereinafter referred to as MDI) was charged into this high molecular weight polyol solution, and a urethanization reaction was carried out at 70 °C for 4 hours under a nitrogen stream. The completion of the reaction was confirmed by the disappearance of isocyanate residues in the infrared absorption spectrum. Thereafter, 350 g of methyl ethyl ketone (hereinafter referred to as MEK) and 15 g of an aminooxy group-supported carrier were charged and mixed at 40 °C for 1 hour. In this way, a resin solution PU-1 containing 30% by mass of urethane resin as a solid content with a number average molecular weight of 60,000 was obtained. The viscosity at 25 °C was 12,000 mPa·s.

[0064] <GPC: Measurement of Molecular Weight> (1) Measuring Instrument: HLC-8220 (manufactured by Tosoh Corporation) (2) Column: TSKgel (manufactured by Tosoh Corporation) ·G3000H-XL ·G2500H-XL ·G2000H-XL, G1000H-XL (3) Carrier: THF (tetrahydrofuran) (4) Detector: RI (refractive index) detector (5) Temperature: 40 °C (6) Flow Rate: 1.000 ml / min (7) Calibration Curve: Standard Polystyrene (manufactured by Tosoh Corporation) ·F-80 (Molecular Weight: 7.06×10 5 , Molecular Weight Distribution: 1.05) ·F-20 (Molecular Weight: 1.90×10 5 , Molecular Weight Distribution: 1.05) ·F-10 (Molecular Weight: 9.64×10 4 , Molecular Weight Distribution: 1.01) ·F-2 (molecular weight: 1.81×10 4 , molecular weight distribution: 1.01) ·F-1 (molecular weight: 1.02×10 4 , molecular weight distribution: 1.02) ·A-5000 (molecular weight: 5.97×10 3 , molecular weight distribution: 1.02) ·A-2500 (molecular weight: 2.63×10 3 , molecular weight distribution: 1.05) ·A-500 (molecular weight: 5.0×10 2 , molecular weight distribution: 1.14) (8) Sample solution concentration: 0.5% THF solution

[0065] <Example 2> A 2-liter four-neck flask equipped with a stirrer, thermometer, heater, and distillation column was charged with 215.2 g of polyol 1 (1,6-hexanediol-based polycarbonate polyol, number-average molecular weight 2,000), 350 g of DMF, and 350 g of MEK. The mixture was stirred uniformly at 45°C while bubbling with nitrogen gas to prepare a polymer polyol solution. 50.6 g of isophorone diisocyanate (Evonik, NCO content: 37.8% by mass, hereafter referred to as IPDI) was added to the polymer polyol solution, and the urethane reaction was carried out under a nitrogen stream at 75°C for 3 hours to obtain an isocyanate-terminated urethane prepolymer solution. The NCO content of this prepolymer was 1.0% by mass. The resulting isocyanate-terminated urethane prepolymer solution was subjected to a chain extension reaction with 16.2 g of isophorone diamine (IPDA) at 40°C for 4 hours under a nitrogen stream. 3 g of monoethanolamine (MEA) was then added, and the isocyanate groups were blocked at 40°C for 2 hours under a nitrogen stream. The reaction was terminated when no isocyanate residues were detected by infrared absorption spectroscopy. Then, 15 g of an aminooxy group-supported carrier was added and mixed at 40°C for 1 hour. This yielded resin solution PU-2, which had a number-average molecular weight of 75,000 and contained 30% urethane resin by weight as solids. Its viscosity at 25°C was 14,000 mPa·s.

[0066] Example 3 A 2-liter four-neck flask equipped with a stirrer, thermometer, heater, and distillation column was charged with 203.9 g of polyol 1 (1,6-hexanediol-based polycarbonate polyol, number-average molecular weight 2,000), 350 g of DMF, and 350 g of MEK. The mixture was stirred uniformly at 45°C while bubbling with nitrogen gas to prepare a polymer polyol solution. 47.9 g of IPDI was added to this polymer polyol solution, and a urethane reaction was carried out under a nitrogen stream at 75°C for 3 hours to obtain an isocyanate-terminated urethane prepolymer solution. The NCO content of this prepolymer was 1.0% by mass. The resulting isocyanate-terminated urethane prepolymer solution was subjected to a chain extension reaction with 15.4 g of IPDA under a nitrogen stream at 40°C for 4 hours. Then, 2.8 g of MEA was added and the isocyanate group was blocked under a nitrogen stream at 40°C for 2 hours. The reaction was terminated when no isocyanate residues were detected by infrared absorption spectroscopy. Then, 30 g of aminooxy group-supported carrier was added and mixed at 40°C for 1 hour. This yielded resin solution PU-3, which had a number-average molecular weight of 74,000 and contained 30% urethane resin by weight as solids. The viscosity at 25°C was 17,000 mPa·s.

[0067] <Comparative Example 1> A 2-liter four-neck flask equipped with a stirrer, thermometer, heater, and distillation column was charged with 226.5 g of polyol 1 (1,6-hexanediol-based polycarbonate polyol, number-average molecular weight 2,000), 350 g of DMF, and 350 g of MEK. The mixture was stirred uniformly at 45°C while bubbling with nitrogen gas to prepare a polymer polyol solution. 53.3 g of IPDI was added to this polymer polyol solution, and a urethane reaction was carried out under a nitrogen stream at 75°C for 3 hours to obtain an isocyanate-terminated urethane prepolymer solution. The NCO content of this prepolymer was 1.1% by mass. The resulting isocyanate-terminated urethane prepolymer solution was subjected to a chain extension reaction with 17.1 g of IPDA under a nitrogen stream at 40°C for 4 hours. 3 g of MEA was then added, and the isocyanate groups were blocked under a nitrogen stream at 40°C for 2 hours. The reaction was completed when no isocyanate residues were detected by infrared absorption spectroscopy. This yielded resin solution PU-4, with a number-average molecular weight of 73,000 and a urethane resin solids content of 30% by weight. The viscosity at 25°C was 13,000 mPa·s.

[0068] <Comparative Example 2> A 2-liter four-neck flask equipped with a stirrer, thermometer, heater, and distillation column was charged with 215.2 g of polyol 1 (1,6-hexanediol-based polycarbonate polyol, number-average molecular weight 2,000), 350 g of DMF, and 350 g of MEK. The mixture was stirred uniformly at 45°C while bubbling with nitrogen gas to prepare a polymer polyol solution. 50.6 g of IPDI was added to this polymer polyol solution, and a urethane reaction was carried out at 75°C for 3 hours under a nitrogen stream to obtain an isocyanate-terminated urethane prepolymer solution. The NCO content of this prepolymer was 1.0% by mass. The resulting isocyanate-terminated urethane prepolymer solution was subjected to a chain extension reaction with 16.2 g of IPDA under a nitrogen stream at 40°C for 4 hours. 3 g of MEA was then added, and the isocyanate group was blocked under a nitrogen stream at 40°C for 2 hours. The reaction was completed when no isocyanate residues were detected by infrared absorption spectroscopy. Then, 15 g of Kesmon NS-750 was added and mixed at 40°C for 1 hour. This resulted in the resin solution PU-5, which had a number-average molecular weight of 75,000 and contained 30% urethane resin by weight as solids. Its viscosity at 25°C was 15,000 mPa·s. Kesmon NS-750 is an amino group-supported inorganic aldehyde scavenger manufactured by Toagosei Co., Ltd.

[0069] <Comparative Example 3> A 2-liter four-neck flask equipped with a stirrer, thermometer, heater, and distillation column was charged with 215.2 g of polyol 1 (1,6-hexanediol-based polycarbonate polyol, number-average molecular weight 2,000), 350 g of DMF, and 350 g of MEK. The mixture was stirred uniformly at 45°C while bubbling with nitrogen gas to prepare a polymer polyol solution. 50.6 g of IPDI was added to this polymer polyol solution, and a urethane reaction was carried out at 75°C for 3 hours under a nitrogen stream to obtain an isocyanate-terminated urethane prepolymer solution. The NCO content of this prepolymer was 1.0% by mass. The resulting isocyanate-terminated urethane prepolymer solution was subjected to a chain extension reaction with 16.2 g of IPDA under a nitrogen stream at 40°C for 4 hours. 3 g of MEA was then added, and the isocyanate group was blocked under a nitrogen stream at 40°C for 2 hours. The reaction was completed when no isocyanate residues were detected by infrared absorption spectroscopy. Then, 15 g of a 3% aqueous solution of aminooxyacetic acid was added and mixed at 40°C for 1 hour. This yielded resin solution PU-6, with a number-average molecular weight of 75,000 and a urethane resin solids content of 30% by weight. The viscosity at 25°C was 13,000 mPa·s.

[0070] Table 1 shows the blending amounts and properties of the raw materials used in PU-1 to PU-6, the film properties, and the aldehyde capture rate.

[0071] [Table 1]

[0072] The abbreviations used in Table 1 are as follows: MDI: 4,4'-diphenylmethane diisocyanate IPDI: Isophorone diisocyanate Polyol: 1,6-hexanediol-based polycarbonate polyol, number average molecular weight 2,000 MEA: Monoethanolamine IPDA: Isophoronediamine DMF: N,N-dimethylformamide MEK: Methyl ethyl ketone NS-750: Kesmon NS-750, manufactured by Toagosei Co., Ltd.

[0073] Evaluation test 1: <Tensile properties> The resin-forming compositions of PU-1 to PU-6 were cast onto release paper to a thickness of 100 μm, allowed to stand at room temperature for 30 minutes, then heat-treated in a dryer at 60°C for 2 hours and at 120°C for 2 hours, and then aged for 7 days in an environment at 23°C and 50% relative humidity to prepare test specimens. The tensile properties of the resulting test specimens were measured in accordance with JIS K6251. The evaluation results are shown in Table 1. Testing equipment: Tensilon UTA-500 (manufactured by A&D) Measurement conditions: 25°C x 50% RH Head speed: 200mm / min Dumbbells: No. 4 ·Film tensile property test 100% modulus: Tensile stress at 100% elongation Tensile strength at break: Maximum stress at break of test piece Elongation at break: The elongation ratio of the gauge length when the test piece breaks

[0074] Evaluation test 2: <Acetaldehyde capture rate test> Test specimens (film thickness 60 μm) prepared in the same manner as in Evaluation Test 1 were cut into 5 cm x 5 cm pieces and sealed in 5 L Tedlar bags. One liter of nitrogen gas containing 1 ppm acetaldehyde was then added. After standing at room temperature for 96 hours, the gas in the Tedlar bags was adsorbed onto a cartridge (Fujifilm Wako Pure Chemical Industries, Ltd., Presep-C DNPH) loaded with 2,4-dinitrophenylhydrazine (DNPH). The cartridge was treated with acetonitrile to elute the DNPH-aldehyde condensate. The residual acetaldehyde concentration of the eluate was then quantified using a liquid chromatograph (Shimadzu Corporation, LC-2030C Plus). The evaluation results are shown in Table 1.

[0075] As shown in Table 1, it was found that the coating materials according to Examples 1 to 3 were excellent in aldehyde capture rate. On the other hand, the coating materials according to Comparative Examples 1 to 3 were inferior in aldehyde capture rate.

Claims

1. Polyol (A), Polyisocyanate (B), a chain extender (C); an aldehyde scavenger (D); an optional organic solvent; and water as an optional component, the aldehyde scavenger (D) is an aminooxyalkyl group-carrying carrier in which the compound represented by formula (1) and the carrier are chemically bonded, A polyurethane resin-forming composition, wherein the aminooxyalkyl group-supported carrier has one or more structures represented by formula (2): 【Chemistry 1】 【Chemistry 2】 During the ceremony, R represents an alkyl group having 1 to 4 carbon atoms; When m is 2, two R's may be the same or different; X represents an alkoxy group having 1 to 4 carbon atoms; When m is 0 or 1, multiple Xs may be the same or different; m represents an integer of 0 to 2; m' represents an integer of 0 to 1, and in the structure represented by formula (2), m' is 1 in the second structure from the left; n represents an integer of 1 to 12.

2. In the polyurethane resin-forming composition, The content of the organic solvent is 0% by mass or more and 90% by mass or less, The polyurethane resin-forming composition according to claim 1 , wherein the water content is 0% by mass or more and 10% by mass or less.

3. During the ceremony, R is a methyl group; 3. The polyurethane resin-forming composition according to claim 1, wherein each X is independently a methoxy group, an ethoxy group, or an isopropoxy group.

4. 4. The polyurethane resin-forming composition according to claim 1, wherein the carrier is silica gel, alumina, zeolite, magnesia, titania, zirconia, ceria, diatomaceous earth, activated carbon, cellulose, or hydroxyapatite.

5. The polyurethane resin-forming composition according to claim 1 , wherein the carrier is silica gel.

6. The polyurethane resin-forming composition according to any one of claims 1 to 5, wherein the chain extender (C) is one or more selected from the group consisting of ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,3-butanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 1,4-bis(β-hydroxyethoxy)benzene, neopentyl glycol, methyloctanediol, 1,9-nonanediol, bisphenol, cyclohexanedimethanol, dimethylolheptane, polypropylene glycol, isophoronediamine, cyclohexanediamine, norbornanediamine, hydrogenated tolylenediamine, hydrogenated xylenediamine, and hydrogenated tetramethylxylenediamine.

7. A molded article which is a cured product of the polyurethane resin-forming composition according to any one of claims 1 to 6.

8. A coating material, which is a cured product of the polyurethane resin-forming composition according to any one of claims 1 to 6.

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