Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/08—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
  • C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen

Definitions

• This disclosure relates to a urethane prepolymer composition, a urethane resin composition, and a cured product of the urethane resin composition.
• Polymer materials exhibit high mechanical strength and durability based on strong covalent bonds, but they are poorly reprocessable and reusable, and it is difficult to repair scratches or breaks, especially to self-repair.
• Patent Documents 1 and 2 describe a urethane resin composition containing a specific aromatic disulfide diol and a cured product thereof, and state that the cured product of the urethane resin composition has self-repairing properties.
• the cured product obtained from the urethane resin composition containing the aromatic disulfide diol described in Patent Documents 1 and 2 may have insufficient self-repairing properties, and furthermore, there is a problem in that the cured product becomes discolored.
• the present disclosure has been made in consideration of the above problems, and aims to provide a urethane prepolymer composition, a urethane resin composition, and a cured product thereof that have an excellent balance between self-repairing properties and the ability to inhibit discoloration, i.e., discoloration resistance.
• the present disclosure relates to a urethane prepolymer composition that contains a urethane prepolymer obtained by reacting at least one type of polyol compound with at least one type of isocyanate compound, and is characterized in that the polyol compound contains a hydroxyl group-containing compound having an NSSN bond.
• the hydroxyl-containing compound having an NSSN bond is preferably a compound represented by the following general formula (2) or (3).
• R 21 , R 22 , R 23 , R 24 , R 25 , R 26 , R 27 and R 28 each independently represent an unsubstituted or substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms, or the aliphatic hydrocarbon group in which one or more methylene groups are replaced with a divalent group selected from Group I-2 below.
• One or more hydrogen atoms in the substituted aliphatic hydrocarbon group are replaced with an atom or group selected from Group II-2 below.
• Group I-2 -O-, -OCO-, -OCO-NR'-
• Group II-2 halogen atom, cyano group, nitro group X21 and X22 each independently represent a direct bond, an unsubstituted or substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms, or the above-mentioned aliphatic hydrocarbon group in which one or more methylene groups are replaced with a divalent group selected from the following Group I-3.
• One or more hydrogen atoms in the above-mentioned substituted aliphatic hydrocarbon group are replaced with an atom or group selected from the following Group II-3.
• Group I-3 -O-, -OCO-, -OCO-NR'-
• Group II-3 halogen atom, cyano group, nitro group
• Each R' independently represents a hydrogen atom or an unsubstituted aliphatic hydrocarbon group. When a plurality of R's are present, they may be the same or different.
• n2 is an integer from 1 to 5.
• R 31 , R 32 , R 33 and R 34 each independently represent a hydrogen atom, a group represented by the following general formula (3-1), an unsubstituted or substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms, or the above-mentioned aliphatic hydrocarbon group in which one or more methylene groups are replaced by a divalent group selected from the following Group I-4.
• One or more hydrogen atoms in the above-mentioned substituted aliphatic hydrocarbon group are replaced by an atom or group selected from the following Group II-4.
• Group I-4 -O-, -COO-, -OCO-, -CO-, -NR'-, -NR'-CO-, -CO-NR'-, -NR'-COO-, -OCO-NR'-
• Group II-4 an acrylic group, a methacrylic group, a halogen atom, a cyano group, and a nitro group
• R' each independently represents a hydrogen atom or an unsubstituted aliphatic hydrocarbon group. When a plurality of R's are present, they may be the same or different.
• At least one of R 31 and R 32 represents a group represented by the following general formula (3-1), and at least one of R 33 and R 34 represents a group represented by the following general formula (3-1).
• L 41 represents a direct bond, an aliphatic hydrocarbon group having 1 to 20 carbon atoms, or the aliphatic hydrocarbon group in which one or more methylene groups have been replaced with a divalent group selected from the following group I-5.
• n3 is an integer from 1 to 5.
• the hydroxyl-containing compound having an NSSN bond is preferably a compound represented by general formula (2).
• the hydroxyl-containing compound having an NSSN bond is preferably a compound represented by general formula (3).
• the present disclosure relates to a urethane resin composition that contains a hydroxyl group-containing compound that does not have an NSSN bond and the above-mentioned urethane prepolymer composition.
• the present disclosure relates to a cured product of the above urethane resin composition.
• the present disclosure relates to a urethane resin composition that contains a hydroxyl group-containing compound that does not have an NSSN bond, an isocyanate compound, and a hydroxyl group-containing compound that has an NSSN bond.
• the present disclosure relates to a cured product of the above urethane resin composition.
• the present disclosure makes it possible to provide a urethane prepolymer composition, a urethane resin composition, and a cured product thereof that have an excellent balance between self-repairing ability and color resistance.
• the present disclosure relates to a urethane prepolymer composition, a urethane resin composition, and a cured product of the urethane resin composition.
• the present disclosure will be described in detail below.
• the urethane prepolymer composition of the present disclosure is a urethane prepolymer composition containing a urethane prepolymer obtained by reacting at least one polyol compound with at least one isocyanate compound, and is characterized in that the polyol compound contains a hydroxyl group-containing compound having an NSSN bond.
• the urethane prepolymer composition of the present disclosure can easily form a product having an excellent balance of self-repairability and color resistance.
• excellent self-repairing properties refers to, for example, the ability to repair even large damage, the number of times repairs can be made, the ability to recover sufficient mechanical strength even when repaired from a damaged state, etc.
• the cured product of the urethane resin composition of the present disclosure has excellent self-repairing properties that can be repaired to the state of the material before damage.
• Methods for evaluating whether a material has excellent self-repairing properties include, for example, measuring the time and temperature required for self-repairing.
• a polyol compound is a compound having two or more hydroxyl groups in one molecule.
• examples of polyol compounds include hydroxyl group-containing compounds having an NSSN bond and hydroxyl group-containing compounds not having an NSSN bond. These may be used alone or in combination of two or more.
• the polyol compound is characterized by containing at least a hydroxyl group-containing compound having an NSSN bond.
• the amount of the hydroxyl group-containing compound having an NSSN bond is preferably 25 parts by mass to 100 parts by mass, more preferably 50 parts by mass to 100 parts by mass, even more preferably 75 parts by mass to 100 parts by mass, and most preferably 100 parts by mass of the hydroxyl group-containing compound having an NSSN bond, i.e., the polyol compound is most preferably made of a hydroxyl group-containing compound having an NSSN bond.
• hydroxyl-containing compound having an NSSN bond is a compound represented by the following general formula (1) and containing two or more hydroxyl groups. These may be used alone or in combination of two or more.
• n1 is an integer of 1 to 5.
• the structure of the compound represented by general formula (1) is not particularly limited, and for example, the bonds may form a ring.
• the hydroxyl-containing compound having an NSSN bond represented by general formula (1) include compounds represented by general formula (2) or general formula (3) described below.
• the hydroxyl-containing compound having an NSSN bond is preferably a compound represented by general formula (2) or general formula (3) from the viewpoint of easily forming a urethane prepolymer composition having an excellent balance between self-repairability and coloring resistance.
• the compound represented by general formula (1) and containing two or more hydroxyl groups can be produced, for example, by adding sodium acetate and dimethylformamide to an amino compound having a polymerizable functional group with 1 to 50 carbon atoms, dropping disulfur dichloride under a nitrogen atmosphere, and collecting the resulting precipitate by filtration, washing with water, and concentrating it, or by reacting a diaminodisulfide compound having a hydroxyl group with a compound having a corresponding polymerizable reactive group with 1 to 50 carbon atoms.
• R 21 , R 22 , R 23 , R 24 , R 25 , R 26 , R 27 and R 28 each independently represent an unsubstituted or substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms, or the aliphatic hydrocarbon group in which one or more methylene groups are replaced with a divalent group selected from Group I-2 below.
• One or more hydrogen atoms in the substituted aliphatic hydrocarbon group are replaced with an atom or group selected from Group II-2 below.
• Group I-2 -O-, -OCO-, -OCO-NR'-
• Group II-2 halogen atom, cyano group, nitro group
• X21 and X22 each independently represent a direct bond, an unsubstituted or substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms, or the aliphatic hydrocarbon group in which one or more methylene groups are replaced with a divalent group selected from Group I-3 below.
• One or more hydrogen atoms in the substituted aliphatic hydrocarbon group are replaced with an atom or group selected from Group II-3 below.
• Group I-3 -O-, -OCO-, -OCO-NR'-
• Group II-3 halogen atom, cyano group, nitro group
• Each R' independently represents a hydrogen atom or an unsubstituted aliphatic hydrocarbon group. When a plurality of R's are present, they may be the same or different.
• halogen atom in group II-2 used for substituting the aliphatic hydrocarbon groups represented by R 21 , R 22 , R 23 , R 24 , R 25 , R 26 , R 27 and R 28 in general formula (2) (hereinafter also referred to as "halogen atom used for substituting R 21 , etc.") include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, and the like.
• the unsubstituted or substituted aliphatic hydrocarbon groups having 1 to 20 carbon atoms represented by R 21 , R 22 , R 23 , R 24 , R 25 , R 26 , R 27 and R 28 in general formula (2) may be any groups not containing an aromatic hydrocarbon ring or a heterocycle. Examples of the aliphatic hydrocarbon groups represented by R 21 etc.
• alkyl groups having 1 to 20 carbon atoms include alkyl groups having 1 to 20 carbon atoms, alkenyl groups having 2 to 20 carbon atoms, cycloalkyl groups having 3 to 20 carbon atoms, cycloalkylalkyl groups having 4 to 20 carbon atoms, and groups in which one or more hydrogen atoms of these groups are substituted by the substituents described in Group I-3.
• the aliphatic hydrocarbon group represented by R 21 or the like is preferably an unsubstituted aliphatic hydrocarbon group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 20 carbon atoms, even more preferably an alkyl group having 1 to 20 carbon atoms, even more preferably an alkyl group having 1 to 10 carbon atoms, and most preferably a methyl group.
• examples of the halogen atom in group II-3 used to substitute the aliphatic hydrocarbon group represented by X 21 and X 22 include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
• X21 and X22 each independently preferably represent a direct bond or an unsubstituted aliphatic hydrocarbon group having 1 to 20 carbon atoms, and more preferably a direct bond.
• the aliphatic hydrocarbon groups represented by X21 and X22 are preferably unsubstituted aliphatic hydrocarbon groups having 1 to 10 carbon atoms, and more preferably unsubstituted aliphatic hydrocarbon groups having 1 to 5 carbon atoms.
• n2 is an integer from 1 to 5. From the viewpoint of easily forming a urethane prepolymer composition that has an excellent balance of self-repairing properties and coloration resistance, n2 is preferably an integer from 1 to 3, and more preferably 1.
• the number of carbon atoms in a group specifies the number of carbon atoms in the group after the substitution when a hydrogen atom in the group is substituted with a substituent.
• the number of carbon atoms of 1 to 20 refers to the number of carbon atoms after the hydrogen atom is substituted, not the number of carbon atoms before the hydrogen atom is substituted.
• the number of carbon atoms in a group in which a methylene group in a group having a predetermined number of carbon atoms is replaced with a divalent group is defined as the same as the number of carbon atoms in the group before the substitution.
• the number of carbon atoms in a group in which a methylene group in an alkyl group having 1 to 20 carbon atoms is replaced with a divalent group is defined as 1 to 20.
• the compound represented by formula (2) includes the following compounds No. 1-1 to No. 1-5, but the present disclosure is not limited to these compounds.
• the compound represented by general formula (2) is preferably compound No. 1-1, from the viewpoint of easily forming a urethane prepolymer composition having an excellent balance between self-repairing properties and coloration resistance.
• R 31 , R 32 , R 33 and R 34 each independently represent a hydrogen atom, a group represented by the following general formula (3-1), an unsubstituted or substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms, or the above-mentioned aliphatic hydrocarbon group in which one or more methylene groups are replaced with a divalent group selected from the following Group I-4.
• One or more hydrogen atoms in the above-mentioned substituted aliphatic hydrocarbon group are replaced with an atom or group selected from the following Group II-4.
• Group I-4 -O-, -COO-, -OCO-, -CO-, -NR'-, -NR'-CO-, -CO-NR'-, -NR'-COO-, -OCO-NR'- Group II-4: an acrylic group, a methacrylic group, a halogen atom, a cyano group, a nitro group
• R' independently represents a hydrogen atom or an unsubstituted aliphatic hydrocarbon group. When a plurality of R' or R" are present, they may be the same or different.
• At least one of R 31 and R 32 represents a group represented by the following general formula (3-1), and at least one of R 33 and R 34 represents a group represented by the following general formula (3-1).
• L 41 represents a direct bond, an aliphatic hydrocarbon group having 1 to 20 carbon atoms, or the aliphatic hydrocarbon group in which one or more methylene groups have been replaced with a divalent group selected from the following group I-5.
• Examples of the halogen atom in Group II-4 used to substitute the aliphatic hydrocarbon group represented by R 31 , R 32 , R 33 , and R 34 in general formula (3) include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
• R 31 , R 32 , R 33 , and R 34 each independently represent a group represented by general formula (3-1), an unsubstituted or substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms, or the above-mentioned aliphatic hydrocarbon group in which one or more methylene groups have been replaced by a divalent group selected from Group I-4, and more preferably a group represented by general formula (3-1) or an unsubstituted aliphatic hydrocarbon group having 1 to 20 carbon atoms.
• R 32 and R 33 are preferably a hydrogen atom or the same unsubstituted aliphatic hydrocarbon group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 20 carbon atoms, and even more preferably an alkyl group having 1 to 10 carbon atoms.
• the unsubstituted or substituted aliphatic hydrocarbon groups having 1 to 20 carbon atoms represented by R 31 , R 32 , R 33 , and R 34 in general formula (3) may be any groups not containing an aromatic hydrocarbon ring or a heterocycle. Examples of the aliphatic hydrocarbon groups represented by R 31 , etc.
• alkyl groups having 1 to 20 carbon atoms include alkyl groups having 1 to 20 carbon atoms, alkenyl groups having 2 to 20 carbon atoms, cycloalkyl groups having 3 to 20 carbon atoms, cycloalkylalkyl groups having 4 to 20 carbon atoms, and groups in which one or more hydrogen atoms of these groups are substituted by the substituents of Group II-4.
• examples of the alkyl group having 1 to 20 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a sec-butyl group, a tert-butyl group, an isobutyl group, an amyl group, an isopentyl group, a tert-pentyl group, a cyclopentyl group, a hexyl group, a 2-hexyl group, a 3-hexyl group, a cyclohexyl group, a 4-methylcyclohexyl group, a heptyl group, a 2-heptyl group, a 3-heptyl group, an isoheptyl group, a tert-heptyl group, a 1-octyl group, an isooctyl group, a tert-octyl group, and an alkyl group,
• the alkyl group having 1 to 20 carbon atoms is preferably a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a sec-butyl group, a tert-butyl group, or an isobutyl group, from the viewpoint of easily forming a urethane prepolymer composition having an excellent balance of self-repairing properties and coloration resistance, more preferably an ethyl group, a propyl group, an isopropyl group, a butyl group, a sec-butyl group, a tert-butyl group, or an isobutyl group, and even more preferably a tert-butyl group.
• examples of the alkenyl group having 2 to 20 carbon atoms include a vinyl group, an ethylene group, a 2-propenyl group, a 3-butenyl group, a 2-butenyl group, a 4-pentenyl group, a 3-pentenyl group, a 2-hexenyl group, a 3-hexenyl group, a 5-hexenyl group, a 2-heptenyl group, a 3-heptenyl group, a 4-heptenyl group, a 3-octenyl group, a 3-nonenyl group, a 4-decenyl group, a 3-undecenyl group, a 4-dodecenyl group, a 4,8,12-tetradecatrienylallyl group, and a cyclopentadienyl group.
• a cycloalkylalkyl group having 4 to 20 carbon atoms means a group having 4 to 20 carbon atoms in which some of the hydrogen atoms of an alkyl group are replaced with a cycloalkyl group.
• n3 is an integer from 1 to 5. From the viewpoint of easily forming a urethane prepolymer composition that has an excellent balance of self-repairability and coloration resistance, n3 is preferably an integer from 1 to 3, and more preferably 1.
• L 41 is preferably an aliphatic hydrocarbon group having 1 to 20 carbon atoms, from the viewpoint of easily forming a urethane prepolymer composition having an excellent balance of self-repairing properties and discoloration resistance.
• the aliphatic hydrocarbon group having 1 to 20 carbon atoms represented by L 41 is preferably an aliphatic hydrocarbon group having 1 to 10 carbon atoms, and more preferably an aliphatic hydrocarbon group having 1 to 5 carbon atoms, from the viewpoint of easily forming a urethane prepolymer composition having an excellent balance of self-repairability and discoloration resistance.
• examples of the aliphatic hydrocarbon group having 1 to 5 carbon atoms include a methanediyl group, a 1,2-ethanediyl group, a 1,2-propanediyl group, a 1,3-propanediyl group, a 1,4-butanediyl group, and a 1,5-pentanediyl group.
• the aliphatic hydrocarbon group having 1 to 5 carbon atoms is preferably a methanediyl group or a 1,2-ethanediyl group, more preferably a 1,2-ethanediyl group, from the viewpoint of easily forming a urethane prepolymer composition having an excellent balance of self-repairability and coloration resistance.
• the compound represented by formula (3) includes the following compounds No. 2-1 to No. 2-5, but the present disclosure is not limited to these compounds.
• "t-Bu” represents a tert-butyl group.
• the compound represented by general formula (3) is preferably compound No. 2-1, from the viewpoint of easily forming a urethane prepolymer composition having excellent self-repairing properties.
• examples of the hydroxyl-containing compound having no NSSN bond include low molecular weight polyols, polycarbonate polyols, polyether polyols, polyester polyols, polylactone polyols, polyolefin polyols, polymethacrylate diols, and polysiloxane polyols. These may be used alone or in combination of two or more.
• low molecular weight polyols examples include aliphatic polyols with a molecular weight of about 50 to 200, such as ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, neopentyl glycol, and 1,3-butanediol; polyols with an aliphatic cyclic structure, such as cyclohexanedimethanol; and polyols with an aromatic structure, such as bisphenol A and bisphenol F.
• aliphatic polyols with a molecular weight of about 50 to 200 such as ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, neopentyl glycol, and 1,3-butanediol
• polyols with an aliphatic cyclic structure such as cyclohexanedim
• polycarbonate polyol examples include polytetramethylene carbonate diol, polypentamethylene carbonate diol, polyneopentyl carbonate diol, polyhexamethylene carbonate diol, poly(1,4-cyclohexanedimethylene carbonate) diol, and random/block copolymers thereof.
• polycarbonate polyol commercially available products may be used, and examples thereof include DN-980, DN-981 (manufactured by Nippon Polyurethane Industry Co., Ltd.), Priplast (registered trademark) 3196, 3190, 2033 (manufactured by Unichema), PNOC-2000, PNOC-1000 (manufactured by Kuraray Co., Ltd.), PLACCEL (registered trademark) CD220, CD210, CD208, CD205 (manufactured by Daicel Corporation), and PC-THF-CD (manufactured by BASF).
• polyether polyols examples include those obtained by polymerizing or copolymerizing any one of alkylene oxides (ethylene oxide, propylene oxide, butylene oxide, etc.) and heterocyclic ethers (tetrahydrofuran, etc.). Specific examples include polyethylene glycol, polypropylene glycol, polyethylene glycol-polytetramethylene glycol (block or random), polytetramethylene ether glycol, and polyhexamethylene glycol.
• polyether polyol commercially available products may be used, and examples thereof include PTG-2000SN (polytetramethylene ether glycol) (manufactured by Hodogaya Chemical Co., Ltd.), Preminol (registered trademark) S3003 (polypropylene glycol) (manufactured by AGC Corporation), Pandex (registered trademark) GCB-41 (manufactured by DIC Corporation), and Adeka polyether polyol (manufactured by ADEKA Corporation).
• PTG-2000SN polytetramethylene ether glycol
• S3003 polypropylene glycol
• Pandex registered trademark
• GCB-41 manufactured by DIC Corporation
• Adeka polyether polyol manufactured by ADEKA Corporation
• polyester polyols include those obtained by condensation polymerization of at least one of aliphatic dicarboxylic acids (e.g., succinic acid, adipic acid, sebacic acid, glutaric acid, azelaic acid, etc.) and aromatic dicarboxylic acids (e.g., isophthalic acid, terephthalic acid, etc.) and low molecular weight glycols (e.g., ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,3-butylene glycol, 1,4-butylene glycol, 1,6-hexamethylene glycol, neopentyl glycol, 1,4-bishydroxymethylcyclohexane, etc.).
• aliphatic dicarboxylic acids e.g., succinic acid, adipic acid, sebacic acid, glutaric acid, azelaic acid, etc.
• aromatic dicarboxylic acids e.g., isophthalic acid
• polyethylene adipate diol polybutylene adipate diol, polyhexamethylene adipate diol, polyneopentyl adipate diol, polyethylene/butylene adipate diol, polyneopentyl/hexyl adipate diol, poly-3-methylpentane adipate diol, and polybutylene isophthalate diol.
• polyester polyol commercially available products may be used, and examples thereof include Teslac (registered trademark) 2464 (manufactured by Resonac Co., Ltd.), Nipporan (registered trademark) 163 (manufactured by Tosoh Corporation), HS2P-103S (manufactured by Toyokuni Oil Mills Co., Ltd.), Kuraray Polyol P-2010 (manufactured by Kuraray Co., Ltd.), and Adeka New Ace (registered trademark) (manufactured by ADEKA Corporation).
• Teslac registered trademark
• 2464 manufactured by Resonac Co., Ltd.
• Nipporan registered trademark 163
• HS2P-103S manufactured by Toyokuni Oil Mills Co., Ltd.
• Kuraray Polyol P-2010 manufactured by Kuraray Co., Ltd.
• Adeka New Ace registered trademark
• polylactone polyols examples include polycaprolactone diol and poly-3-methylvalerolactone diol.
• Polyolefin polyols include polybutadiene glycol, polyisoprene glycol, and their hydrogenated derivatives.
• polymethacrylate diols examples include ⁇ , ⁇ -polymethyl methacrylate diol and ⁇ , ⁇ -polybutyl methacrylate diol.
• polysiloxane polyol is dimethylpolysiloxane.
• the isocyanate compound is not particularly limited, and examples thereof include diisocyanates having two isocyanate groups in one molecule, isocyanates having three or more isocyanate groups in one molecule, etc. These may be used alone or in combination of two or more.
• Diisocyanates having two isocyanate groups per molecule include, for example, aromatic diisocyanates such as tolylene diisocyanate, diphenylmethane-4,4'-diisocyanate, p-phenylene diisocyanate, xylylene diisocyanate, 1,5-naphthylene diisocyanate, 3,3'-dimethyldiphenyl-4,4'-diisocyanate, dianisidine diisocyanate, and tetramethylxylylene diisocyanate; isophorone diisocyanate.
• aromatic diisocyanates such as tolylene diisocyanate, diphenylmethane-4,4'-diisocyanate, p-phenylene diisocyanate, xylylene diisocyanate, 1,5-naphthylene diisocyanate, 3,3'-dimethyldiphenyl-4,4'-diisocyanate, dian
• Alicyclic diisocyanates such as dicyclohexylmethane-4,4'-diisocyanate, trans-1,4-cyclohexane diisocyanate, cis-1,4-cyclohexane diisocyanate, and norbornene diisocyanate; and aliphatic diisocyanates such as 1,6-hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, and lysine diisocyanate. These may be used alone or in combination of two or more.
• diisocyanates commercially available products may be used, such as VESTANAT (registered trademark) IPDI (isophorone diisocyanate), TMDI (2,2,4-trimethylhexamethylene diisocyanate) (manufactured by Evonik), and HDI (hexamethylene diisocyanate) (manufactured by Tosoh Corporation).
• VESTANAT registered trademark
• IPDI isophorone diisocyanate
• TMDI 2,2,4-trimethylhexamethylene diisocyanate
• HDI hexamethylene diisocyanate
• isocyanates having three or more isocyanate groups in one molecule include triphenylmethane triisocyanate, 1-methylbenzene-2,4,6-triisocyanate, and dimethyltriphenylmethane tetraisocyanate; modified products of these isocyanates, such as carbodiimide-modified, isocyanurate-modified, and biuret-modified products; blocked isocyanates in which these modified products are blocked with various blocking agents; and isocyanurate trimers and biuret trimers of the diisocyanates mentioned above.
• an isocyanate having three or more isocyanate groups in one molecule a commercially available product may be used, such as Duranate (registered trademark) TKA-100 (isocyanurate) (manufactured by Asahi Kasei Corporation) or Lupranate (registered trademark) M20S (manufactured by BASF INOAC Polyurethanes Co., Ltd.).
• Duranate registered trademark
• TKA-100 isocyanurate
• Lupranate registered trademark
• M20S manufactured by BASF INOAC Polyurethanes Co., Ltd.
• the isocyanate compound preferably has a molecular weight in the range of 50 to 1,000, more preferably has a molecular weight in the range of 50 to 500, and even more preferably has a molecular weight in the range of 100 to 500.
• the method for producing the urethane prepolymer composition is not particularly limited, and the urethane prepolymer composition can be produced by reacting a polyol compound containing at least one hydroxyl group-containing compound having an NSSN bond with an isocyanate compound in the presence of a solvent and a catalyst as necessary, either all at once or in stages.
• the reaction conditions of the polyol compound and the isocyanate compound are not particularly limited, but it is preferable to react them at a temperature of 10°C to 100°C for 1.0 to 6.0 hours, and it is more preferable to react them at a temperature of 30°C to 80°C for 1.5 to 4.5 hours.
• the urethane prepolymer composition of the present disclosure may contain an unreacted polyol compound or an unreacted isocyanate compound.
• the production of the urethane prepolymer composition is preferably carried out in the presence of a solvent from the viewpoint of ease of reaction control and improved workability.
• a solvent examples include ketones such as methyl ethyl ketone, methyl ethyl ketone, methyl amyl ketone, diethyl ketone, acetone, methyl isopropyl ketone, and cyclohexanone; ethers such as tetrahydrofuran, 1,2-dimethoxyethane, and 1,2-diethoxyethane; esters such as ethyl acetate and n-butyl acetate; alcohols such as isobutanol, n-butanol, isopropanol, n-propanol, and amyl alcohol; ether alcohols such as methyl cellosolve, ethyl cellosolve, and butyl cellosolve; aromatic hydrocarbons such as benzene,
• the solvent is preferably a ketone, more preferably methyl ethyl ketone, from the viewpoint of easily forming a urethane prepolymer composition that has an excellent balance of self-repairing properties and color resistance.
• the amount of the solvent is not particularly limited, but from the standpoint of safety and environmental impact, it is preferably 0 to 150 parts by mass, more preferably 0 to 100 parts by mass, even more preferably 0 to 60 parts by mass, and most preferably 10 to 50 parts by mass, per 100 parts by mass of the polyol compound containing a hydroxyl group-containing compound having an NSSN bond and the isocyanate compound.
• the production of the urethane prepolymer composition is preferably carried out in the presence of a catalyst from the viewpoint of ease of production of the urethane prepolymer composition.
• a catalyst a metal catalyst or an amine catalyst can be used.
• tin catalysts such as dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin dilaurate, dibutyltin dioctate, etc.
• lead catalysts such as lead octoate, lead octenate, lead naphthenate, etc.
• bismuth catalysts such as bismuth octoate, bismuth neodecanoate, etc.
• amine catalyst there can be mentioned diethylenetriamine, etc.
• a tin catalyst from the viewpoint of easily forming a urethane prepolymer composition having an excellent balance of self-repairing properties and color resistance, and there can be more preferably dibutyltin dilaurate.
• the amount of catalyst used is not particularly limited, but from the standpoint of safety and environmental impact, it is preferably 0 to 20 parts by mass, more preferably 0 to 10 parts by mass, and even more preferably 0.01 to 5 parts by mass, per 100 parts by mass of the total of the polyol compound containing a hydroxyl group-containing compound having an NSSN bond and the isocyanate compound.
• Ratio of hydroxyl group equivalent to isocyanate group equivalent In the production of the urethane prepolymer composition in the present disclosure, when the ratio (NCO/OH) of the total isocyanate group equivalent of the isocyanate compound to the total hydroxyl group equivalent of the polyol compound containing a hydroxyl group-containing compound having an NSSN bond is less than 1.0, a urethane prepolymer composition containing a urethane prepolymer having a hydroxyl group at the end is obtained, and when NCO/OH is 1.0 or more, a urethane prepolymer composition containing a urethane prepolymer having an isocyanate group at the end is obtained.
• the ratio (NCO/OH) of the total isocyanate group equivalent of the isocyanate compound to the total hydroxyl group equivalent of the polyol compound containing a hydroxyl group-containing compound having an NSSN bond is a theoretical value calculated from the amount of raw materials used to produce the urethane prepolymer composition.
• the ratio (NCO/OH) of the total isocyanate group equivalent of the isocyanate compound to the total hydroxyl group equivalent of the polyol compound containing a hydroxyl group-containing compound having an NSSN bond is preferably 1.0 or more, more preferably 1.0 to 15.0, even more preferably 1.1 to 12.0, even more preferably 1.5 to 10.0, and most preferably 3.0 to 10.0.
• the urethane prepolymer composition of the present disclosure includes a urethane prepolymer obtained by reacting a polyol compound containing a hydroxyl group-containing compound having an NSSN bond with an isocyanate compound.
• a wide variety of compounds are used as raw materials for the polyol compound and the isocyanate compound, and the polyol compound and the isocyanate compound react with each other arbitrarily, so that the structure of the obtained urethane prepolymer cannot be expressed by a general formula, and this is common technical knowledge for those skilled in the art.
• the structure is not specified, the properties of the substance determined accordingly cannot be easily known, and therefore it is impossible to express it by its properties.
• the urethane prepolymer composition of the present disclosure cannot be directly specified by its structure or properties, and can only be specified by the manufacturing method for obtaining the urethane prepolymer composition.
• the urethane prepolymer contained in the urethane prepolymer composition must be defined as "a urethane prepolymer obtained by reacting at least one polyol compound with at least one isocyanate compound". Therefore, with respect to the urethane prepolymer composition of the present disclosure, there are circumstances in which it is impossible or nearly impractical to "directly identify the urethane prepolymer composition by its structure or properties at the time of filing.”
• the urethane resin composition according to the first aspect of the present disclosure is characterized by comprising a hydroxyl group-containing compound having no NSSN bond and a urethane prepolymer composition.
• the hydroxyl-containing compound that does not have an NSSN bond is preferably a polyether polyol, more preferably a polyethylene glycol or polytetramethylene ether glycol, from the viewpoint of easily forming a compound that has an excellent balance between self-repairability and color resistance.
• the urethane prepolymer composition may be the same as that described in the section "A. Urethane prepolymer composition", and therefore a description thereof will be omitted here. From the viewpoint of easily forming a urethane prepolymer composition having an excellent balance between self-repairability and color resistance, it is preferable that the urethane prepolymer composition contains a urethane prepolymer having an isocyanate group at the end.
• Ratio of hydroxyl group equivalent to isocyanate group equivalent In the urethane resin composition according to the first aspect of the present disclosure, from the viewpoint of easily forming a composition with excellent self-repairing properties, the ratio (NCO/OH) of the total isocyanate group equivalent of the urethane prepolymer (when contained in the urethane prepolymer composition) and the unreacted isocyanate compound (when contained in the urethane prepolymer composition) having an isocyanate group at the end to the total hydroxyl group equivalent of the urethane prepolymer (when contained in the urethane prepolymer composition) having an isocyanate group at the end, from the viewpoint of easily forming a composition with excellent self-repairing properties.
• the ratio is in the range of 0.001 to 2.5, more preferably in the range of 0.01 to 1.5, and even more preferably in the range of 0.1 to 1.1.
• the ratio (NCO/OH) of the total isocyanate group equivalent of a urethane prepolymer having an isocyanate group at its terminal (when contained in a urethane prepolymer composition) and an unreacted isocyanate compound (when contained in a urethane prepolymer composition) to the total hydroxyl group equivalent of a hydroxyl group-containing compound having no NSSN bond, a urethane prepolymer having a hydroxyl group at its terminal (when contained in a urethane prepolymer composition), and an unreacted polyol compound (when contained in a urethane prepolymer composition) is a theoretical value calculated from the amounts of raw materials charged to prepare the urethane resin composition.
• the urethane resin composition according to the first aspect of the present disclosure may contain components such as an isocyanate compound, a solvent, various additives, a catalyst, etc. These may be used alone or in combination of two or more.
• isocyanate compound As the isocyanate compound, the same ones as those described in “A-2. Isocyanate compound” of "A. Urethane prepolymer composition” can be used, so a detailed description is omitted here.
• Solvents include, for example, ketones such as methyl ethyl ketone, methyl amyl ketone, diethyl ketone, acetone, methyl isopropyl ketone, and cyclohexanone; ethers such as tetrahydrofuran, 1,2-dimethoxyethane, and 1,2-diethoxyethane; esters such as ethyl acetate and n-butyl acetate; alcohols such as iso- or n-butanol, iso- or n-propanol, and amyl alcohol; ether alcohols such as methyl cellosolve, ethyl cellosolve, and butyl cellosolve; aromatic hydrocarbons such as benzene, toluene, and xylene; halogenated aliphatic hydrocarbons such as carbon tetrachloride, chloroform, trichloroethylene, and methylene chloride; halogenated
• the solvent is preferably a ketone, more preferably methyl ethyl ketone, from the viewpoint of easily forming a composition having an excellent balance between self-repairing properties and coloration resistance.
• the blending amount of the solvent is not particularly limited, but from the viewpoints of safety and environmental load, the blending amount is preferably 1 to 10,000 parts by mass, more preferably 5 to 500 parts by mass, even more preferably 10 to 300 parts by mass, and most preferably 20 to 100 parts by mass, relative to 100 parts by mass of the total amount of the hydroxyl group-containing compound having no NSSN bond and the urethane prepolymer composition.
• additives such as plasticizers, fillers, pigments, dyes, stabilizers, flame retardants, and other known additives, may be used to the extent that they do not impair the effects of the present disclosure.
• the catalyst may be, for example, a metal catalyst or an amine catalyst that is normally used in the production of polyurethane resins.
• Metal catalysts include tin catalysts such as dibutyltin dilaurate, dioctyltin dilaurate, and dibutyltin dioctate; lead catalysts such as lead octoate, lead octenate, and lead naphthenate; and bismuth catalysts such as bismuth octoate and bismuth neodecanoate.
• An example of an amine catalyst is diethylenetriamine.
• the amount of catalyst used is not particularly limited, but from the standpoint of safety and environmental impact, it is preferably 0 to 20 parts by mass, and more preferably 0 to 10 parts by mass, per 100 parts by mass of the total amount of the hydroxyl group-containing compound not having an NSSN bond and the urethane prepolymer composition.
• the urethane resin composition according to the second aspect of the present disclosure is characterized by comprising a hydroxyl group-containing compound having no NSSN bond, an isocyanate compound, and a hydroxyl group-containing compound having an NSSN bond.
• Hydroxyl-containing compound having no NSSN bond In the urethane resin composition according to the second aspect of the present disclosure, as the hydroxyl-containing compound having no NSSN bond, the same compounds as those described in the section "A-1-2. Hydroxyl-containing compound having no NSSN bond" in "A. Urethane prepolymer composition" can be used, and therefore description thereof will be omitted here.
• the isocyanate compound in the urethane resin composition according to the second aspect of the present disclosure, may be the same as that described in the section "A-2. Isocyanate compound" of "A. Urethane prepolymer composition", and therefore a description thereof will be omitted here.
• Hydroxyl-containing compound having an NSSN bond In the urethane resin composition according to the second aspect of the present disclosure, the hydroxyl-containing compound having an NSSN bond may be the same as that described in the section "A-1-1. Hydroxyl-containing compound having an NSSN bond" in "A. Urethane prepolymer composition", and therefore a description thereof will be omitted here.
• Ratio of hydroxyl group equivalent to isocyanate group equivalent In the urethane resin composition according to the second aspect of the present disclosure, from the viewpoint of easily forming a composition with excellent self-repairing properties, the ratio of the isocyanate group equivalent of the isocyanate compound to the total hydroxyl group equivalent of the hydroxyl group-containing compound having an NSSN bond and the hydroxyl group-containing compound not having an NSSN bond (NCO / OH) is preferably in the range of 0.001 to 2.5, more preferably in the range of 0.01 to 1.5, and even more preferably in the range of 0.1 to 1.1.
• the ratio of the isocyanate group equivalent of the isocyanate compound to the total hydroxyl group equivalent of the hydroxyl group-containing compound having an NSSN bond and the hydroxyl group-containing compound not having an NSSN bond is a theoretical value calculated from the amount of raw materials used to prepare the urethane resin composition.
• the urethane resin composition according to the second embodiment of the present disclosure may contain other components such as a solvent, various additives, and a catalyst, as necessary.
• a solvent such as a solvent, various additives, and a catalyst, those similar to those described in the section "B-1-4.
• Other Components can be used, and therefore description thereof will be omitted here.
• the urethane resin composition according to the third aspect of the present disclosure is characterized by comprising an isocyanate compound and a urethane prepolymer composition.
• the isocyanate compound in the urethane resin composition according to the third aspect of the present disclosure, may be the same as that described in the section "A-2. Isocyanate compound" of "A. Urethane prepolymer composition", and therefore a description thereof will be omitted here.
• the urethane prepolymer composition may be the same as that described in the section "A. Urethane prepolymer composition", and therefore a description thereof will be omitted here. From the viewpoint of easily forming a urethane prepolymer composition having an excellent balance between self-repairability and coloring resistance, it is preferable that the urethane prepolymer composition contains a urethane prepolymer having a hydroxyl group at the end.
• Ratio of hydroxyl group equivalent to isocyanate group equivalent In the urethane resin composition according to the third aspect of the present disclosure, from the viewpoint of easily forming a composition having excellent self-repairing properties, the ratio (NCO / OH) of the isocyanate group equivalent of the isocyanate compound to the total hydroxyl group equivalent of the urethane prepolymer (when contained in the urethane prepolymer composition) having a hydroxyl group at the end and the unreacted polyol compound (when contained in the urethane prepolymer composition) is preferably in the range of 0.001 to 2.5, more preferably in the range of 0.01 to 1.5, and even more preferably in the range of 0.1 to 1.1.
• the ratio (NCO / OH) of the isocyanate group equivalent of the isocyanate compound to the total hydroxyl group equivalent of the urethane prepolymer (when contained in the urethane prepolymer composition) having a hydroxyl group at the end and the unreacted polyol compound (when contained in the urethane prepolymer composition) is a theoretical value calculated from the amount of raw materials used to prepare the urethane resin composition.
• the urethane resin composition according to the third aspect of the present disclosure may contain a solvent, various additives, and a catalyst, if necessary. Each of these may be used alone or in combination of two or more.
• the solvents, various additives, and catalysts that can be used are the same as those described in the section "B-1-4. Other Components," and therefore will not be described here.
• the cured product of the present disclosure can be, for example, one obtained by heating, curing, and molding the urethane resin composition described in the section "B. Urethane resin composition.”
• Examples of the method for hot molding include a method in which the urethane resin composition is injected into a cylindrical mold and then heat-cured, and a method in which the composition is applied to a substrate and then dried.
• Examples of the substrate that can be used include fibrous substrates such as nonwoven fabric, woven fabric, and knitted fabric; resin films, and glass.
• methods for applying the urethane resin composition to a substrate include coating methods using an applicator, a bar coater, a knife coater, a T-die coater, a roll coater, and the like.
• the applied urethane resin composition When the urethane resin composition is applied to a substrate and then dried, the applied urethane resin composition can be dried, for example, at a temperature of 50° C. to 140° C. for 30 seconds to 48 hours.
• the thickness of the resulting cured product is appropriately determined depending on the application, but is, for example, in the range of 0.001 mm to 10 mm.
• the urethane reaction of the urethane resin composition is preferably completed.
• Applications of the cured products of the present disclosure include, for example, transparent rigid plastics, waterproof materials, sheets, bands, belts, tubes, blades, speakers, sensors, outsoles, threads, paints, fibers, nonwoven fabrics, cosmetics, footwear, insulation materials, coating materials, sealing materials, tape materials, sealing materials, solar power generation components, robot components, android components, wearable components, clothing products, hygiene products, makeup products, furniture products, food packaging components, sporting goods, leisure goods, medical supplies, nursing care products, housing components, acoustic components, lighting components, vibration-proofing components, soundproofing components, daily necessities, miscellaneous goods, cushions, bedding, stress absorbing materials, stress relaxation materials, automotive interior materials, automotive exterior materials, railway components, aircraft components, optical components, office equipment components, miscellaneous goods surface protection components, semiconductor sealing materials, self-repairing materials, health equipment, eyeglass lenses, toys, gaskets, cable sheaths, wire harnesses, telecommunications cables, automotive wiring, computer wiring, industrial products, shock absorbing materials, semiconductor products, and self
• urethane prepolymer composition A1 (molecular weight: 376.62 g/mol) as a hydroxyl group-containing compound having an NSSN bond, 25 parts by mass of methyl ethyl ketone (MEK) as a solvent, and 0.1 parts by mass of dibutyltin dilaurate as a catalyst were added, and the mixture was heated at 60° C. for 3 hours to react, thereby obtaining a urethane prepolymer composition A1.
• the ratio (NCO/OH) of the isocyanate group equivalent to the hydroxyl group equivalent when producing the urethane prepolymer composition A1 was 4.75.
• Example 1 To 93 parts by mass of the urethane prepolymer composition A1, 24 parts by mass of polytetramethylene ether glycol (PTMG1000; manufactured by Mitsubishi Chemical Corporation, average molecular weight 1000, number of functional groups 2) as a hydroxyl group-containing compound having no NSSN bond and 33 parts by mass of polyether polyol (G300; manufactured by ADEKA Corporation, average molecular weight 300, number of functional groups 3) were mixed in 14 parts by mass of methyl ethyl ketone (MEK) as a solvent, and a solution was added to obtain the urethane resin composition of Example 1.
• PTMG1000 polytetramethylene ether glycol
• MEK methyl ethyl ketone
• the ratio (NCO/OH) of the isocyanate group equivalent to the hydroxyl group equivalent in the urethane resin composition of Example 1 was 0.95.
• the urethane resin composition of Example 1 was applied onto a slide glass substrate using a No. 42 bar coater (96 ⁇ m) and heated at 80° C. for 18 hours to prepare a film-like cured product.
• Example 2 To 84 parts by mass of the urethane prepolymer composition A2, 24 parts by mass of polytetramethylene ether glycol (PTMG1000; manufactured by Mitsubishi Chemical Corporation, average molecular weight 1000, number of functional groups 2) as a hydroxyl group-containing compound having no NSSN bond and 38 parts by mass of polyether polyol (G300; manufactured by ADEKA Corporation, average molecular weight 300, number of functional groups 3) were mixed in 15 parts by mass of methyl ethyl ketone (MEK) as a solvent to obtain a urethane resin composition of Example 2. The ratio (NCO/OH) of the isocyanate group equivalent to the hydroxyl group equivalent in the urethane resin composition of Example 2 was 0.95. The urethane resin composition of Example 2 was applied onto a slide glass substrate using a No. 42 bar coater (96 ⁇ m) and heated at 80° C. for 18 hours to prepare a film-like cured product.
• PTMG1000 polytetramethylene
• Example 3 To 90 parts by mass of the urethane prepolymer composition A3, 25 parts by mass of polytetramethylene ether glycol (PTMG1000; manufactured by Mitsubishi Chemical Corporation, average molecular weight 1000, number of functional groups 2) as a hydroxyl group-containing compound having no NSSN bond and 35 parts by mass of polyether polyol (G300; manufactured by ADEKA Corporation, average molecular weight 300, number of functional groups 3) were mixed in 15 parts by mass of methyl ethyl ketone (MEK) as a solvent, and a solution was added to obtain a urethane resin composition of Example 3.
• PTMG1000 polytetramethylene ether glycol
• MEK methyl ethyl ketone
• the ratio (NCO/OH) of the isocyanate group equivalent to the hydroxyl group equivalent in the urethane resin composition of Example 3 was 0.91.
• the urethane resin composition of Example 3 was applied onto a slide glass substrate using a No. 42 bar coater (96 ⁇ m) and heated at 80° C. for 18 hours to prepare a film-like cured product.
• Example 4 To 93 parts by mass of the urethane prepolymer composition A1, 9 parts by mass of polyethylene glycol (PEG400; manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., average molecular weight 400, number of functional groups 2) as a hydroxyl group-containing compound having no NSSN bond and 33 parts by mass of polyether polyol (G300; manufactured by ADEKA Corporation, average molecular weight 300, number of functional groups 3) were mixed in 11 parts by mass of methyl ethyl ketone (MEK) as a solvent, and a solution was added to obtain a urethane resin composition of Example 4.
• PEG400 polyethylene glycol
• MEK methyl ethyl ketone
• the ratio (NCO/OH) of the isocyanate group equivalent to the hydroxyl group equivalent in the urethane resin composition of Example 4 was 0.95.
• the urethane resin composition of Example 4 was applied onto a slide glass substrate using a No. 42 bar coater (96 ⁇ m) and heated at 80° C. for 18 hours to prepare a film-like cured product.
• Example 5 To 89 parts by mass of the urethane prepolymer composition A3, 10 parts by mass of polyethylene glycol (PEG400; manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., average molecular weight 400, number of functional groups 2) as a hydroxyl group-containing compound having no NSSN bond and 35 parts by mass of polyether polyol (G300; manufactured by ADEKA Corporation, average molecular weight 300, number of functional groups 3) were mixed in 11 parts by mass of methyl ethyl ketone (MEK) as a solvent to obtain a urethane resin composition of Example 5.
• MEK methyl ethyl ketone
• the ratio (NCO/OH) of the isocyanate group equivalent to the hydroxyl group equivalent in the urethane resin composition of Example 5 was 0.91.
• the urethane resin composition of Example 5 was applied onto a slide glass substrate using a No. 42 bar coater (96 ⁇ m) and heated at 80° C. for 18 hours to prepare a
• Comparative Example 1 To 81 parts by mass of the urethane prepolymer composition B1, 24 parts by mass of polytetramethylene ether glycol (PTMG1000; manufactured by Mitsubishi Chemical Corporation, average molecular weight 1000, number of functional groups 2) as a hydroxyl group-containing compound having no NSSN bond and 38 parts by mass of polyether polyol (G300; manufactured by ADEKA Corporation, average molecular weight 300, number of functional groups 3) were mixed in 15 parts by mass of methyl ethyl ketone (MEK) as a solvent, and a urethane resin composition of Comparative Example 1 was obtained.
• PTMG1000 polytetramethylene ether glycol
• MEK methyl ethyl ketone
• the ratio (NCO/OH) of the isocyanate group equivalent to the hydroxyl group equivalent in the urethane resin composition of Comparative Example 1 was 0.95.
• the urethane resin composition of Comparative Example 1 was applied onto a slide glass substrate using a No. 42 bar coater (96 ⁇ m) and heated at 80° C. for 18 hours to prepare a film-like cured product.
• Comparative Example 2 To 82 parts by mass of the urethane prepolymer composition B2, 25 parts by mass of polytetramethylene ether glycol (PTMG1000; manufactured by Mitsubishi Chemical Corporation, average molecular weight 1000, number of functional groups 2) as a hydroxyl group-containing compound having no NSSN bond and 35 parts by mass of polyether polyol (G300; manufactured by ADEKA Corporation, average molecular weight 300, number of functional groups 3) were mixed in 15 parts by mass of methyl ethyl ketone (MEK) as a solvent to obtain a urethane resin composition of Comparative Example 2.
• PTMG1000 polytetramethylene ether glycol
• MEK methyl ethyl ketone
• the ratio (NCO/OH) of the isocyanate group equivalent to the hydroxyl group equivalent in the urethane resin composition of Comparative Example 2 was 0.91.
• the urethane resin composition of Comparative Example 2 was applied onto a slide glass substrate using a No. 42 bar coater (96 ⁇ m) and heated at 80° C. for 18 hours to prepare a film-like cured product.
• Comparative Example 3 To 81 parts by mass of the urethane prepolymer composition B1, 9 parts by mass of polyethylene glycol (PEG400; manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., average molecular weight 400, number of functional groups 2) as a hydroxyl group-containing compound having no NSSN bond and 38 parts by mass of polyether polyol (G300; manufactured by ADEKA Corporation, average molecular weight 300, number of functional groups 3) were mixed in 12 parts by mass of methyl ethyl ketone (MEK) as a solvent to obtain a urethane resin composition of Comparative Example 3.
• PEG400 polyethylene glycol
• MEK methyl ethyl ketone
• the ratio (NCO/OH) of the isocyanate group equivalent to the hydroxyl group equivalent in the urethane resin composition of Comparative Example 3 was 0.95.
• the urethane resin composition of Comparative Example 3 was applied onto a slide glass substrate using a No. 42 bar coater (96 ⁇ m) and heated at 80° C. for 18 hours to prepare a film-like cured product.
• urethane resin composition of Example 6 24 parts by mass of polytetramethylene ether glycol (PTMG1000; manufactured by Mitsubishi Chemical Corporation, average molecular weight 1000, number of functional groups 2) as a hydroxyl group-containing compound not having an NSSN bond and 38 parts by mass of polyether polyol (G300; manufactured by ADEKA Corporation, average molecular weight 300, number of functional groups 3) were mixed in 15 parts by mass of methyl ethyl ketone (MEK) as a solvent to obtain a urethane resin composition of Example 6.
• MEK methyl ethyl ketone
• the ratio (NCO/OH) of the isocyanate group equivalent to the hydroxyl group equivalent in the urethane resin composition of Example 6 was 0.95.
• the urethane resin composition of Example 6 was applied onto a slide glass substrate using a No. 42 bar coater (96 ⁇ m) and heated at 80° C. for 18 hours to prepare a film-like cured product.
• Comparative Example 4 50 parts by mass of isophorone diisocyanate as an isocyanate compound, 6 parts by mass of 4,4'-dithiodiphenol as a hydroxyl group-containing compound having no NSSN bond, 25 parts by mass of methyl ethyl ketone (MEK) as a solvent, and 0.1 parts by mass of dibutyltin dilaurate as a catalyst were mixed.
• the ratio (NCO/OH) of the isocyanate group equivalent to the hydroxyl group equivalent in the urethane resin composition of Comparative Example 4 was 0.95.
• the urethane resin composition of Comparative Example 4 was applied onto a slide glass substrate using a No. 42 bar coater (96 ⁇ m) and heated at 80° C. for 18 hours to prepare a film-like cured product.
• Comparative Example 5 50 parts by mass of isophorone diisocyanate as an isocyanate compound, 4 parts by mass of triethylene glycol (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., functional group number 2) as a hydroxyl group-containing compound having no NSSN bond, 25 parts by mass of methyl ethyl ketone (MEK) as a solvent, and 0.1 parts by mass of dibutyltin dilaurate as a catalyst were mixed.
• triethylene glycol manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., functional group number 2
• MEK methyl ethyl ketone
• the ratio of the isocyanate group equivalent to the hydroxyl group equivalent (NCO/OH) in the urethane resin composition of Comparative Example 5 was 0.95.
• the urethane resin composition of Comparative Example 5 was applied onto a slide glass substrate using a No. 42 bar coater (96 ⁇ m) and heated at 80° C. for 18 hours to prepare a film-like cured product.

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