Polyurethane, method for producing polyurethane, conductive paste composition, conductive wiring, and method for producing conductive wiring

Abstract

The present invention relates to a polyurethane, a method for producing the polyurethane, a conductive paste composition, a conductive wiring, and a method for producing the conductive wiring. The present invention is a polyurethane characterized by containing a phenolic hydroxyl group represented by the following general formula (1A). The present invention provides a conductive paste composition for forming a stretchable conductive wiring having less change in conductivity upon stretching, and a polyurethane of the composition.[Chem. 1]

Description

Technical Field

[0001] This invention relates to polyurethane, a method for manufacturing polyurethane, a conductive paste composition, conductive wiring, and a method for manufacturing conductive wiring. Existing technology

[0002] In recent years, with the popularization of IoT (Internet of Things), the development of wearable devices that can be installed on the human body has also progressed. Particular anticipation is high for their application in the fields of medical care, health care, and sports. Some researchers have already explored using real-time biometric monitoring, such as motion data and body movement sensing, to enable early disease detection and health management.

[0003] Wearable devices that continuously measure biometric information come in various forms, including jewelry such as watches, glasses, and headphones; clothing; and patches that are directly attached to the body. To stably and accurately measure biometric information, they need to conform to the body surface, especially in clothing and patch-type devices, where high flexibility, elasticity, and durability against repeated stretching and contraction are crucial. Therefore, the development of technologies and materials that provide flexibility to wiring and sensors is important.

[0004] For example, the wearable device described in Patent Document 1 uses a bellows-shaped stretchable silver wire covered with a stretchable urethane membrane. Even though the metal wire itself is not stretchable, the design of the wire is used to simulate stretchability and ensure conductivity.

[0005] Furthermore, there are also reports of methods for forming woven fabrics by incorporating conductive yarns to make them stretchable (Patent Document 2), and methods for forming stretchable conductive composite yarns by wrapping conductive fibers into stretchable elastic fibers (Patent Document 3).

[0006] However, the method of weaving conductive yarns has problems such as low freedom of pattern shape and lower production volume compared to forming patterns by printing. In addition, the method of Patent Document 1 also has limitations on pattern shape, and dense wiring design is more difficult. Therefore, the development of stretchable conductive pastes and inks that can still achieve conductivity when stretched by printing is in full swing.

[0007] For example, there have been many proposals and applications using gallium-indium-tin alloy (Galinstan), flexible wiring using liquid metal composed of gallium-indium, flexible wiring using silver nanowires mixed in the form of metal additives (Patent Document 4), flexible wiring using silver nanoparticles generated by combining fluororubber, surfactant and silver filler during annealing (Patent Document 5), flexible wiring using silver flakes with appropriate tap density and average particle size (Patent Document 6), and flexible wiring using silver powder with appropriate particle size, particle size distribution and porosity (Patent Document 7).

[0008] Existing technical documents

[0009] Patent documents

[0010] Patent Document 1: Japanese Patent No. 3923861

[0011] Patent Document 2: Japanese Patent No. 6657525

[0012] Patent Document 3: Japanese Patent Application Publication No. 2019-076214

[0013] Patent Document 4: International Publication No. 2017 / 217509

[0014] Patent Document 5: International Publication No. 2018 / 110632

[0015] Patent Document 6: Japanese Patent Application Publication No. 2019-110093

[0016] Patent Document 7: International Publication No. 2018 / 235734 Summary of the Invention

[0017] [The problem that the invention aims to solve]

[0018] The present invention was made to solve the above-mentioned problems, and the object is to provide a conductive paste composition for forming a flexible conductive wiring with minimal change in conductivity during stretching and contraction, and a polyurethane composition thereof.

[0019] [Methods for solving the problem]

[0020] To address the aforementioned issues, the present invention provides a polyurethane containing phenolic hydroxyl groups, represented by the following general formula (1A).

[0021] [Chemistry 1]

[0022]

[0023] In the formula, Az represents a straight-chain, branched, or cyclic (ka+2) valence hydrocarbon group or a fluorinated hydrocarbon group with 1 to 20 carbon atoms, and the -CH2- constituting the aforementioned (ka+2) valence hydrocarbon group can also be replaced by -O- or -NR. 4 -、-C(=O-、or-Si(R) 2 R 3 )-. R 2 R 3 It is a straight-chain, branched, or cyclic alkyl or phenyl group having 1 to 6 carbon atoms, R 4 The first group represents a hydrogen atom, or a straight-chain or branched alkyl group having 1 to 4 carbon atoms. Z represents a single bond or an oxygen atom. Xf independently represents a hydrogen atom, a halogen atom, a straight-chain, branched, or cyclic monovalent hydrocarbon group having 1 to 10 carbon atoms that may be substituted with a fluorine atom, an alkoxy group having 1 to 10 carbon atoms that may be substituted with a fluorine atom, or an electron-withdrawing group. Cycle ZZ independently represents an aromatic monocyclic or polycyclic ring having 5 to 20 carbon atoms. The carbon atoms in the aforementioned cycle ZZ may also be substituted with nitrogen, oxygen, or sulfur atoms. ka represents an integer from 0 to 2. kb and kd represent 1 or 2. kc and ke represent integers from 0 to 2, and dashed lines represent atomic bonds.

[0024] If it is such a polyurethane, it is a conductive paste composition that can provide for forming a flexible conductive wiring with minimal change in conductivity during expansion and contraction.

[0025] Furthermore, in this invention, the aforementioned polyurethane is preferably one containing phenolic hydroxyl groups as represented by the following general formula (1B).

[0026] [Chemistry 2]

[0027]

[0028] In the formula, Az' represents a straight-chain, branched, or cyclic (ka+2) valence hydrocarbon group or a fluorinated hydrocarbon group with 1 to 19 carbon atoms, and the -CH2- constituting the aforementioned (ka+2) valence hydrocarbon group can also be replaced by -O- or -NR. 4 -、-C(=O-、or-Si(R) 2 R 3 )-. ka represents an integer from 0 to 2. kb, kc, kd, and ke represent 1 or 2. R 2 R 3 R 4 As mentioned above, dashed lines represent atomic bonds.

[0029] If the polyurethane is of this type, then when preparing a conductive paste composition for forming a stretchable conductive wiring, it is possible to produce one that exhibits less change in conductivity during stretching.

[0030] Furthermore, in this invention, the aforementioned polyurethane is preferably one that contains one or more weakly acidic functional groups represented by the following general formulas (1a) to (1c).

[0031] [Chemistry 3]

[0032]

[0033] In the formula, R represents a hydrogen atom, a fluorine atom, or a straight-chain, branched, or cyclic hydrocarbon group with 1 to 10 carbon atoms that can also be fluorinated; Rf represents a fluorine atom or a straight-chain, branched, or cyclic fluorinated hydrocarbon group with 1 to 10 carbon atoms. n is an integer of 1 or 2, and the dashed line represents an atomic bond.

[0034] If the polyurethane is of this type, then when preparing a conductive paste composition for forming a stretchable conductive wiring, it is possible to make it exhibit even less change in conductivity during stretching.

[0035] Furthermore, in this invention, the aforementioned polyurethane is preferably a structure containing one or more of the following general formulas (2a) to (2c).

[0036] [Chemistry 4]

[0037]

[0038] In the formula, R 1 A is a hydrogen atom or a monovalent hydrocarbon group having 1 to 3 carbon atoms. a It represents a single bond, or a straight-chain, branched, or cyclic divalent hydrocarbon group with 1 to 20 carbon atoms, and the -CH2- group can also be substituted with -O-, -C(=O)-, -C(=O)O-, or -C6H4-, and can also be -NR. 4 -C(=O)-。 A b and A c Each can be independently represented by -O-, -OC (=O)-NR 4 -、-NR 4 Any one of the following groups: - or -C(=O)O-. 1 n 2 n 4 n is an integer between 0 and 10. 3 An integer that is either 0 or 1. R 4 As mentioned above, dashed lines represent atomic bonds.

[0039] If such a polyurethane is included in a conductive paste composition used to form a stretchable conductive wiring, it can be made to exhibit even less change in conductivity during stretching.

[0040] Furthermore, the present invention provides a method for manufacturing polyurethane, which is the method for manufacturing polyurethane described above, characterized in that: after the chain extension reaction, an alcohol or amine represented by the following general formula (1C) is used to introduce the aforementioned phenolic hydroxyl groups into the polyurethane.

[0041] [Chemistry 5]

[0042]

[0043] In the formula, "Az" represents a straight-chain, branched, or cyclic (ka+2) valence hydrocarbon group or a fluorinated hydrocarbon group with 1 to 19 carbon atoms, and the -CH2- constituting the aforementioned (ka+2) valence hydrocarbon group can also be replaced by -O-, -C(=O)-, or -Si(R 2 R 3 )-. X represents an oxygen atom or NR. 4 ka represents an integer from 0 to 2. kb, kc, kd, and ke represent 1 or 2. R 2 R 3 R 4 Same as above.

[0044] If such a method is used to manufacture polyurethane, the aforementioned polyurethane can be easily synthesized.

[0045] At this time, it is advisable to use one or more alcohols represented by the following general formulas (3a) to (3c) as chain extenders to introduce weak acid functional groups into polyurethane.

[0046] [Chemistry 6]

[0047]

[0048] In the formula, R 1 A is a hydrogen atom or a monovalent hydrocarbon group having 1 to 3 carbon atoms. a It represents a single bond, or a straight-chain, branched, or cyclic divalent hydrocarbon group with 1 to 20 carbon atoms, and the -CH2- group can also be substituted with -O-, -C(=O)-, -C(=O)O-, or -C6H4-, and can also be -NR. 4 -C(=O)-。 R 4 It consists of hydrogen atoms, or straight-chain or branched alkyl groups having 1 to 4 carbon atoms. 1 n 2 n 4 Integers from 0 to 10.

[0049] If such a method is used to manufacture polyurethane, then weakly acidic functional groups can be easily introduced into the polyurethane.

[0050] Furthermore, the present invention provides a conductive paste composition, characterized by containing:

[0051] (A) Conductive filler,

[0052] (B) The above-mentioned polyurethane, and

[0053] (C) Solvent.

[0054] If the conductive paste composition is such, a flexible conductive wiring with minimal change in conductivity during stretching can be formed.

[0055] Furthermore, in this invention, the aforementioned conductive paste composition preferably contains (D) phenolic compounds.

[0056] If the conductive paste composition is such, a flexible conductive wiring with less change in conductivity during stretching can be formed.

[0057] Furthermore, in this invention, the phenolic compound of component (D) mentioned above preferably contains a structure represented by the following general formula (2A).

[0058] [Chemistry 7]

[0059]

[0060] In the formula, R 6 Represents a hydrogen atom, halogen atom, cyano group, or hydroxyl group. Ay represents a straight-chain, branched, or cyclic (ka+2) valence hydrocarbon group or a fluorinated hydrocarbon group having 1 to 20 carbon atoms, and the -CH2- constituting the aforementioned (ka+2) valence hydrocarbon group can also be substituted with -O-, -C(=O)-, or -Si(R)-. 2 R 3 )-. ka represents an integer from 0 to 2. kb and kd represent 1 or 2. kc and ke represent integers from 0 to 2. Z, Xf, ZZ, R 2 R 3 Same as above.

[0061] If the conductive paste composition is such, a flexible conductive wiring with less change in conductivity during stretching can be formed.

[0062] Furthermore, in this invention, the phenolic compound of the aforementioned component (D) preferably contains a structure represented by the following general formula (2B).

[0063] [Chemistry 8]

[0064]

[0065] In the formula, Ay' represents a straight-chain, branched, or cyclic (ka+2) valence hydrocarbon group or a fluorinated hydrocarbon group with 1 to 19 carbon atoms, and the -CH2- constituting the aforementioned (ka+2) valence hydrocarbon group can also be substituted with -O-, -C(=O)-, or -Si(R 2 R 3)-. ka represents an integer from 0 to 2. kb, kc, kd, and ke represent 1 or 2. R 2 R 3 R 6 Same as above.

[0066] If the conductive paste composition is such, then a flexible conductive wiring with less change in conductivity during stretching can be formed.

[0067] At this point, it is advisable to use a conductive filler containing the aforementioned component (A) in a proportion of more than 70 parts by mass relative to the total of 100 parts by mass of components (A) and (B).

[0068] If the conductive paste composition is such, a stretchable conductive wiring with sufficient conductivity and less change in conductivity during stretching can be formed.

[0069] Furthermore, in this invention, the conductive filler of the aforementioned component (A) is preferably a powder selected from gold, silver, silver chloride, platinum, copper, tin, iron, magnesium, titanium, nickel, palladium, aluminum, tungsten, molybdenum, ruthenium, chromium, indium, solder, and carbon, or a composite thereof.

[0070] If such a conductive paste composition is used, a flexible conductive wiring with improved electrical conductivity can be formed.

[0071] At this point, silver powder is the best conductive filler for the aforementioned component (A).

[0072] Considering both conductivity and price, this type of conductive filler offers a relatively ideal overall performance.

[0073] Furthermore, in this invention, the average particle size of the conductive filler of the aforementioned component (A) is preferably 5 nm to 10 μm.

[0074] It would be ideal to incorporate such a conductive filler into a conductive paste composition.

[0075] Furthermore, the present invention provides a conductive wiring formed on a substrate and composed of a calcined product of the conductive paste composition described above.

[0076] If the conductive wiring is of this type, the change in conductivity during expansion and contraction will be minimal.

[0077] At this point, the aforementioned substrate should preferably be elastic.

[0078] Such a substrate is ideal for the conductive wiring of the present invention.

[0079] In this case, the aforementioned substrate should preferably be thermoplastic polyurethane.

[0080] Such a substrate is more ideal for the conductive wiring of the present invention.

[0081] Furthermore, the resistance of the conductive wiring of the present invention at 20% elongation should preferably be less than 500% of the resistance before elongation.

[0082] With such conductive wiring, the conductivity changes little during stretching and can be used to conform to the body surface.

[0083] Furthermore, the maximum resistance of the conductive wiring of the present invention when it is repeatedly stretched and contracted 1000 times with an elongation of 20% should preferably be less than 5000% of the resistance before stretching and contraction.

[0084] Such conductive wiring provides ideal conductivity stability during repeated expansion and contraction.

[0085] Furthermore, the present invention provides a method for manufacturing conductive wires, which is a method for manufacturing conductive wires by forming conductive wires on a substrate using the conductive paste composition described above, characterized in that the calcination temperature during the formation of the aforementioned conductive wires is set to 60 to 160°C.

[0086] If such a method of manufacturing conductive wiring is adopted, conductive wiring can be formed on a substrate with low heat resistance, and conductive wiring with minimal change in conductivity during expansion and contraction can be reliably obtained.

[0087] Furthermore, the present invention can also form conductive wiring on a substrate by printing the above-mentioned conductive paste composition.

[0088] By using printing to create wiring patterns, the design and production of wiring can be improved.

[0089] [The effects of the invention]

[0090] As described above, if the conductive paste composition contains the polyurethane of the present invention, it is possible to form conductive wiring that exhibits minimal change in conductivity during stretching and contraction, efficiently transmits electrical signals to the device (i.e., excellent conductivity), is lightweight, and can be manufactured at low cost. Furthermore, due to its excellent conductivity stability during repeated stretching and contraction, it is possible to form conductive wiring suitable for wearable devices that experience strain due to human body movements. Detailed Implementation

[0091] In existing technologies, conductive wiring using conductive pastes made by mixing metal fillers into resins contains insulating components, resulting in higher resistance compared to metal wiring. Furthermore, resistance inevitably increases with elongation, and deterioration occurs due to repeated stretching and contraction, sometimes leading to wire breakage. Additionally, the changes in conductivity during stretching and contraction may affect the operation of the device. Therefore, there is a need to develop conductive material compositions with higher conductivity and less change in conductivity during stretching and contraction.

[0092] Through repeated and in-depth investigations to solve the aforementioned problems, the inventors discovered that by using a conductive paste composition containing (A) a conductive filler, (B) a polyurethane containing phenolic hydroxyl groups as represented by the following general formula (1A), and (C) a solvent, conductive wiring with low resistance, minimal decrease in conductivity during elongation, and excellent conductive stability during repeated stretching and contraction can be obtained. In particular, the polyurethane containing phenolic hydroxyl groups as represented by the following general formula (1A) is previously unknown.

[0093] That is, the present invention is a polyurethane, characterized in that it contains phenolic hydroxyl groups as represented by the following general formula (1A).

[0094] [Chemistry 9]

[0095]

[0096] In the formula, Az represents a straight-chain, branched, or cyclic (ka+2) valence hydrocarbon group or a fluorinated hydrocarbon group with 1 to 20 carbon atoms, and the -CH2- constituting the aforementioned (ka+2) valence hydrocarbon group can also be replaced by -O- or -NR. 4 -、-C(=O-、or-Si(R) 2 R 3 )-. R 2 R 3 It is a straight-chain, branched, or cyclic alkyl or phenyl group having 1 to 6 carbon atoms, R 4 The first group represents a hydrogen atom, or a straight-chain or branched alkyl group having 1 to 4 carbon atoms. Z represents a single bond or an oxygen atom. Xf independently represents a hydrogen atom, a halogen atom, a straight-chain, branched, or cyclic monovalent hydrocarbon group having 1 to 10 carbon atoms that may be substituted with a fluorine atom, an alkoxy group having 1 to 10 carbon atoms that may be substituted with a fluorine atom, or an electron-withdrawing group. Cycle ZZ independently represents an aromatic monocyclic or polycyclic ring having 5 to 20 carbon atoms. The carbon atoms in the aforementioned cycle ZZ may also be substituted with nitrogen, oxygen, or sulfur atoms. ka represents an integer from 0 to 2. kb and kd represent 1 or 2. kc and ke represent integers from 0 to 2, and dashed lines represent atomic bonds.

[0097] The present invention will now be described in detail, but it is not limited thereto. Furthermore, in the following description, depending on the structure represented by the chemical formula, there may be asymmetric carbons, and there may be enantiomers and diastereomers; in such cases, the isomers are represented by a single formula. These isomers can be used individually or in mixtures.

[0098] [Polyurethane] The polyurethane of the present invention is one containing phenolic hydroxyl groups as represented by the following general formula (1A).

[0099] [Chemistry 10]

[0100]

[0101] In the formula, Az represents a straight-chain, branched, or cyclic (ka+2) valence hydrocarbon group or a fluorinated hydrocarbon group with 1 to 20 carbon atoms, and the -CH2- constituting the aforementioned (ka+2) valence hydrocarbon group can also be replaced by -O- or -NR. 4 -、-C(=O-、or-Si(R) 2 R 3 )-. R 2 R 3 It is a straight-chain, branched, or cyclic alkyl or phenyl group having 1 to 6 carbon atoms, R 4 The first group represents a hydrogen atom, or a straight-chain or branched alkyl group having 1 to 4 carbon atoms. Z represents a single bond or an oxygen atom. Xf independently represents a hydrogen atom, a halogen atom, a straight-chain, branched, or cyclic monovalent hydrocarbon group having 1 to 10 carbon atoms that may be substituted with a fluorine atom, an alkoxy group having 1 to 10 carbon atoms that may be substituted with a fluorine atom, or an electron-withdrawing group. Cycle ZZ independently represents an aromatic monocyclic or polycyclic ring having 5 to 20 carbon atoms. The carbon atoms in the aforementioned cycle ZZ may also be substituted with nitrogen, oxygen, or sulfur atoms. ka represents an integer from 0 to 2. kb and kd represent 1 or 2. kc and ke represent integers from 0 to 2, and dashed lines represent atomic bonds.

[0102] The following are specific examples of straight-chain, branched, or cyclic (ka+2) valence hydrocarbon groups with 1 to 20 carbon atoms in the aforementioned Az.

[0103] [Chemistry 11]

[0104]

[0105] In the formula, the dashed lines represent atomic bonds.

[0106] [Chemistry 12]

[0107]

[0108] In the formula, the dashed lines represent atomic bonds.

[0109] [Chemistry 13]

[0110]

[0111] In the formula, the dashed lines represent atomic bonds.

[0112] Az is a straight-chain, branched, or cyclic (ka+2) valence fluorinated hydrocarbon group with 1 to 20 carbon atoms. Specific examples include hydrocarbon groups in which some or all of the hydrogen atoms are replaced by fluorine atoms.

[0113] The -CH2- group constituting the aforementioned (ka+2) valence hydrocarbon group can also be substituted with -O- or -NR.4 -、-C(=O-、or-Si(R) 2 R 3 )-.

[0114] R 2 R 3 Specific examples of alkyl groups having 1 to 6 carbon atoms in a straight-chain, branched, or cyclic form include: methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, etc.

[0115] R 4 Examples of straight-chain or branched alkyl groups having 1 to 4 carbon atoms include methyl, ethyl, propyl, isopropyl, etc.

[0116] Z represents a single bond or an oxygen atom, preferably an oxygen atom.

[0117] Specific examples of halogen atoms in Xf include: fluorine atoms, chlorine atoms, bromine atoms, etc.

[0118] Examples of linear, branched, or cyclic monovalent hydrocarbon groups of Xf with 1 to 10 carbon atoms that can be substituted by fluorine atoms include: methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, cyclopropyl, cyclobutyl, and other alkyl groups; trifluoromethyl, 2,2,2-trifluoroethyl, etc.

[0119] Examples of alkoxy groups with 1 to 10 carbon atoms in Xf that can be substituted by fluorine atoms include: methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, sec-butoxy, tert-butoxy, cyclopropoxy, trifluoromethoxy, 2,2,2-trifluoroethoxy, etc.

[0120] Specific examples of electron-withdrawing groups of Xf include: carbonyl, alkoxycarbonyl, cyano, nitro, sulfonyl, formyl, sulfonate, amide, -OC(=O)-G- (G is a sulfur atom or NH), etc.

[0121] Aromatic monocyclic or polycyclic rings with 5 to 20 carbon atoms in the ZZ ring can be exemplified as follows. As described below, the ZZ ring may also have substituents.

[0122] [Chemistry 14]

[0123]

[0124] ka represents an integer from 0 to 2, kb and kd represent 1 or 2, and kc and ke represent integers from 0 to 2.

[0125] (1A) Specific examples of polyurethanes containing phenolic hydroxyl groups can be listed as polyurethanes obtained by reacting the following polyisocyanate, high molecular weight polyol, and chain extender. The polyisocyanate, high molecular weight polyol, and chain extender can be used alone or in combination of two or more.

[0126] Examples of polyisocyanates include: ethylene diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate (HDI), octamethylene diisocyanate, nonamethylene diisocyanate, 2-methylpentane-1,5-diisocyanate, 3-methylpentane-1,5-diisocyanate, 2,2'-dimethylpentane diisocyanate, 2,2,4-trimethylhexane diisocyanate, decamethylene diisocyanate, butylene diisocyanate, 1,3-butadiene-1,4-diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, 1,6,11-undecylene triisocyanate, 1,3,6-hexamethylene triisocyanate, 1,8-diisocyanate... Cyanate-4-isocyanoxymethyl octane, 2,5,7-trimethyl-1,8-diisocyanate-5-isocyanoxymethyl octane, bis(isocyanoxyethyl) carbonate, bis(isocyanoxyethyl) ether, 1,4-butanediol dipropyl ether-ω,ω'-diisocyanate, lysine isocyanate methyl ester, lysine triisocyanate, 2-isocyanoxyethyl-2,6-diisocyanate hexanoate, 2-isocyanoxypropyl-2,6-diisocyanate hexanoate, bis(4-isocyanate-n-butylene)neopentetrol, 2,6-diisocyanate methyl hexanoate, isophorone diisocyanate (IPDI), 1,3-cyclohexyl diisocyanate, 1,4-cyclohexyl diisocyanate, 1,3-bis(isocyanoxymethyl) 1,4-bis(isocyanoxymethyl)cyclohexane, 1,3-bis(isocyanoxyethyl)cyclohexane, 1,4-bis(isocyanoxyethyl)cyclohexane, methylcyclohexane diisocyanate, 2,2'-dimethyldicyclohexylmethane diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, dimer acid diisocyanate, 2,5-diisocyanoxymethylbicyclo[2,2,1]-heptane, 2,6-diisocyanoxymethylbicyclo[2,2,1]-heptane, 2-isocyanoxymethyl 2-(3-isocyanoxypropyl)-5-isocyanoxymethylbicyclo-[2,2,1]-heptane, 2-isocyanoxymethyl-2-(3-isocyanoxypropyl)-6-isocyanoxymethylbicyclo-[2,2,1]- Heptane, 2-isocyanoxymethyl 3-(3-isocyanoxypropyl)-5-(2-isocyanoxyethyl)-bicyclo-[2,2,1]-heptane, 2-isocyanoxymethyl 3-(3-isocyanoxypropyl)-6-(2-isocyanoxyethyl)-bicyclo-[2,2,1]-heptane, 2-isocyanoxymethyl 2-(3-isocyanoxypropyl)-5-(2-isocyanoxyethyl)-bicyclo-[2,2,1]-heptane, 2-isocyanoxymethyl 2-(3-isocyanoxypropyl)-6-(2-isocyanoxyethyl)-bicyclo-[2,2,1]-heptane, and other aliphatic and alicyclic polyisocyanates; 2,4-toluene diisocyanate or 2,6-toluene diisocyanate and mixtures of their isomers (TDI);4,4'-Diphenylmethane diisocyanate or 2,4'-diphenylmethane diisocyanate and their isomer mixtures (MDI); aromatic polyisocyanates such as toluidine diisocyanate (TODI), p-phenylene diisocyanate, naphthalene diisocyanate (NDI), and 4,4'-dibenzyl diisocyanate; aromatic aliphatic polyisocyanates such as o-xylene diisocyanate, m-xylene diisocyanate, p-xylene diisocyanate, 1,3-tetramethylxylene diisocyanate, and 1,4-tetramethylxylene diisocyanate; and further examples include their carbamate-modified polymers, biuret-modified polymers, carbodiimine-modified polymers, uretonimine-modified polymers, uretdione-modified polymers, isocyanurate-modified polymers, and urethane-modified polymers.

[0127] High molecular weight polyols can be listed as follows: polyoxypropylene glycol, polyoxyethylene glycol, polyoxytetramethylene glycol, and their copolymers, as well as polyether polyols; polyester polyols, polyester-amide polyols, polycarbonate polyols, acrylic polyols, terminally hydroxylated polyolefins, polysiloxane polyols, and vegetable oil polyols, etc.

[0128] Specific examples of polyoxypropylene glycol and polyoxyethylene glycol include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, neopentyl glycol, and 3-methyl-1,5-pentanediol. 3,3-Dimethylolheptane, 2,2,2-Trimethylpentanediol, 1,4-Dihydroxy-2-butene, 2,6-Dimethyl-1-octene-3,8-diol, diethylene glycol, triethylene glycol, dipropylene glycol, cyclohexane-1,3-diol, cyclohexane-1,4-diol, cyclohexane-1,3-diethanol, cyclohexane-1,4-diethanol, 1,3-adamantanediethanol, dimer Addition polymers of ethylene oxide, propylene oxide, and epoxide, including diols such as hydroquinone di(2-hydroxyethyl ether), bisphenol A, bis(β-hydroxyethyl)benzene, and bis(hydroxyethyl)benzene; triols such as glycerol, trimethylolpropane, and triisopropanolamine; tetraols such as neopentyl tertetrol, α-methyl glucoside, and diglycerol, or polyols such as sorbitol and sucrose; low molecular weight amino alcohols such as monoethanolamine, diethanolamine, and triethanolamine; and addition polymers of ethylene oxide, propylene oxide, and butylene oxide, pentamethylenediamine, hexamethylenediamine, isophorone diamine, piperazine, toluene diamine, m-phenylenediamine, diphenylmethane diamine, phenylenediamine, dimethylthiotoluene diamine, and 4,4-methylenebis-o-chloroaniline, using low molecular weight polyamines as initiators. In addition, the epoxy alkane components of polyester polyols can be used alone or in combination of two or more types. Polyoxyalkylene polyols formed by combining two or more types can be either block or random structures.

[0129] Specific examples of polyoxytetramethylene glycol include: crystalline polyoxytetramethylene glycol, or amorphous polyoxytetramethylene glycol synthesized by copolymerizing THF with alkyl-substituted tetrahydrofuran or the above-mentioned dihydric alcohols.

[0130] Polyester polyols can include the low molecular weight polyols mentioned above, as well as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, octanoic acid, pentenic acid, azelaic acid, sebacic acid, 1,1-dimethyl-1,3-dicarboxypropane, 3-methyl-3-ethylglutaric acid, 1,4-cyclohexyldicarboxylic acid, hexahydrophthalic acid, maleic acid, fumaric acid, itaconic acid, mucoconic acid, α-hydromucoconic acid, β-hydromucoconic acid, phthalic acid, and phthalic acid. Polymer condensates of acids, terephthalic acid, isophthalic acid, toluenedicarboxylic acid, naphthalenedicarboxylic acid, chlorobridged acid, dimer acid, hydrogenated dimer acid, and other polycarboxylic acids, as well as their derivatives, anhydrides, and acyl halides; ring-opening polymers of lactones such as β-propiolactone, β-butyrolactone, γ-butyrolactone, γ-valerolactone, δ-valerolactone, and ε-caprolactone, or lactides such as L-lactide and D-lactide, using the aforementioned low molecular weight polyols as initiators. Furthermore, the low molecular weight polyols, polycarboxylic acids, oligomeric acids, lactones, or lactides constituting the polyester polyol may be used individually or in combination of two or more.

[0131] Polyester-amide polyols can be exemplified by polymer condensates obtained by replacing a portion of the low molecular weight polyols of polyester polyols with the aforementioned low molecular weight polyamines and amino alcohols.

[0132] Specific examples of polycarbonate polyols include the aforementioned low molecular weight polyols and polycondensates of carbonate compounds such as dimethyl carbonate, diethyl carbonate, ethylene carbonate, propylene carbonate, diphenyl carbonate, dinaphthyl carbonate, dianthryl carbonate, diphenoxy carbonate, diindene carbonate, and tetrahydronaphthyl carbonate. Furthermore, the low molecular weight polyols or carbonate compounds constituting polycarbonate polyols can be used individually or in combination of two or more.

[0133] Specific examples of acrylic polyols can be listed by including hydroxyl-containing (meth)acrylates such as 2-hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxybutyl methacrylate, 3-hydroxy-2,2-dimethylpropyl acrylate, 2,2-dihydroxymethylbutyl methacrylate, neopentyltetrol tri(meth)acrylate, polyhydroxyalkyl maleate, polyhydroxyalkyl fumarate, etc., and methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, butyl methacrylate, isobutyl methacrylate, sec-butyl methacrylate, tert-butyl methacrylate, pentyl methacrylate, isoamyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, octyl methacrylate, nonyl methacrylate, isononyl methacrylate, decyl methacrylate, etc. The copolymers are obtained by copolymerizing dodecyl acrylate, cyclohexyl acrylate, phenyl acrylate, benzyl acrylate, allyl acrylate, ethylene glycol di(meth)acrylate, butanediol di(meth)acrylate, hexanediol di(meth)acrylate, oligoethylene glycol di(meth)acrylate, and other meth acrylates; aromatic vinyl monomers such as styrene, vinyltoluene, and α-methylstyrene; cyanide vinyl monomers such as methacrylonitrile; carboxyl-containing vinyl monomers or their alkyl esters such as fumaric acid, maleic acid, and itaconic acid; isocyanate-containing vinyl monomers such as 3-(2-isocyanate-2-propyl)-α-methylstyrene; fluorinated vinyl monomers such as tetrafluoroethylene, chlorotrifluoroethylene, trichlorofluoroethylene, hexafluoropropylene, vinylidene fluoride, fluorinated vinylidene, and trifluoromethyltrifluoroethylene; and polysiloxane monomers such as γ-(meth)acryloyloxypropyltrimethoxysilane. In addition, the (meth)acrylates or vinyl monomers that make up the components of acrylic polyols can be used alone or in combination of two or more.

[0134] Specific examples of terminally hydroxylated polyolefins include compounds obtained by polymerizing one or more of ethylene, propylene, butadiene, isoprene, styrene, acrylonitrile, vinyl ether, vinyl acetate, and olefins whose structures are partially replaced by halogens such as fluorine, chlorine, and bromine, and then hydroxylating the ends of the polymers.

[0135] Specific examples of polysiloxane polyols include vinyl-containing polysiloxane compounds synthesized by polymerizing γ-methacryloyloxypropyltrimethoxysilane, and polysiloxanes such as α,ω-dihydroxy polydimethylsiloxane and α,ω-dihydroxy polydiphenylsiloxane having at least one terminal hydroxyl group in the molecule.

[0136] Specific examples of vegetable oil-based polyols include ester-modified castor oil polyols, dehydrated castor oil, partially dehydrated castor oil, and hydrogenated castor oil, which are obtained by reacting castor oil, coconut oil, and other hydroxyl-containing vegetable oils, as well as castor oil fatty acids and polyols.

[0137] Chain extenders that can be used include: ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, 3,3-dihydroxymethylheptane, 2,2,2-trimethylpentanediol, 1,4-dihydroxy-2-butene, 2,6-dimethyl-1-octen-3,8-diol, diethylene glycol, triethylene glycol, dipropylene glycol, cyclohexane-1,3-diol, and cyclohexane. Diols such as 1,4-diol, cyclohexane-1,3-diethanol, cyclohexane-1,4-diethanol, 1,3-adamantanediethanol, dimer glycol, 1,2-benzene glycol, 1,3-benzene glycol, 1,4-benzene glycol, hydroquinone di(2-hydroxyethyl ether), bisphenol A, bis(β-hydroxyethyl)benzene, and diol; amines such as ethanolamine, diethanolamine, triethanolamine, ethylenediamine, propylenediamine, butanediamine, pentamethylmethylenediamine, hexamethylenediamine, isophorone diamine, piperazine, toluenediamine, m-phenylenediamine, diphenylmethanediamine, phenylenediamine, dimethylthiotoluenediamine, and 4,4-methylenebis-o-chloroaniline.

[0138] Furthermore, the following chain extenders containing weakly acidic functional groups can be listed.

[0139] [Chemistry 15]

[0140]

[0141] In the formula, R 1 R 4 R 7 R 8 Same as above.

[0142] [Chemistry 16]

[0143]

[0144] [Chemistry 17]

[0145]

[0146] In the formula, R 1 Same as above.

[0147] The following chain extenders containing phenol can also be listed.

[0148] [Chemistry 18]

[0149]

[0150] (1A) Specific examples of polyurethanes containing phenolic hydroxyl groups can be listed as polyurethanes obtained by reacting the above-mentioned polyisocyanate, high molecular weight polyol and chain extender.

[0151] Polyurethanes obtained by reacting the aforementioned polyisocyanate, high molecular weight polyol, chain extender and the following end-capping agent can also be cited as examples.

[0152] [Chemistry 19]

[0153]

[0154] In the formula, X represents an oxygen atom or NR. 4 R 4 Same as above.

[0155] [Chemistry 20]

[0156]

[0157] In the formula, X represents an oxygen atom or NR. 4 R 4 Same as above. Examples of polyurethane can be listed below.

[0158] [Chemistry 21]

[0159]

[0160] In the formula, la is 7 to 30, lb is 2 to 30, lc is 3 to 30, ld is 1 to 5, and le is an integer from 2 to 20.

[0161] The polyurethane containing phenolic hydroxyl groups represented by the above general formula (1A) is particularly preferred to be the polyurethane containing phenolic hydroxyl groups represented by the following general formula (1B).

[0162] [Chemistry 22]

[0163]

[0164] In the formula, Az' represents a straight-chain, branched, or cyclic (ka+2) valence hydrocarbon group or a fluorinated hydrocarbon group with 1 to 19 carbon atoms, and the -CH2- constituting the aforementioned (ka+2) valence hydrocarbon group can also be replaced by -O- or -NR. 4 -、-C(=O-、or-Si(R) 2 R 3 )-. ka represents an integer from 0 to 2. kb, kc, kd, and ke represent 1 or 2. R 2 R 3 R4 As mentioned above, dashed lines represent atomic bonds.

[0165] Az' represents a straight-chain, branched, or cyclic (ka+2) valence hydrocarbon group or a fluorinated hydrocarbon group with 1 to 19 carbon atoms, and the -CH2- constituting the aforementioned (ka+2) valence hydrocarbon group can also be replaced by -O- or -NR. 4 -、-C(=O-、or-Si(R) 2 R 3 Ka represents an integer from 0 to 2, while kb, kc, kd, and ke represent 1 or 2.

[0166] The specific structures represented by the above general formulas (1A) and (1B) can be illustrated as follows.

[0167] [Chemistry 23]

[0168]

[0169] In the formula, X represents an oxygen atom or NR. 4 The dashed line represents an atomic bond. R 4 Same as above.

[0170] [Chemistry 24]

[0171]

[0172] In the formula, X represents an oxygen atom or NR. 4 The dashed line represents an atomic bond. R 4 Same as above.

[0173] [Chemistry 25]

[0174]

[0175] In the formula, X represents an oxygen atom or NR. 4 The dashed line represents an atomic bond. R 4 Same as above.

[0176] [Chemistry 26]

[0177]

[0178] In the formula, X represents an oxygen atom or NR. 4 The dashed line represents an atomic bond. R 4 Same as above.

[0179] [Chemistry 27]

[0180]

[0181] In the formula, X represents an oxygen atom or NR. 4 The dashed line represents an atomic bond. R4 Same as above.

[0182] [Chemistry 28]

[0183]

[0184] In the formula, X represents an oxygen atom or NR. 4 The dashed line represents an atomic bond. R 4 Same as above.

[0185] Furthermore, in this invention, the aforementioned polyurethane preferably contains one or more weakly acidic functional groups represented by the following general formulas (1a) to (1c).

[0186] [Chemistry 29]

[0187]

[0188] In the formula, R represents a hydrogen atom, a fluorine atom, or a straight-chain, branched, or cyclic hydrocarbon group with 1 to 10 carbon atoms that can also be fluorinated; Rf represents a fluorine atom or a straight-chain, branched, or cyclic fluorinated hydrocarbon group with 1 to 10 carbon atoms. n is an integer of 1 or 2, and the dashed line represents an atomic bond.

[0189] R represents a hydrogen atom, a fluorine atom, or a straight-chain, branched, or cyclic hydrocarbon group with 1 to 10 carbon atoms that can also be fluorinated. Specific examples include: hydrogen atom, fluorine atom, methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, difluoromethyl, trifluoromethyl, 2,2,2-trifluoroethyl, etc.

[0190] Rf represents a fluorine atom or a straight-chain, branched, or cyclic fluorinated hydrocarbon group having 1 to 10 carbon atoms. Specific examples include fluorine atoms, difluoromethyl, trifluoromethyl, 2,2,2-trifluoroethyl, etc.

[0191] n is an integer that is either 1 or 2.

[0192] Specific examples of weakly acidic functional groups (1a) can be listed below, including groups of fluorinated alcohols.

[0193] [Chemistry 30]

[0194]

[0195] In the formula, R 7 R 8 Each of the following independently represents a hydrogen atom and a linear, branched, or cyclic hydrocarbon group having 1 to 6 carbon atoms; R 7 With R 8 They can also bond with each other and together with the carbon atoms they bond with, form non-aromatic rings with 3 to 8 carbon atoms. The dashed lines represent atomic bonds.

[0196] Specific examples of weakly acidic functional groups (1b) can be listed below, such as cyclic fluorinated alcohol groups.

[0197] [Chemistry 31]

[0198]

[0199] In the formula, R 1 It consists of a hydrogen atom or a monovalent hydrocarbon group having 1 to 3 carbon atoms. The dashed part represents an atomic bond.

[0200] Specific examples of weakly acidic functional groups (1c) can be listed below, including sulfonamide-containing groups.

[0201] [Chemistry 32]

[0202]

[0203] The polyurethane of the present invention is even more preferably composed of one or more structures represented by the following general formulas (2a) to (2c).

[0204] [Chemistry 33]

[0205]

[0206] In the formula, R 1 A is a hydrogen atom or a monovalent hydrocarbon group having 1 to 3 carbon atoms. a It represents a single bond, or a straight-chain, branched, or cyclic divalent hydrocarbon group with 1 to 20 carbon atoms, and the -CH2- group can also be substituted with -O-, -C(=O)-, -C(=O)O-, or -C6H4-, and can also be -NR. 4 -C(=O)-。 A b and A c Each can be independently represented by -O-, -OC (=O)-NR 4 -、-NR 4 Any one of the following groups: - or -C(=O)O-. 1 n 2 n 4 n is an integer between 0 and 10. 3 An integer that is either 0 or 1. R 4 As mentioned above, dashed lines represent atomic bonds.

[0207] R 1 It is a hydrogen atom or a monovalent hydrocarbon group having 1 to 3 carbon atoms, preferably a hydrogen atom, methyl, or ethyl.

[0208] [Manufacturing method of polyurethane]

[0209] The aforementioned polyurethane can be obtained, for example, by reacting polyisocyanates with polyols, polyamines, or polycarboxylic acids using known methods such as one-shot methods or prepolymer methods. The prepolymer method is ideally applicable.

[0210] The prepolymer method synthesizes polyurethane using the following steps: (a) reacting diisocyanate and high molecular weight polyol in excess of isocyanate groups to obtain a reaction mixture containing isocyanate-terminated prepolymers; (b) increasing the molecular weight of the prepolymer by reacting it with a low molecular weight diol, diamine, or dicarboxylic acid (chain extender). Furthermore, polyurethanes with crosslinked structures can also be obtained by adding polyisocyanates with a reactive element number of 3 or more, or polyols, polyamines, or polycarboxylic acids with a reactive element number of 3 or more.

[0211] Furthermore, after the polymerization in (b) above is carried out in excess of isocyanate groups, functional groups from the end-capping agent can also be introduced into the urethane terminus by adding an end-capping agent having reactive groups (hydroxyl, amino, carboxyl, etc.) that can react with isocyanate groups.

[0212] The polyurethane with phenolic hydroxyl groups of the present invention can be synthesized in the reactions (a) and (b) above by replacing all or part of at least one of high molecular weight polyol, chain extender, and capping agent with a compound containing phenolic hydroxyl groups. However, it is more preferable to introduce phenolic hydroxyl groups as capping agents after the chain extension reaction, that is, to introduce the aforementioned phenolic hydroxyl groups into the polyurethane using an alcohol or amine represented by the following general formula (1C) after the chain extension reaction.

[0213] [Chemistry 34]

[0214]

[0215] In the formula, "Az" represents a straight-chain, branched, or cyclic (ka+2) valence hydrocarbon group or a fluorinated hydrocarbon group with 1 to 19 carbon atoms, and the -CH2- constituting the aforementioned (ka+2) valence hydrocarbon group can also be replaced by -O-, -C(=O)-, or -Si(R 2 R 3 )-. X represents an oxygen atom or NR. 4 ka represents an integer from 0 to 2. kb, kc, kd, and ke represent 1 or 2. R 2 R 3 R 4 Same as above.

[0216] "Az" represents a straight-chain, branched, or cyclic (ka+2) valence hydrocarbon group with 1 to 19 carbon atoms, and the -CH2- constituting the aforementioned (ka+2) valence hydrocarbon group can also be substituted with -O-, -C(=O)-, or -Si(R)-. 2 R 3)-.

[0217] X represents an oxygen atom or NR. 4 .

[0218] Ka represents an integer from 0 to 2, and kb, kc, kd, and ke represent 1 or 2.

[0219] R 2 R 3 R 4 Same as above.

[0220] In addition, since phenolic hydroxyl groups can react with isocyanates, when introducing phenolic hydroxyl groups into high molecular weight polyols or chain extenders, polyurethaneization should be carried out under the protection of appropriate protecting groups, followed by deprotection.

[0221] Furthermore, in reactions (a) and (b), polyurethanes containing phenolic hydroxyl groups and weak acidic functional groups can be synthesized by replacing all or part of at least one of the high molecular weight polyol, chain extender, and capping agent with a compound containing a weak acidic functional group.

[0222] [Polyisocyanates]

[0223] Polyurethanes can be composed of the following polyisocyanates: ethylene diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate (HDI), octamethylene diisocyanate, nonamethylene diisocyanate, 2-methylpentane-1,5-diisocyanate, 3-methylpentane-1,5-diisocyanate, 2,2'-dimethylpentane diisocyanate, 2,2,4-trimethylhexane diisocyanate, decamethylene diisocyanate, butylene diisocyanate, 1,3-butadiene-1,4-diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, 1,6,11-undecylene triisocyanate, and 1,3,6-hexamethylene triisocyanate. 1,8-Diisocyanate-4-isocyanoxymethyl octane, 2,5,7-trimethyl-1,8-diisocyanate-5-isocyanoxymethyl octane, bis(isocyanoxyethyl) carbonate, bis(isocyanoxyethyl) ether, 1,4-butanediol dipropyl ether-ω,ω'-diisocyanate, lysine methyl isocyanate, lysine triisocyanate, 2-isocyanoxyethyl-2,6-diisocyanate hexanoate, 2-isocyanoxypropyl-2,6-diisocyanate hexanoate, bis(4-isocyanate-n-butylene)neopentetrol, 2,6-diisocyanate methyl hexanoate, isophorone diisocyanate (IPDI), 1,3-cyclohexyl diisocyanate, 1,4-cyclohexyl diisocyanate, 1,3-bis(isocyanate-4 ... 2,4-diisocyanate methyl hexanoate, 2,5,7-trimethyl-1,8-diisocyanate methyl hexanoate, 2,5,7-trimethyl-1,8-diisocyanate methyl hexanoate, 2,5,7-trimethyl-1,8-diisocyan Cyanooxymethyl)cyclohexane, 1,4-bis(isocyanoxymethyl)cyclohexane, 1,3-bis(isocyanoxyethyl)cyclohexane, 1,4-bis(isocyanoxyethyl)cyclohexane, methylcyclohexane diisocyanate, 2,2'-dimethyldicyclohexylmethane diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, dimer acid diisocyanate, 2,5-diisocyanoxymethylbicyclo[2,2,1]-heptane, 2,6-diisocyanoxymethylbicyclo[2,2,1]-heptane, 2-isocyanoxymethyl 2-(3-isocyanoxypropyl)-5-isocyanoxymethylbicyclo-[2,2,1]-heptane, 2-isocyanoxymethyl-2-(3-isocyanoxypropyl)-6-isocyanoxymethylbicyclo-[2,2,1]-heptane [2,2,1]-heptane, 2-isocyanoxymethyl 3-(3-isocyanoxypropyl)-5-(2-isocyanoxyethyl)-bicyclo-[2,2,1]-heptane, 2-isocyanoxymethyl 3-(3-isocyanoxypropyl)-6-(2-isocyanoxyethyl)-bicyclo-[2,2,1]-heptane, 2-isocyanoxymethyl 2-(3-isocyanoxypropyl)-5-(2-isocyanoxyethyl)-bicyclo-[2,2,1]-heptane, 2-isocyanoxymethyl 2-(3-isocyanoxypropyl)-6-(2-isocyanoxyethyl)-bicyclo-[2,2,1]-heptane, etc. (aliphatic and alicyclic polyisocyanates); 2,4-toluene diisocyanate or 2,6-toluene diisocyanate and mixtures of their isomers (TDI);4,4'-Diphenylmethane diisocyanate or 2,4'-diphenylmethane diisocyanate and their isomer mixtures (MDI); aromatic polyisocyanates such as toluidine diisocyanate (TODI), p-phenylene diisocyanate, naphthalene diisocyanate (NDI), and 4,4'-dibenzyl diisocyanate; aromatic aliphatic polyisocyanates such as o-xylene diisocyanate, m-xylene diisocyanate, p-xylene diisocyanate, 1,3-tetramethylxylene diisocyanate, and 1,4-tetramethylxylene diisocyanate; and further examples include their carbamate-modified polymers, biuret-modified polymers, carbodiimine-modified polymers, uretonimine-modified polymers, uretdione-modified polymers, isocyanurate-modified polymers, and urethane-modified polymers.

[0224] The above-mentioned polyisocyanates can be used alone or in combination of two or more.

[0225] [High molecular weight polyols]

[0226] The high molecular weight polyols that make up polyurethane can be polyols with two or more hydroxyl groups that can react with isocyanate groups, and a number average molecular weight of 500 to 5,000. Examples include: polyether polyols, polyester polyols, polycarbonate polyols, acrylic polyols, terminally hydroxylated polyolefins, polysiloxane polyols, and vegetable oil-based polyols.

[0227] Examples of polyether polyols include: polyoxypropylene glycol, polyoxyethylene glycol, polyoxytetramethylene glycol, and copolymers thereof.

[0228] Polyoxypropylene glycol and polyoxyethylene glycol are addition polymers of epoxide alkane using low molecular weight polyols, polyamines, and amino alcohols as initiators. Examples of low molecular weight 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, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, 3,3-dihydroxymethylheptane, 2,2,2-trimethylpentanediol, 1,4-dihydroxy-2-butene, 2 Diols such as 6-dimethyl-1-octen-3,8-diol, diethylene glycol, triethylene glycol, dipropylene glycol, cyclohexane-1,3-diol, cyclohexane-1,4-diol, cyclohexane-1,3-diethanol, cyclohexane-1,4-diethanol, 1,3-adamantanediethanol, dimer glycol, 1,2-benzenediol, 1,3-benzenediol, 1,4-benzenediol, hydroquinone di(2-hydroxyethyl ether), bisphenol A, bis(β-hydroxyethyl)benzene, and succinate diol; triols such as glycerol, trimethylolpropane, and triisopropanolamine; tetraols such as neopentyl tertrol, α-methyl glucoside, and diglycerol; or polyols such as sorbitol and sucrose. Examples of low molecular weight amino alcohols include: monoethanolamine, diethanolamine, and triethanolamine. Examples of low molecular weight polyamines include: ethylenediamine, propylenediamine, butanediamine, pentamethylmethylenediamine, hexamethylenediamine, isophorone diamine, piperazine, toluenediamine, m-phenylenediamine, diphenylmethanediamine, phenylenediamine, dimethylthiotoluenediamine, and 4,4-methylenebis-o-chloroaniline. Initiators can be used alone or in combination of two or more.

[0229] Alternatively, polyether polyols containing phenolic hydroxyl groups or weakly acidic functional groups can also be obtained by using the aforementioned low molecular weight polyols containing phenolic hydroxyl groups or weakly acidic functional groups. Furthermore, the phenolic hydroxyl groups and weakly acidic functional groups should preferably be polymerized under protected conditions and subsequently deprotected.

[0230] Examples of epoxides include ethylene oxide, propylene oxide, and butane oxide, which can be used alone or in combination of two or more. Polyoxyalkylene polyols formed by combining two or more of these compounds can use either block or random structures.

[0231] Polyoxytetramethylene glycol is a ring-opening polymer obtained by cationic polymerization of tetrahydrofuran (THF). Examples include crystalline polyoxytetramethylene glycol and amorphous polyoxytetramethylene glycol, which is obtained by copolymerizing THF with alkyl-substituted tetrahydrofuran or the above diols.

[0232] Polyester polyols can be exemplified by polymer condensates of the aforementioned low molecular weight polyols and polycarboxylic acids, oligomeric acids, or ring-opening polymers of lactones or lactides using low molecular weight polyols as initiators.

[0233] Examples of polycarboxylic acids include: oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, octanoic acid, pentenic acid, azelaic acid, sebacic acid, 1,1-dimethyl-1,3-dicarboxypropane, 3-methyl-3-ethylglutaric acid, 1,4-cyclohexyldicarboxylic acid, hexahydrophthalic acid, maleic acid, fumaric acid, itaconic acid, mucoconic acid, α-hydromucoconic acid, β-hydromucoconic acid, phthalic acid, terephthalic acid, isophthalic acid, toluenedicarboxylic acid, naphthalenedicarboxylic acid, chlorobridged acid, dimer acid, and hydrogenated dimer acid. Their derivatives, anhydrides, and acyl halides can also be used.

[0234] Examples of lactones include: β-propiolactone, β-butyrolactone, γ-butyrolactone, γ-valerolactone, δ-valerolactone, ε-caprolactone, etc. Examples of lactides include: L-lactide, D-lactide.

[0235] The low molecular weight polyols, polycarboxylic acids, oligomeric acids, lactones, or lactide components of polyester polyols can be used individually or in combination of two or more.

[0236] Alternatively, polyester-amide polyols obtained by replacing a portion of the low molecular weight polyols of polyester polyols with the aforementioned low molecular weight polyamines and amino alcohols can also be used.

[0237] Polycarbonate polyols can be exemplified as polycondensates of the aforementioned polyols and carbonate compounds.

[0238] Examples of carbonate compounds include: dimethyl carbonate, diethyl carbonate, ethylene carbonate, propylene carbonate, diphenyl carbonate, dinaphthyl carbonate, dianthryl carbonate, diphenoxy carbonate, diindene carbonate, tetrahydronaphthyl carbonate, etc.

[0239] The low molecular weight polyols or carbonate compounds that make up polycarbonate polyols can be used alone or in combination of two or more.

[0240] Acrylic polyols can be exemplified by copolymers obtained by copolymerizing hydroxyl-containing (meth)acrylates and vinyl monomers.

[0241] Examples of hydroxyl-containing (meth)acrylates include: 2-hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, 3-hydroxy-2,2-dimethylpropyl (meth)acrylate, 2,2-dihydroxymethylbutyl (meth)acrylate, neopentyl terephthalol tri(meth)acrylate, polyhydroxyalkyl maleate, polyhydroxyalkyl fumarate, etc. These hydroxyl-containing (meth)acrylates can be used alone or in combination of two or more.

[0242] Examples of vinyl monomers include: methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, butyl methacrylate, isobutyl methacrylate, sec-butyl methacrylate, tert-butyl methacrylate, amyl methacrylate, isoamyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, octyl methacrylate, nonyl methacrylate, isononyl methacrylate, decyl methacrylate, dodecyl methacrylate, cyclohexyl methacrylate, phenyl methacrylate, benzyl methacrylate, allyl methacrylate, and ethylene glycol di(methyl)methacrylate. Acrylic esters, butanediol di(meth)acrylate, hexanediol di(meth)acrylate, oligoethylene glycol di(meth)acrylate, and other (meth)acrylate monomers; aromatic vinyl monomers such as styrene, vinyltoluene, and α-methylstyrene; cyanide vinyl monomers such as (meth)acrylonitrile; carboxyl-containing vinyl monomers or their alkyl esters such as fumaric acid, maleic acid, and itaconic acid; isocyanate-containing vinyl monomers such as 3-(2-isocyanato-2-propyl)-α-methylstyrene; fluorinated vinyl monomers such as tetrafluoroethylene, chlorotrifluoroethylene, trichlorofluoroethylene, hexafluoropropylene, vinylidene fluoride, fluorinated vinylidene, and trifluoromethyltrifluoroethylene; and polysiloxane monomers such as γ-(meth)acryloyloxypropyltrimethoxysilane. The above vinyl monomers can be used alone or in combination of two or more.

[0243] Terminally hydroxylated polyolefins can be categorized as compounds formed by hydroxylating the ends of one or more olefin polymers. Examples of olefins include ethylene, propylene, butadiene, isoprene, styrene, acrylonitrile, vinyl ether, and vinyl acetate. Furthermore, a portion of the above structures can be substituted with halogens such as fluorine, chlorine, and bromine.

[0244] Examples of polysiloxane polyols include vinyl-containing polysiloxane compounds polymerized from γ-methacryloyloxypropyltrimethoxysilane, and polysiloxanes such as α,ω-dihydroxy polydimethylsiloxane and α,ω-dihydroxy polydiphenylsiloxane, which have at least one terminal hydroxyl group in their molecules.

[0245] Vegetable oil polyols can be categorized into ester-modified castor oil polyols, dehydrated castor oil, partially dehydrated castor oil, and hydrogenated castor oil, which are obtained by reacting castor oil, coconut oil, and other hydroxyl-containing vegetable oils, as well as castor oil fatty acids and polyols.

[0246] The number average molecular weight of high molecular weight polyols should preferably be in the range of 500 to 5,000, preferably 1,000 to 3,000, and even more preferably 1,000 to 2,000.

[0247] By setting the number average molecular weight of high molecular weight polyols above the lower limit, excessive increases in the concentration of urethane groups in polyurethane can be suppressed, along with the associated decreases in hardness and elasticity. Conversely, by setting the number average molecular weight below the upper limit, excessive decreases in the concentration of urethane groups can be suppressed, and the reduction in strength originating from urethane bonds can be prevented, thus achieving a balance between appropriate strength and elasticity.

[0248] High molecular weight polyols should preferably be difunctional or trifunctional polyols, with difunctional polyols being more preferred.

[0249] [Chain elongation agent]

[0250] Chain extenders that can be used include: ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, 3,3-dihydroxymethylheptane, 2,2,2-trimethylpentanediol, 1,4-dihydroxy-2-butene, 2,6-dimethyl-1-octen-3,8-diol, diethylene glycol, triethylene glycol, dipropylene glycol, cyclohexane-1,3-diol, and cyclohexane. Diols such as 1,4-diol, cyclohexane-1,3-diethanol, cyclohexane-1,4-diethanol, 1,3-adamantanediethanol, dimer glycol, 1,2-benzene glycol, 1,3-benzene glycol, 1,4-benzene glycol, hydroquinone di(2-hydroxyethyl ether), bisphenol A, bis(β-hydroxyethyl)benzene, and diol; amines such as ethanolamine, diethanolamine, triethanolamine, ethylenediamine, propylenediamine, butanediamine, pentamethylmethylenediamine, hexamethylenediamine, isophorone diamine, piperazine, toluenediamine, m-phenylenediamine, diphenylmethanediamine, phenylenediamine, dimethylthiotoluenediamine, and 4,4-methylenebis-o-chloroaniline.

[0251] In addition, one or more alcohols represented by the following general formulas (3a) to (3c) can be used as chain extenders to introduce weakly acidic functional groups into polyurethane. The chain extenders can be the polyols described in (3a) to (3c) alone, or they can be used in combination.

[0252] [Chemistry 35]

[0253]

[0254] In the formula, R 1 A is a hydrogen atom or a monovalent hydrocarbon group having 1 to 3 carbon atoms. a It represents a single bond, or a straight-chain, branched, or cyclic divalent hydrocarbon group with 1 to 20 carbon atoms, and the -CH2- group can also be substituted with -O-, -C(=O)-, -C(=O)O-, or -C6H4-, and can also be -NR. 4 -C(=O)-。 R 4 It consists of hydrogen atoms, or straight-chain or branched alkyl groups having 1 to 4 carbon atoms. 1 n 2 n 4 Integers from 0 to 10.

[0255] By using such a chain extender, polyurethane containing the structure represented by the above general formulas (2a) to (2c) can be obtained.

[0256] R 1 It is a hydrogen atom or a monovalent hydrocarbon group having 1 to 3 carbon atoms, preferably a hydrogen atom, methyl, or ethyl.

[0257] A a It represents a single bond, or a straight-chain, branched, or cyclic divalent hydrocarbon group with 1 to 20 carbon atoms, and the -CH2- group can also be substituted with -O-, -C(=O)-, -C(=O)O-, or -C6H4-, and can also be -NR. 4 -C(=O)-. The above A a Examples of linear, branched, or cyclic divalent hydrocarbon groups with 1 to 20 carbon atoms are listed below.

[0258] [Chemistry 36]

[0259]

[0260] The above A can be further exemplified. a Any of the -CH2- groups is replaced by -O-, -C(=O)-, -C(=O)O-, -C6H4-, or -NR. 4 -C(=O)- R 4 It consists of hydrogen atoms, or straight-chain or branched alkyl groups having 1 to 4 carbon atoms, n 1 n 2 n 4 Integers from 0 to 10.

[0261] Specific examples of polyols represented by the above general formulas (3a) to (3c) are shown below, but are not limited thereto.

[0262] [Chemistry 37]

[0263]

[0264] In the formula, R 1 R 4 R 7 R 8 Same as above.

[0265] [Chemistry 38]

[0266]

[0267] [Chemistry 39]

[0268]

[0269] In the formula, R 1 Same as above.

[0270] The total amount of the aforementioned chain-extending agent with weakly acidic functional groups relative to the constituent components of the carbamate should preferably be 5-50% by mass, with 20-40% by mass being more preferred.

[0271] [Cross-linking agent]

[0272] Crosslinking agents can be triols such as glycerol, trimethylolpropane, and triisopropanolamine; or polyols such as neopentyl tertetrol, α-methyl glucoside, and diglycerides.

[0273] The amount of crosslinking agent added relative to the total amount of the components of the carbamate should preferably be in the range of 0 to 5% by mass, and 0 to 3% by mass is more preferred.

[0274] If the amount of crosslinking agent added is below the upper limit, the strength will not increase excessively without compromising softness and elasticity, thus making it suitable for use in conductive paste compositions containing the polyurethane of the present invention.

[0275] [Organic solvents]

[0276] Polyurethanes are synthesized using either bulk polymerization or solution polymerization. Examples of organic solvents that can be used in solution polymerization include: toluene, xylene, cumene, 1,2,3-trimethylbenzene, 1,2,4-trimethylbenzene, 1,3,5-trimethylbenzene, styrene, α-methylstyrene, styrene-butadiene, sec-butadiene, isobutadiene, isopropyltoluene, diethylbenzene, 2-ethyl-p-xylene, 2-propyltoluene, 3-propyltoluene, 4-propyltoluene, 1,2,3,5-tetramethyltoluene, 1,2,4,5-tetramethyltoluene, tetrahydronaphthalene, 4-phenyl-1-butene, tert-pentanebenzene, pentamene, 2-tert-butyltoluene, 3-tert-butyltoluene, 4-tert-butyltoluene, 5-isopropyl-m-xylene, 3-methylethylbenzene, tert-butyl-3-ethylbenzene, 4-tert-butyl-o-xylene, 5-tert-butyl-m-xylene. Aromatic hydrocarbon solvents such as toluene, tert-butyl-p-xylene, 1,2-diisopropylbenzene, 1,3-diisopropylbenzene, 1,4-diisopropylbenzene, dipropylbenzene, pentamethylbenzene, hexamethylbenzene, hexylene, and 1,3,5-triethylbenzene; solvents such as n-heptane, isoheptane, n-hexane, octane, 3-methylhexane, 2,3-dimethylpentane, 3-ethylpentane, 1,6-heptadiene, 5-methyl-1-hexyne, norbornene, norbornene, dicyclopentadiene, 1-methyl-1,4-cyclohexadiene, 1-heptyne, 2-heptyne, cycloheptane, cycloheptene, 1,3-dimethylcyclopentane, ethylcyclopentane, cyclohexane, methylcyclohexane, 1-methyl-1-cyclohexene, 3-methyl-1-cyclohexene, methylenecyclohexane, and 4-methyl-1-cyclohexene. Hexene, 2-methyl-1-hexene, 2-methyl-2-hexene, 1-heptene, 2-heptene, 3-heptene, n-octane, 2,2-dimethylhexane, 2,3-dimethylhexane, 2,4-dimethylhexane, 2,5-dimethylhexane, 3,3-dimethylhexane, 3,4-dimethylhexane, 3-ethyl-2-methylpentane, 3-ethyl-3-methylpentane, 2-methylheptane, 3-methylheptane, 4-methylheptane, 2,2,3-trimethylpentane, 2,2,4-trimethylpentane, cyclooctane, cyclooctene, 1,2-dimethylcyclohexane, 1,3-dimethylcyclohexane, 1,4-dimethylcyclohexane, ethylcyclohexane, vinylcyclohexane, isopropylcyclopentane, 2,2-dimethyl-3-hexene 2,4-Dimethyl-1-hexene, 2,5-Dimethyl-1-hexene, 2,5-Dimethyl-2-hexene, 3,3-Dimethyl-1-hexene, 3,4-Dimethyl-1-hexene, 4,4-Dimethyl-1-hexene, 2-Ethyl-1-hexene, 2-Methyl-1-heptene, 1-Octenene, 2-Octenene, 3-Octenene, 4-Octenene, 1,7-Ocadiene, 1-Octyne, 2-Octyne, 3-Octyne, 4-Octyne, n-Nonane, 2,3-Dimethylheptane, 2,4-Dimethylheptane, 2,5-Dimethylheptane, 3,3-Dimethylheptane, 3,4-Dimethylheptane, 3,5-Dimethylheptane, 4-Ethylheptane, 2-Methyloctane, 3-Methyloctane, 4-Methyloctane, 2,2,4-4-Tetramethylpentane, 2,2,4-trimethylhexane, 2,2,5-trimethylhexane, 2,2-dimethyl-3-heptene, 2,3-dimethyl-3-heptene, 2,4-dimethyl-1-heptene, 2,6-dimethyl-1-heptene, 2,6-dimethyl-3-heptene, 3,5-dimethyl-3-heptene, 2,4,4-trimethyl-1-hexene, 3,5,5-trimethyl-1-hexene, 1-ethyl-2-methylcyclohexane, 1-ethyl-3-methylcyclohexane, 1-ethyl-4-methylcyclohexane, propylcyclohexane, isopropylcyclohexane, 1,1,3-trimethylcyclohexane, 1, 1,4-Trimethylcyclohexane, 1,2,3-Trimethylcyclohexane, 1,2,4-Trimethylcyclohexane, 1,3,5-Trimethylcyclohexane, Allylcyclohexane, Hydindane, 1,8-Nonadiene, 1-Nonyne, 2-Nonyne, 3-Nonyne, 4-Nonyne, 1-Nonene, 2-Nonene, 3-Nonene, 4-Nonene, n-Decane, 3,3-Dimethyloctane, 3,5-Dimethyloctane, 4,4-Dimethyloctane, 3-Ethyl-3-methylheptane, 2-Methylnonane, 3-Methylnonane, 4-Methylnonane, tert-Butylcyclohexane, Butylcyclohexane, Isobutylcyclohexane 4-Isopropyl-1-methylcyclohexane, pentylcyclopentane, 1,1,3,5-tetramethylcyclohexane, cyclododecane, 1-decene, 2-decene, 3-decene, 4-decene, 5-decene, 1,9-decadiene, decahydronaphthalene, 1-decyne, 2-decyne, 3-decyne, 4-decyne, 5-decyne, 1,5,9-decadiene, 2,6-dimethyl-2,4,6-octtriene, limonene, myrcene, 1,2,3,4,5-pentamethylcyclopentadiene, α-phellandrene, pinene, terpinene, tetrahydrodicyclopentadiene, 5,6-dihydro Dicyclopentadiene, dicyclopentadiene, 1,4-decadiyne, 1,5-decadiyne, 1,9-decadiyne, 2,8-decadiyne, 4,6-decadiyne, n-Undecane, pentylcyclohexane, 1-Undecane, 1,10-Undecanediene, 1-Undecaneyne, 3-Undecaneyne, 5-Undecaneyne, tricyclo[6.2.1.02,7]undecane-4-ene, n-Dodecane, 2-Methylundecane, 3-Methylundecane, 4-Methylundecane, 5-Methylundecane, 2,2,4,6,6-Pentamethylheptane, 1,3-Dimethyladamantane, 1-Ethyladamantane, 1,5,9-Cyclododecanetriene, 1,2,4-Trivinylcyclohexane, isoalkanes, and other aliphatic hydrocarbon solvents; cyclohexanone, cyclopentanone, acetone, methyl ethyl ketone, 2-octanone, 2-nonanone, 2-heptanone, 3-heptanone, 4-heptanone, 2-hexanone, 3-hexanone, diisobutyl ketone, methyl isobutyl ketone, methyl cyclohexanone, methyl n-pentanone, and other ketone solvents; ethylene glycol dimethyl ether, propylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, diethylene glycol ethyl methyl ether, di... Ethylene glycol butyl methyl ether, diethyl ether, diisopropyl ether, di-n-butyl ether, di(sec-butyl) ether, diisobutyl ether, pentyl ether, isopentyl ether, di(tert-pentyl) ether, methyl cyclopentyl ether, methyl cyclohexyl ether, methyl tert-butyl ether, di-n-hexyl ether, anisole, dihydroterpene acetate, tetrahydrofuran, dioxane, and other ether solvents; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol diacetate, propylene glycol Monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, propylene glycol monotert-butyl ether acetate, propylene glycol diacetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monopropyl ether acetate, diethylene glycol monobutyl ether acetate, methyl acetate, ethyl acetate, butyl acetate, isobutyl acetate, tert-butyl acetate, ethyl pyruvate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate Ester solvents such as tert-butyl propionate, 3-methoxybutyl acetate, and ethyl 3-ethoxypropionate; lactone solvents such as γ-butyrolactone; nitrile solvents such as acetonitrile; halogen solvents such as chloromethane, dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, and 1,1,2,2-tetrachloroethane; and polar aprotic solvents such as N-methylpyrrolidone, N,N'-dimethylformamide, N,N'-dimethylacetamide, dimethyl sulfoxide, and hexamethylphosphoramide.

[0277] In addition, the amount of organic solvent added should preferably be set to 20 parts by mass or more and 500 parts by mass or less, and more preferably 25 parts by mass or more and 100 parts by mass or less, relative to the total amount of polyurethane components (polyisocyanate, high molecular weight polyol, chain extender, crosslinking agent) of 100 parts by mass.

[0278] Organic solvents can be removed after polymerization by vacuum distillation or crystallization, or they can be used directly in the conductive paste composition as a polyurethane solution without removal.

[0279] [catalyst]

[0280] In the synthesis of polyurethane, a catalyst should be added as needed to promote the formation of urethane bonds.

[0281] Carbamate catalysts can be appropriately selected from known catalysts, such as amine catalysts, ammonium salt catalysts, potassium salt catalysts, organometallic catalysts, etc.

[0282] Examples of amine catalysts include: triethylamine, N,N-dimethylcyclohexylamine, ethylenediamine, 2-methylethylenediamine, N,N,N',N'-tetramethylethylenediamine, N,N,N',N'-tetramethylpropanediamine, N,N,N',N”,N”-pentamethyldiethylenetriamine, N,N,N',N”,N”-pentamethyl-(3-aminopropyl)ethylenediamine, N,N,N',N”,N”-pentamethyldipropanetriamine, N,N,N',N’-tetramethylhexamethylenediamine, bis(2-dimethylaminoethyl) ether, dimethylethanolamine, dimethylisopropanolamine, dimethylaminoethoxyethanol, N,N-dimethylhexanolamine, N,N-dimethyl-N'-(2-hydroxy) Ethylene(ethylenediamine), N,N-dimethyl-N'-(2-hydroxyethyl)propanediamine, N,N,N'-trimethylaminoethylethanolamine, bis(dimethylaminopropyl)amine, bis(dimethylaminopropyl)isopropanolamine, N-methyl-N'-(2-dimethylaminoethyl)piperazine, N-methyl-N'-(2-hydroxyethyl)piperazine, N-methylmorpholine, N-ethylmorpholine, 1-methylimidazolium, 1,2-dimethylimidazolium, 1-isobutyl-2-methylimidazolium, 1-dimethylaminopropylimidazolium, 1-(2-hydroxyethyl)imidazolium, 1-(2-hydroxypropyl)imidazolium, 1-(2-hydroxyethyl)-2-methylimidazolium, 1-(2-hydroxypropyl)-2-methylimidazolium, etc.

[0283] Ammonium salt catalysts can be exemplified by quaternary ammonium salts such as tetraethylammonium hydroxide, or ammonium salts composed of 1,8-diazabicyclo(5,4,0)-undecene-7 or 1,5-diazabicyclo(4,3,0)-nonene-5 with octanoic acid, oleic acid, p-toluenesulfonic acid, formic acid, phenolic acid, phthalic acid, acetic acid, maleic acid, or boric acid.

[0284] Potassium salt catalysts include, for example, potassium carbonate, potassium acetate, and potassium octanoate.

[0285] Organometallic catalysts include, for example, tin acetate, tin octanoate (2-ethylhexanoate), tin oleate, tin laurate, dibutyltin diacetate, dimethyltin dilaurate, dibutyltin dilaurate, dibutyltin dithiol, dibutyltin maleate, dibutyltin dilaurate, dibutyltin dineodecanate, dioctyltin dithiol, dioctyltin dilaurate, dibutyltin dichlorodi ...

[0286] Considering that the polyurethane of this invention contains weakly acidic functional groups, which may hinder the activity of alkaline catalysts, it is advisable to use an organometallic catalyst, and organobismuth compounds are more ideal.

[0287] These urethane esterification catalysts can be used alone or in combination of two or more. Furthermore, the amount of urethane esterification catalyst used relative to 100 parts by mass of the total polyurethane components should preferably be between 0 and 5 parts by mass, and more preferably between 0.1 and 2 parts by mass.

[0288] [End-capping agent]

[0289] The polyurethane of this embodiment can have its functional groups introduced from the end-capping agent introduced to the end of the polyurethane by adding an end-capping agent after polymerization with an excess of isocyanate groups.

[0290] For example, urethane acrylates can be synthesized by using the following (meth)acrylate hydroxyalkyl ester as a capping agent for the polyurethane end.

[0291] [Chemistry 40]

[0292]

[0293] In the formula, R 5 For hydrogen atoms or methyl groups, Et represents ethyl groups, and Ph represents phenyl groups. R 1 Same as above.

[0294] R 5 It can be a hydrogen atom or a methyl group.

[0295] Carbamate acrylates can be polymerized and hardened by using heat or irradiation with active energy rays such as ultraviolet light, visible light, laser, electron beam, X-ray, gamma ray, plasma, and microwave, as needed, to produce hardened products.

[0296] The aforementioned reactive monomers may include, for example: methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, tert-butyl methacrylate, isobutyl methacrylate, isoamyl methacrylate, lauryl methacrylate, dodecyl methacrylate, stearyl acrylate, cyclohexyl methacrylate, isocamphenyl methacrylate, adamantane methacrylate, and other alkyl methacrylates; phenoxymethyl methacrylate, phenoxyethyl methacrylate, and other aryloxyalkyl methacrylates. ; benzyl methacrylate, phenethyl methacrylate, and other aralkyl methacrylates; phenyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, and other monofunctional methacrylate compounds; butanediol di(meth)acrylate, hexanediol di(meth)acrylate, octanediol di(meth)acrylate, nonanediol di(meth)acrylate, dodecanediol di(meth)acrylate, ethoxylated hexanediol di(meth)acrylate Acrylic esters, propoxylated hexanediol di(meth)acrylate, diethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, ethoxylated neopentyl glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, ethoxylated trimethylolpropane tri(meth)acrylate, propoxylated trimethylolpropane tri(meth)acrylate, tris(2-hydroxyethyl) isocyanurate tri(meth)acrylate, glycerol tri(meth)acrylate, etc. Polyfunctional (meth)acrylate compounds such as tetrapentyl alcohol tri(meth)acrylate, dinepentyl alcohol tri(meth)acrylate, di(trimethylolpropane)tri(meth)acrylate, neopentyl alcohol tetra(meth)acrylate, di(trimethylolpropane)tetra(meth)acrylate, dinepentyl alcohol tetra(meth)acrylate, dinepentyl alcohol penta(meth)acrylate, dinepentyl alcohol hexa(meth)acrylate, and di(trimethylolpropane) hexa(meth)acrylate; or their ethyleneoxy-modified, propyleneoxy-modified, and lactone-modified derivatives. They can be used alone or in combination of two or more.

[0297] Examples of the aforementioned polymerization initiators include: acetophenone, 2,2-diethoxyacetophenone, p-dimethylaminoacetophenone, benzophenone, 2-chlorobenzophenone, 4,4'-bis(diethylamino)benzophenone, benzoin ethyl ether, benzoin n-propyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin n-butyl ether, benzoin dimethyl ketal, 9-oxothiothoxane, p-isopropyl-α-hydroxyisobutylphenyl ketone, 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1-[ [4-(methylthio)phenyl]-2-morpholinylpropane-1-one, 2-hydroxy-2-methyl-1-phenylpropane-1-one, 2,4,6-trimethylbenzophenone, 4-methylbenzophenone, (2,4,6-trimethylbenzoyl)-diphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, 2,2-dimethoxy-1,2-diphenylethyl ketone, etc., are preferred. 1-hydroxycyclohexylphenyl ketone and bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide are also suitable. They can be used alone or in combination of two or more.

[0298] Alternatively, after the chain elongation reaction, an alcohol or amine represented by the following general formula (1C) can be used to introduce the aforementioned phenolic hydroxyl groups into the polyurethane.

[0299] [Chemistry 41]

[0300]

[0301] In the formula, "Az" represents a straight-chain, branched, or cyclic (ka+2) valence hydrocarbon group or a fluorinated hydrocarbon group with 1 to 19 carbon atoms, and the -CH2- constituting the aforementioned (ka+2) valence hydrocarbon group can also be replaced by -O-, -C(=O)-, or -Si(R 2 R 3 )-. X represents an oxygen atom or NR. 4 ka represents an integer from 0 to 2. kb, kc, kd, and ke represent 1 or 2. R 2 R 3 R 4 Same as above.

[0302] "Az" represents a straight-chain, branched, or cyclic (ka+2) valence hydrocarbon group or a fluorinated hydrocarbon group with 1 to 19 carbon atoms, and the -CH2- constituting the aforementioned (ka+2) valence hydrocarbon group can also be substituted with -O-, -C(=O)-, or -Si(R)-. 2 R 3 )-.

[0303] X represents an oxygen atom or NR. 4 .

[0304] Ka represents an integer from 0 to 2, and kb, kc, kd, and ke represent 1 or 2.

[0305] R 2 R 3 R 4 Same as above.

[0306] The following are specific examples of the straight-chain, branched, or cyclic (ka+2) valence hydrocarbon groups with carbon numbers of 1 to 19 in the above-mentioned "Az".

[0307] [Chemistry 42]

[0308]

[0309] In the formula, the dashed lines represent atomic bonds.

[0310] [Chemistry 43]

[0311]

[0312] In the formula, the dashed lines represent atomic bonds.

[0313] [Chemistry 44]

[0314]

[0315] In the formula, the dashed lines represent atomic bonds.

[0316] Specific examples of alcohols or amines represented by the above general formula (1C) may be shown below, but are not limited thereto.

[0317] [Chemistry 45]

[0318]

[0319] In the formula, X represents an oxygen atom or NR. 4 R 4 Same as above.

[0320] [Chemistry 46]

[0321]

[0322] In the formula, X represents an oxygen atom or NR. 4 R 4 Same as above.

[0323] [Chemistry 47]

[0324]

[0325] In the formula, X represents an oxygen atom or NR. 4 R 4 Same as above.

[0326] The total amount of the aforementioned capping agent with phenolic hydroxyl groups relative to the constituent components of the carbamate should preferably be 1-20% by mass, and more preferably 1-5% by mass.

[0327] The reaction temperature during polyurethane synthesis varies depending on the type of reaction matrix, and is generally suitable at 30–200℃, with 40–120℃ being even better.

[0328] The weight-average molecular weight of polyurethane is preferably 10,000–500,000, more preferably 15,000–200,000, and even more preferably 20,000–150,000. The weight-average molecular weight (Mw) is determined using gel permeation chromatography (GPC) in the form of a polystyrene equivalent.

[0329] The polyurethane in this embodiment may also contain antioxidants, defoamers, ultraviolet absorbers, etc. as additives, depending on the needs.

[0330] <Conductive paste composition>

[0331] The conductive paste composition of the present invention contains (A) a conductive filler, (B) the polyurethane containing phenolic hydroxyl groups of the present invention, and (C) a solvent, and preferably further contains (D) a phenolic compound. The components are described in more detail below.

[0332] [(A) Conductive filler]

[0333] Components (A) used to improve electrical conductivity can include: gold, silver, platinum, copper, tin, iron, magnesium, titanium, nickel, palladium, aluminum, tungsten, molybdenum, ruthenium, chromium, indium, solder, and their silver plating powders, etc.; or carbon, carbon black, carbon nanotubes, silver chloride, zinc oxide, titanium oxide, indium tin oxide, etc.

[0334] From the perspective of conductivity, gold, silver, and platinum are preferable. From the perspective of price, silver, copper, tin, iron, titanium, nickel, aluminum, tungsten, molybdenum, ruthenium, chromium, and stainless steel are preferable. Considering all factors, silver (silver powder) is the best.

[0335] The shapes of conductive filler particles can be listed as: spherical, granular, angular, dendritic, flake-like, needle-like, irregular, etc., and multiple fillers can also be used in combination.

[0336] There are no particular restrictions on the average particle size of conductive fillers, but it is preferable to be 5 nm to 10 μm.

[0337] There are no particular limitations on the method for determining the average particle size; for example, a laser diffraction particle size distribution device can be used.

[0338] The amount of conductive filler added should preferably be more than 70 parts by weight relative to the total of (A) conductive filler and (B) polyurethane containing phenolic hydroxyl groups per 100 parts by weight, and more preferably 80 parts by weight or more and less than 90 parts by weight.

[0339] [(B) Polyurethane containing phenolic hydroxyl groups]

[0340] The polyurethanes containing phenolic hydroxyl groups can be listed above.

[0341] Polyurethanes containing phenolic hydroxyl groups can be used alone or in combination. Furthermore, a portion of the polyurethane containing phenolic hydroxyl groups can be replaced with polyurethanes that do not contain phenolic hydroxyl groups.

[0342] The content of polyurethane without phenolic hydroxyl groups relative to the total amount of polyurethane with phenolic hydroxyl groups and polyurethane without phenolic hydroxyl groups should preferably be 0 to 30% by mass.

[0343] The aforementioned polyurethanes containing phenolic hydroxyl groups should preferably contain the aforementioned weakly acidic functional groups.

[0344] It is presumed that when the conductive filler is a metal particle or alloy particle, especially silver powder, the conductive paste composition of the present invention utilizes the phenolic hydroxyl groups or weakly acidic functional groups in the polyurethane and the oxide film of the silver powder to form a silver salt, which is then reduced by heat to generate silver nanoparticles. In this case, it is believed that silver salts formed with functional groups exhibiting strong acidity are more stable, making heat-induced reduction difficult, and silver salts are less likely to form in weakly acidic conditions, thus hindering the generation of silver nanoparticles. Therefore, it is believed that by using a polyurethane containing functional groups with appropriate acidity, silver salts can be formed and reduced even at lower calcination temperatures, easily generating silver nanoparticles.

[0345] [(C) Solvent]

[0346] (C) is a solvent. By including (C), the viscosity of the conductive paste composition becomes ideal, and its workability is improved.

[0347] (C) The solvents for which the components are listed include: toluene, xylene, cumene, 1,2,3-trimethylbenzene, 1,2,4-trimethylbenzene, 1,3,5-trimethylbenzene, styrene, α-methylstyrene, styrene-butadiene, sec-butadiene, isobutadiene, isopropyltoluene, diethylbenzene, 2-ethyl-p-xylene, 2-propyltoluene, 3-propyltoluene, 4-propyltoluene, 1,2,3,5-tetramethyltoluene, 1,2,4,5-tetramethyltoluene, tetrahydronaphthalene, 4-phenyl-1-butene, tert-pentanebenzene, pentanene, 2-tert-butyltoluene, 3-tert-butyltoluene, 4-tert-butyltoluene, 5-isopropyl-m-xylene, 3-methylethylbenzene, tert-butyl-3-ethylbenzene, 4-tert-butyl-o-xylene, 5-tert-butyl-m-xylene, tert-butyl-p-xylene Aromatic hydrocarbon solvents such as toluene, 1,2-diisopropylbenzene, 1,3-diisopropylbenzene, 1,4-diisopropylbenzene, dipropylbenzene, pentamethylbenzene, hexamethylbenzene, hexylbenzene, and 1,3,5-triethylbenzene; solvents containing n-heptane, isoheptane, 3-methylhexane, 2,3-dimethylpentane, 3-ethylpentane, 1,6-heptadiene, 5-methyl-1-hexyne, norbornene, norbornene, dicyclopentadiene, 1-methyl-1,4-cyclohexadiene, 1-heptyne, 2-heptyne, cycloheptane, cycloheptene, 1,3-dimethylcyclopentane, ethylcyclopentane, methylcyclohexane, 1-methyl-1-cyclohexene, 3-methyl-1-cyclohexene, methylenecyclohexane, 4-methyl-1-cyclohexene, 2-methyl-1-hexene, 2-methyl-2-hexene, 1- Heptene, 2-Heptene, 3-Heptene, n-Octane, 2,2-Dimethylhexane, 2,3-Dimethylhexane, 2,4-Dimethylhexane, 2,5-Dimethylhexane, 3,3-Dimethylhexane, 3,4-Dimethylhexane, 3-Ethyl-2-methylpentane, 3-Ethyl-3-methylpentane, 2-Methylheptane, 3-Methylheptane, 4-Methylheptane, 2,2,3-Trimethylpentane, 2,2,4-Trimethylpentane, Cyclooctane, Cyclooctene, 1,2-Dimethylcyclohexane, 1,3-Dimethylcyclohexane, 1,4-Dimethylcyclohexane, Ethylcyclohexane, Vinylcyclohexane, Isopropylcyclopentane, 2,2-Dimethyl-3-hexene, 2,4-Dimethyl-1-hexene, 2,5-Dimethyl-1-hexene, 2,5 -Dimethyl-2-hexene, 3,3-dimethyl-1-hexene, 3,4-dimethyl-1-hexene, 4,4-dimethyl-1-hexene, 2-ethyl-1-hexene, 2-methyl-1-heptene, 1-octene, 2-octene, 3-octene, 4-octene, 1,7-octadiene, 1-octyne, 2-octyne, 3-octyne, 4-octyne, n-nonane, 2,3-dimethylheptane, 2,4-dimethylheptane, 2,5-dimethylheptane, 3,3-dimethylheptane, 3,4-dimethylheptane, 3,5-dimethylheptane, 4-ethylheptane, 2-methyloctane, 3-methyloctane, 4-methyloctane, 2,2,4,4-tetramethylpentane, 2,2,4-trimethylhexane, 2,2,5-trimethylhexane, 2,2-Dimethyl-3-heptene, 2,3-Dimethyl-3-heptene, 2,4-Dimethyl-1-heptene, 2,6-Dimethyl-1-heptene, 2,6-Dimethyl-3-heptene, 3,5-Dimethyl-3-heptene, 2,4,4-Trimethyl-1-hexene, 3,5,5-Trimethyl-1-hexene, 1-Ethyl-2-methylcyclohexane, 1-Ethyl-3-methylcyclohexane, 1-Ethyl-4-methylcyclohexane, Propylcyclohexane, Isopropylcyclohexane, 1,1,3-Trimethylcyclohexane, 1,1,4-Trimethylcyclohexane, 1,2,3-Trimethylcyclohexane, 1 2,4-Trimethylcyclohexane, 1,3,5-Trimethylcyclohexane, Allylcyclohexane, Hydindane, 1,8-Nonadiene, 1-Nonyne, 2-Nonyne, 3-Nonyne, 4-Nonyne, 1-Nonene, 2-Nonene, 3-Nonene, 4-Nonene, n-Decane, 3,3-Dimethyloctane, 3,5-Dimethyloctane, 4,4-Dimethyloctane, 3-Ethyl-3-methylheptane, 2-Methylnonane, 3-Methylnonane, 4-Methylnonane, tert-Butylcyclohexane, Butylcyclohexane, Isobutylcyclohexane, 4-Isopropyl-1-methylcyclohexane, Pentyl Cyclopentane, 1,1,3,5-Tetramethylcyclohexane, Cyclododecane, 1-Decene, 2-Decene, 3-Decene, 4-Decene, 5-Decene, 1,9-Decadiene, Decahydronaphthalene, 1-Decayne, 2-Decayne, 3-Decayne, 4-Decayne, 5-Decayne, 1,5,9-Decatriene, 2,6-Dimethyl-2,4,6-Octatriene, Limonene, Myrcene, 1,2,3,4,5-Pentamethylcyclopentadiene, α-Phellandrene, Pinene, Terpinene, Tetrahydrodicyclopentadiene, 5,6-Dihydrodicyclopentadiene, Dicyclopentadiene Diene, 1,4-decadiyne, 1,5-decadiyne, 1,9-decadiyne, 2,8-decadiyne, 4,6-decadiyne, n-Undecane, Pentylcyclohexane, 1-Undecane, 1,10-Undecanediene, 1-Undecaneyne, 3-Undecaneyne, 5-Undecaneyne, Tricyclo[6.2.1.02,7]Undecane-4-ene, n-Dodecane, 2-Methylundecane, 3-Methylundecane, 4-Methylundecane, 5-Methylundecane, 2,2,4,6,6-Pentamethylheptane, 1,3-Dimethyladamantane, 1-Ethyladamantane, 1,5,9-Cyclododecanetriene, 1,2,4-Trivinylcyclohexane, isoalkanes, and other aliphatic hydrocarbon solvents; cyclohexanone, cyclopentanone, 2-octanone, 2-nonanone, 2-heptanone, 3-heptanone, 4-heptanone, 2-hexanone, 3-hexanone, diisobutyl ketone, methylcyclohexanone, methyl n-pentanone, methyl isobutyl ketone, isophorone, and other ketone solvents; 3-methoxybutanol, 3-methyl-3-methoxybutanol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, and other alcohol solvents; propylene glycol monomethyl ether, ethylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, propylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, diisopropyl ether, diisobutyl ether, diisopentanone, din-n-pentanone, methyl ethyl ether, dimethyl ethyl ether, diethyl ethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, diisopropyl ether, diisobutyl ether, diisopentanone, din-n-pentanone, methyl ethyl ether, diethyl ... Ether solvents such as cyclopentyl ether, methylcyclohexyl ether, di-n-butyl ether, di(sec-butyl) ether, di(sec-pentyl) ether, di(tert-pentyl) ether, di-n-hexyl ether, and anisole; ester solvents such as ethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, propylene glycol diacetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, ethyl lactate, ethyl pyruvate, butyl acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, tert-butyl acetate, tert-butyl propionate, and propylene glycol monotert-butyl ether acetate; lactone solvents such as γ-butyrolactone; and terpene solvents such as α-terpineol, α-pinene, dihydroterpineol, and dihydroterpineol acetate. Solvents can be used alone or in combination of two or more.

[0348] Considering the consideration of solvents not easily evaporating during printing and providing appropriate viscosity for printing, diethylene glycol monobutyl ether, diethylene glycol monoethyl ether acetate, and diethylene glycol monobutyl ether acetate are particularly good choices.

[0349] The amount of solvent (organic solvent) added should preferably be set in the range of 100 to 1,000 parts by weight relative to 100 parts by weight of polyurethane (B).

[0350] [(D)phenolic compounds]

[0351] Furthermore, with regard to phenolic compounds, it is preferable to include phenolic compounds containing the structure represented by the following general formula (2A).

[0352] [Chemistry 48]

[0353]

[0354] In the formula, R 6 Represents a hydrogen atom, halogen atom, cyano group, or hydroxyl group. Ay represents a straight-chain, branched, or cyclic (ka+2) valence hydrocarbon group or a fluorinated hydrocarbon group having 1 to 20 carbon atoms, and the -CH2- constituting the aforementioned (ka+2) valence hydrocarbon group can also be substituted with -O-, -C(=O)-, or -Si(R)-.2 R 3 )-. ka represents an integer from 0 to 2. kb and kd represent 1 or 2. kc and ke represent integers from 0 to 2. Z, Xf, ZZ, R 2 R 3 Same as above.

[0355] R 6 It represents a hydrogen atom, a halogen atom, a cyano group, or a hydroxyl group.

[0356] Ay represents a straight-chain, branched, or cyclic (ka+2) valence hydrocarbon group or a fluorinated hydrocarbon group with 1 to 20 carbon atoms, and the -CH2- constituting the aforementioned (ka+2) valence hydrocarbon group can also be substituted with -O-, -C(=O)-, or -Si(R)-. 2 R 3 )-. The straight-chain, branched, or cyclic (ka+2) valence hydrocarbon groups of Ay with 1 to 20 carbon atoms can be exemplified as follows.

[0357] [Chemistry 49]

[0358]

[0359] In the formula, the dashed lines represent atomic bonds.

[0360] [Transformation 50]

[0361]

[0362] In the formula, the dashed lines represent atomic bonds.

[0363] [Chemistry 51]

[0364]

[0365] In the formula, the dashed lines represent atomic bonds.

[0366] Ay is a straight-chain, branched, or cyclic (ka+2) valent fluorinated hydrocarbon group with 1 to 20 carbon atoms. Specific examples include hydrocarbon groups in which some or all of the hydrogen atoms are replaced by fluorine atoms.

[0367] ka represents an integer from 0 to 2, kb and kd represent 1 or 2, and kc and ke represent integers from 0 to 2.

[0368] Z, Xf, ZZ, R 2 R 3 Same as above.

[0369] The phenolic compound represented by the above general formula (2A) is preferably the phenolic compound represented by the following general formula (2B).

[0370] [Chemistry 52]

[0371]

[0372] In the formula, Ay' represents a straight-chain, branched, or cyclic (ka+2) valence hydrocarbon group or a fluorinated hydrocarbon group with 1 to 19 carbon atoms, and the -CH2- constituting the aforementioned (ka+2) valence hydrocarbon group can also be substituted with -O-, -C(=O)-, or -Si(R 2 R 3 )-. ka represents an integer from 0 to 2. kb, kc, kd, and ke represent 1 or 2. R 2 R 3 R 6 Same as above.

[0373] Ay' represents a straight-chain, branched, or cyclic (ka+2) valence hydrocarbon group or a fluorinated hydrocarbon group with 1 to 19 carbon atoms, and the -CH2- constituting the aforementioned (ka+2) valence hydrocarbon group can also be substituted with -O-, -C(=O)-, or -Si(R)-. 2 R 3 )-.

[0374] Ka represents an integer from 0 to 2, and kb, kc, kd, and ke represent 1 or 2.

[0375] R 2 R 3 R 6 Same as above.

[0376] The compounds represented by the above general formulas (2A) and (2B) can be specifically exemplified as follows.

[0377] [Chemistry 53]

[0378]

[0379] [Chemistry 54]

[0380]

[0381] [Chemistry 55]

[0382]

[0383] [Chemistry 56]

[0384]

[0385] [Chemistry 57]

[0386]

[0387] [Chem.58]

[0388]

[0389] [Chemistry 59]

[0390]

[0391] [Transformation 60]

[0392]

[0393] [Chemistry 61]

[0394]

[0395] [Chemistry 62]

[0396]

[0397] [Chemistry 63]

[0398]

[0399] [Chemistry 64]

[0400]

[0401] [Chemistry 65]

[0402]

[0403] There are no particular restrictions on the synthesis of phenolic compounds represented by the above general formulas (2A) and (2B). The most suitable method can be selected according to the structure. For example, in the case of general formula (2Ba) where kb and kc are 1 in formula (2B), it can be synthesized using steps i) to v) shown in the following reaction formulas.

[0404] [Chemistry 66]

[0405]

[0406] In the formula, R 6 Ay', ka, kc, and ke are as described above. Rp represents an acid-labile group. XA represents a halogen atom.

[0407] Step i) is the step of protecting the halogenated phenolic compound (2Bb) to introduce the intermediate halogenated aryl compound (2Bd).

[0408] The reaction in step i) can be easily carried out under known conditions. For example, when Rp is a tert-butyl, tert-pentyl, methylcyclopentyl, ethylcyclopentyl, methylcyclohexyl, ethylcyclohexyl, methyladamantyl, ethyladamantyl, or other tert-alkyl groups, the halogenated phenolic compound (2Bb) and olefins corresponding to Rp, such as isobutylene and isopentene, can be reacted in the absence of a solvent or in a solvent such as toluene or hexane in the presence of an acid catalyst at a reaction temperature of -20 to 50°C. Examples of acid catalysts used include inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, and perchloric acid; and organic acids such as methanesulfonic acid, trifluoromethanesulfonic acid, p-toluenesulfonic acid, and benzenesulfonic acid.

[0409] Step ii) is the step of entering the intermediate halogenated aryl compound (2Bd) through the nucleophilic substitution reaction of the fluorobenzene compound (2Bc).

[0410] The reaction in step ii) can be easily carried out under known conditions. For example, when Rp is a tert-butyl, tert-pentyl, methylcyclopentyl, ethylcyclopentyl, methylcyclohexyl, ethylcyclohexyl, methyladamantyl, ethyladamantyl, or other tert-alkyl compounds, the fluorobenzene compound (2Bc) and alcohols corresponding to Rp, such as tert-butanol and tert-pentanol, or corresponding alkoxides such as potassium tert-butoxy, can be reacted in the presence of a base in solvents such as tetrahydrofuran and N-methyl-2-pyrrolidone at a reaction temperature of 10–80°C. Examples of bases used include: metal hydrides such as borane, alkylborane, sodium hydride, lithium hydride, potassium hydride, and calcium hydride; alkyl metal compounds such as triphenylmethyllithium, triphenylmethyl sodium, triphenylmethyl potassium, methyllithium, phenyllithium, n-butyllithium, sec-butyllithium, tert-butyllithium, and ethyl magnesium bromide; and alkoxides such as sodium methoxide, sodium ethoxide, lithium methoxide, lithium ethoxide, lithium tert-butoxide, and potassium tert-butoxide.

[0411] Step iii) is the step of oxidizing the halogenated aryl compound (2Bd) to introduce the intermediate phenolic compound (2Be).

[0412] The reaction can be easily carried out using well-known methods, such as the following reaction formula.

[0413] [Chemistry 67]

[0414]

[0415] In the formula, Rp, ke, and XA are as described above. MA represents Li, MgCl, MgBr, and MgI. r It represents a monovalent hydrocarbon group that has 1 to 6 carbon atoms and is either straight-chain, branched, or cyclic.

[0416] First, an organometallic reagent (2Bg) is prepared from a halogenated aryl compound (2Bd) and Li or Mg in solvents such as tetrahydrofuran or diethyl ether. Then, an arylboronic acid derivative (2Bh) is introduced via reaction with a borate ester compound (2J). Finally, an intermediate phenolic compound (2Be) is obtained using oxidizing agents such as hydrogen peroxide, performic acid, peracetic acid, or m-chloroperbenzoic acid. This step can typically be carried out in a single pot without a purification step.

[0417] Step iv) is the step of etherifying the intermediate phenolic compound (2Be) into the aryl ether compound (2Bf).

[0418] The reaction can be easily carried out using well-known methods, such as the following reaction formula.

[0419] [Chemistry 68]

[0420]

[0421] In the formula, Rp, ka, ke, and Ay' are as described above. T 1 Each can be independently represented by a hydroxyl group, a halogen atom, an alkyl sulfonyloxy group, or an aromatic sulfonyloxy group.

[0422] Etherification can be exemplified by treating an intermediate phenolic compound (2Be) and a compound containing a detached group (2Bi) with an alkali to etherify them.

[0423] T 1 Examples of halogen atoms include: chlorine, bromine, and iodine. Also, T 1 Examples of alkyl sulfonyloxy and aromatic sulfonyloxy include: methane sulfonyloxy, trifluoromethane sulfonyloxy, benzene sulfonyloxy, and p-toluene sulfonyloxy.

[0424] Specific examples of alkalis used include: sodium methoxide, sodium ethoxide, lithium methoxide, lithium ethoxide, lithium tert-butoxide, potassium tert-butoxide, and other alkoxide salts; organic amines such as pyridine, triethylamine, N,N-dimethylaniline, and 4-dimethylaminopyridine; inorganic hydroxides such as sodium hydroxide, lithium hydroxide, potassium hydroxide, barium hydroxide, and tetrabutylammonium hydroxide; inorganic carbonates such as sodium carbonate, sodium bicarbonate, lithium carbonate, and potassium carbonate; alkoxides such as sodium methoxide, sodium ethoxide, lithium methoxide, lithium ethoxide, lithium tert-butoxide, potassium tert-butoxide, and other alkoxides; and boranes, alkylboranes, sodium hydride, lithium hydride, and potassium hydride. Metal hydrides such as calcium hydride; alkyl metal compounds such as triphenylmethyllithium, triphenylmethylsodium, triphenylmethylpotassium, methyllithium, phenyllithium, sec-butyllithium, tert-butyllithium, methylmagnesium chloride, ethylmagnesium chloride, and ethylmagnesium bromide; and metal amides such as sodium ammonia, potassium ammonia, diisopropylamine lithium, diisopropylamine potassium, dicyclohexylamine lithium, dicyclohexylamine potassium, 2,2,6,6-tetramethylpiperidinium, bis(trimethylsilylamine lithium), bis(trimethylsilylamine sodium), bis(trimethylsilylamine potassium), isopropylcyclohexylamine lithium, and diisopropylaminomagnesium bromide. The amount of base used relative to 1 mole of the intermediate phenolic compound (2Be) should preferably be 0.9–10 moles, with 1.0–5.0 moles being particularly preferred.

[0425] The solvents can be selected according to the reaction conditions, and can be used alone or in combination: water or ethers such as tetrahydrofuran, diethyl ether, di-n-butyl ether, and 1,4-dioxane; hydrocarbons such as n-hexane, n-heptane, benzene, toluene, xylene, and cumene; alcohols such as methanol, ethanol, isopropanol, and tert-butanol; aprotic polar solvents such as dimethyl sulfoxide (DMSO) and N,N-dimethylformamide (DMF); and chlorinated organic solvents such as dichloromethane, chloroform, and carbon tetrachloride. The bases mentioned above can also be used as solvents.

[0426] The reaction temperature and time vary depending on the reagents and conditions, for example, T 1 When the reaction involves bromine atoms and potassium carbonate is used as the base, the ideal reaction temperature is room temperature to 120°C, with 30°C to 90°C being preferable as it rapidly terminates the reaction. For yield purposes, the ideal reaction time is typically 1 to 60 hours, monitored and terminated using gas chromatography (GC) or silica gel thin-layer chromatography (TLC). The aryl ether compound (2Bf) can be obtained from the reaction mixture using conventional aqueous work-up. Purification can be performed using distillation, chromatography, or other conventional methods if necessary.

[0427] Step v) is the step of introducing the phenolic compound of the present invention through the deprotection reaction of the aryl ether compound (2Bf).

[0428] Solvents can be selected from the following solvents and used alone or in combination of two or more, such as: hydrocarbons such as toluene, xylene, hexane, and heptane; chlorinated solvents such as dichloromethane, chloroform, and dichloroethane; ethers such as diethyl ether, tetrahydrofuran, and dibutyl ether; ketones such as acetone and 2-butanone; esters such as ethyl acetate and butyl acetate; nitrile solvents such as acetonitrile; alcohols such as methanol and ethanol; aprotic polar solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, and dimethyl sulfoxide; and water. Furthermore, the reaction can also be carried out without a solvent.

[0429] Acids that can be used include, for example, inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, and perchloric acid; organic acids such as methanesulfonic acid, trifluoromethanesulfonic acid, p-toluenesulfonic acid, and benzenesulfonic acid; and Lewis acids such as boron trifluoride, trimethylsilyl trifluoromethanesulfonate, aluminum chloride, magnesium chloride, ferric chloride, zinc chloride, and titanium chloride. Furthermore, the amount of acid used relative to 1 mole of the aryl ether compound (2Bf) should preferably be 0.001 to 5 moles, with 0.01 to 0.5 moles being particularly favorable. Using more than 0.001 moles will not slow down the reaction rate, thus avoiding the cost disadvantages caused by increased reaction time. Using less than 5 moles will prevent side reactions caused by strong acidity and will not reduce the yield. Additionally, to suppress acidity, amines such as ammonia, triethylamine, pyridine, dimethylpyridine, trimethylpyridine, and N,N-dimethylaniline can be added.

[0430] The deprotection reaction described above requires an appropriate reaction temperature depending on the reaction conditions. However, at low temperatures, the reaction may sometimes fail to proceed; therefore, a temperature of 40–120°C is generally preferred. Furthermore, to improve the yield, the reaction time should be determined by monitoring the reaction progress using thin-layer chromatography, gas chromatography, or similar methods, typically ranging from about 2 hours to 1 day. The reaction can be carried out by diluting the aryl ether compound (2Bf) with a solvent, adding acid, and heating with stirring. After the reaction is complete, the phenolic compound of this invention can be obtained using conventional aqueous work-up. If necessary, purification can be performed using conventional methods such as distillation, recrystallization, and chromatography.

[0431] When the above-mentioned phenolic compound is incorporated into the conductive paste composition of the present invention, it is preferable to set the amount to be more than 0.5 parts by mass relative to the total of (A) conductive filler, (B) polyurethane containing phenolic hydroxyl groups and (D) phenolic compound, and more preferably 1 part by mass and less than 10 parts by mass.

[0432] The aforementioned phenolic compounds possess the same effects as the phenolic hydroxyl groups and weakly acidic functional groups in the polyurethane of this invention. That is, when the conductive filler is presumably metal particles or alloy particles, especially silver powder, the phenolic hydroxyl groups of the phenolic compound and the oxide film of the silver powder will be used to form silver salts, which will be reduced by heat, thereby generating silver nanoparticles. It is believed that phenolic compounds, especially those with electron-withdrawing groups on the aromatic ring, have improved acidity and are more likely to form silver salts than phenols without functional groups, thus making it easier to generate silver nanoparticles even at low temperatures. Furthermore, when the phenolic compound is presumably of the aforementioned general formula (2B), the aromatic ring has fluorine atoms, which will undergo nucleophilic substitution reactions due to the silver salt, and the silver fluoride byproduct generated in this process will be reduced by heat, which will also generate silver nanoparticles.

[0433] <Conductive wiring>

[0434] Furthermore, the present invention provides conductive wiring formed on a substrate and composed of a calcined product of the aforementioned conductive paste composition. When the substrate is elastic, elastic conductive wiring is provided.

[0435] The conductive wiring of the present invention will be described below, but the present invention is not limited thereto.

[0436] Examples of substrates for forming conductive wiring include: polyurethane, polyester, polysiloxane, nitrile rubber, butadiene rubber, polyethylene, polypropylene, polyolefin, PTFE, and PFA. The substrate should preferably be stretchable, with stretchable sheets or films being preferable, stretchable polyurethane substrates being even better, and thermoplastic polyurethane substrates being particularly desirable. The surface of the sheet can be flat or textured. Textured surfaces allow for the formation of a bellows structure in the direction perpendicular to the substrate, suppressing changes in conductivity during stretching. Alternatively, fabrics made of non-woven or stretchable fibers can also be used.

[0437] The substrate with elasticity should ideally have a maximum elasticity of 1000%. It is believed that the elongation of muscles relative to human movement is 10% for bones such as the chest, 20% for the abdomen, and 50% for joints. The elasticity required for conductive wiring varies depending on the part that is attached to the muscle.

[0438] The following explanation pertains to the use of a stretchable substrate (stretchable substrate), but the same applies to non-stretchable substrates, and is not limited to the following.

[0439] Conductive wiring derived from the conductive paste composition of this invention is formed on a stretchable substrate. There are no particular limitations on the method for forming the conductive wiring on the stretchable substrate; methods such as dip coating, spray coating, spin coating, roll coating, flow coating, blade coating, screen printing, flexographic printing, gravure printing, and inkjet printing are ideal. In particular, using printing to form the wiring pattern can improve productivity, and the wiring width can be freely designed.

[0440] The ideal film thickness for conductive wiring is in the range of 10 nm to 1000 μm, with 5 to 50 μm being even better.

[0441] A conductive paste composition is printed onto a stretchable substrate and then calcined. That is, conductive wiring is formed on the substrate by printing the conductive paste composition. The calcination temperature for forming the conductive wiring is 60–160°C, preferably in the range of 120°C–150°C, and the time is from 1 second to 10 hours, preferably from 10 minutes to 5 hours. Calcination can be carried out in a heated plate or oven, or it can be carried out at a higher temperature and for a shorter time using flash annealing, or it can be carried out using infrared irradiation.

[0442] Conductivity can be evaluated by forming a stretchable conductive wire on a substrate and measuring the resistance between the two ends of the wire. A good stretchable conductive wire exhibits a smaller change in resistance before and during substrate elongation, and a smaller deterioration in conductivity when the elongated substrate shrinks and returns to its original shape. Furthermore, ideally, the wire should not break during repeated stretching and should exhibit minimal change in resistance.

[0443] Furthermore, the resistance of the conductive wiring of the present invention at 20% elongation should preferably be 500% or less of the resistance before elongation. There is no particular limitation on the lower limit, but it should preferably be low, for example, 150% or more. The maximum resistance when repeatedly stretched and contracted 1000 times at an elongation of 20% should preferably be 5000% or less of the resistance before stretching and contraction. There is no particular limitation on the lower limit, but it should preferably be low, for example, 300% or more. The above resistance can be obtained using the measurement method described later.

[0444] In addition, a cover film can be used to encase the conductive wiring. The cover film improves water resistance and mechanical strength. Since both the substrate and the conductive wiring are elastic, the cover film also needs to be elastic. The material of the cover film can be the same as the substrate, and can be selected from polyurethane, urethane acrylate, polyester, polysiloxane, nitrile rubber, butadiene rubber, polyethylene, polypropylene, polyolefin, PTFE, PFA, etc. The ideal thickness of the cover film is in the range of 10 nm to 1 mm.

[0445] Conductive wiring formed using the conductive paste composition of the present invention, especially when containing silver powder, exhibits high conductivity because the silver nanoparticles generated during the calcination process of the wiring are dispersed in the insulating polymer between the silver powder particles. Furthermore, even when the wiring is elongated and the distance between the silver powder particles widens, the conductive path is not easily interrupted due to the silver nanoparticles dispersed between the silver powder particles, thus reducing the likelihood of wire breakage and minimizing changes in conductivity.

[0446] [Example]

[0447] The present invention will now be specifically described using synthetic examples, embodiments, and comparative examples, but the invention is not limited thereto. Furthermore, the weight-average molecular weight (Mw) and number-average molecular weight (Mn) were determined using gel permeation chromatography (GPC) in the form of polystyrene equivalents. The GPC determination conditions are described below.

[0448] Column: TSKgel G4000H XL TSKgel G3000H XL TSKgel G2000H XL 2

[0449] Mobile phase: Tetrahydrofuran

[0450] Column drying oven temperature: 40℃

[0451] Sample concentration: 0.20% by mass

[0452] Sample injection volume: 100 μL

[0453] Flow rate: 1 mL / min

[0454] Polyurethanes containing phenolic hydroxyl groups are synthesized as follows.

[0455] [1] Synthesis of capping agents containing phenolic hydroxyl groups

[0456] [Synthetic Example 1-1] Synthesis of Capping Agent 1

[0457] [Chemistry 69]

[0458]

[0459] [Synthetic Example 1-1-1] Synthesis of Bromobenzene 1

[0460] Under nitrogen atmosphere, methanesulfonic acid (4.8 g) was added at -20 to -10 °C to a solution of bromophenol 1 (76.4 g), isopentenene (112.2 g), and toluene (10 g). After stirring at this temperature for 3 hours, triethylamine (10.1 g) was added dropwise, followed by the addition of a 25% (w / w) aqueous solution of caustic soda (32.0 g) to stop the reaction. A standard aqueous work-up was performed. Bromobenzene 1 (84.6 g, 81% yield) was obtained by vacuum distillation.

[0461] Boiling point: 67℃ / 10Pa.

[0462] [Synthetic Example 1-1-2] Synthesis of intermediate phenol 1

[0463] Under nitrogen atmosphere, geraniol reagent, prepared prior with bromobenzene 1 (52.2 g), magnesium (5.1 g), and tetrahydrofuran 140 mL, was added dropwise to a solution of trimethyl borate (22.9 g) and tetrahydrofuran (310 mL) at an internal temperature below -5 °C. The reaction was stirred continuously at 5 °C for 3 hours. Subsequently, acetic acid (18.0 g) and 35% hydrogen peroxide (25.3 g) were added at an internal temperature below 30 °C. The mixture was stirred continuously at room temperature for 3 hours, and then recrystallized using a toluene / n-hexane mixed solvent according to standard post-treatment methods to obtain intermediate phenol 1 (29.7 g, yield 75%).

[0464] IR(D-ATR): ν=3233,3071,2941,2929,2853,1622,1601,1512,1480,1465, 1447,1378,1334,1311,1205,1196,1158,1111,1097,975,966,870,816cm -1 .

[0465] 1 H-NMR (600MHz in DMSO-d6): δ=9.52(1H,s),6.88(1H,t),6.55(1H,dd),6.46(1H,dd),1.62(2H,q),1.14(6H,s),0.93(3H,t)ppm.

[0466] 19 F-NMR (565MHz in DMSO-d6): δ=-126.6(1F,s)ppm.

[0467] [Synthetic Example 1-1-3] Synthesis of Protected Phenol 1

[0468] Under nitrogen atmosphere, etherifying agent 1 (36.9 g) was added at 60–80 °C to a slurry solution of intermediate phenol 1 (29.5 g), potassium carbonate (20.5 g), sodium iodide (40 mg), and dimethylformaldehyde (74 g). After stirring at this temperature for 20 hours, water (160 g) was added dropwise to stop the reaction. A standard aqueous work-up was performed to obtain protected phenol 1 (53.2 g, crude yield 91%).

[0469] [Synthetic Example 1-1-4] Synthesis of Capping Agent 1

[0470] The solution of the above-obtained protected phenol 1 (53.2 g), p-toluenesulfonic acid 1 hydrate (0.2 g), and toluene (140 g) was heated and stirred continuously at an internal temperature of 70–100 °C for 3 hours. Then, 50 g of water was added at an internal temperature below 30 °C to stop the reaction. Subsequently, a conventional aqueous work-up was performed, followed by recrystallization in an ethyl acetate / n-hexane mixed solvent to obtain capping agent 1 (31.6 g, two-step yield 71%).

[0471] IR(D-ATR): ν=3483,3189,2919,2852,1605,1521,1477,1468,1449,1395,1313 ,1275,1263,1243,1205,1163,1113,1046,1032,1008,955,864,840,799,788cm -1 .

[0472] 1 H-NMR(600MHz in DMSO-d6): δ=9.18(1H,s),6.82(1H,t),6.74(1H,dd),6.54(1H,dd),4.29(1H,s),3.83(2H,t),3.36(2H,t),1.63(2H,m),1.16-1.44(16H,m)ppm.

[0473] 19 F-NMR (565MHz in DMSO-d6): δ=-133.7(1F,t)ppm.

[0474] [Synthetic Examples 1-2] Synthesis of Capping Agent 2

[0475] [Chemistry 70]

[0476]

[0477] [Synthetic Example 1-2-1] Synthesis of Bromobenzene 2

[0478] Under nitrogen atmosphere, fluorobenzene 1 (100 g) was added dropwise at 0–10 °C to a solution containing potassium tert-butoxy (63.9 g) dissolved in THF (360 g). The mixture was stirred at this temperature for 10 hours, then water (150 g) was added dropwise to stop the reaction. A standard aqueous work-up was performed. Bromobenzene 2 (98.6 g, 77% yield) was obtained by vacuum distillation.

[0479] Boiling point: 97-100℃ / 700Pa.

[0480] [Synthetic Example 1-2-2] Synthesis of intermediate phenol 2

[0481] Bromobenzene 1 was replaced with bromobenzene 2, and otherwise intermediate phenol 2 was obtained by the same method as in [Synthetic Example 1-1-2] (yield 77%).

[0482] [Synthetic Examples 1-2-3] Synthesis of Protected Phenol 2

[0483] Intermediate phenol 1 was replaced with intermediate phenol 2. Otherwise, protected phenol 2 was obtained by the same method as in [Synthetic Example 1-1-3] (yield 92%).

[0484] [Synthetic Example 1-2-4] Synthesis of Capping Agent 2

[0485] Protecting phenol 1 was replaced with protecting phenol 2. Otherwise, capping agent 2 was obtained in the same manner as in [Synthetic Example 1-1-4] (yield 78%).

[0486] [Synthetic Examples 1-3] Synthesis of Capping Agent 3

[0487] [Chemistry 71]

[0488]

[0489] [Synthetic Example 1-3-1] Synthesis of Bromobenzene 3

[0490] Bromophenol 1 was replaced with bromophenol 3, and otherwise bromobenzene 3 was obtained by the same method as in [Synthesis Example 1-1-1] (yield 77%).

[0491] Boiling point: 66℃ / 6Pa.

[0492] [Synthetic Example 1-3-2] Synthesis of intermediate phenol 3

[0493] Bromobenzene 1 was replaced with bromobenzene 3, and otherwise intermediate phenol 3 was obtained by the same method as in [Synthetic Example 1-1-2] (yield 62%).

[0494] [Synthetic Example 1-3-3] Synthesis of Protected Phenol 3

[0495] Intermediate phenol 1 was replaced with intermediate phenol 3. Otherwise, protected phenol 3 was obtained by the same method as in [Synthetic Example 1-1-3] (yield 82%).

[0496] [Synthetic Examples 1-3-4] Synthesis of Capping Agent 3

[0497] Protecting phenol 1 was replaced with protecting phenol 3. Otherwise, capping agent 3 was obtained in the same manner as in [Synthetic Example 1-1-4] (yield 92%).

[0498] IR(D-ATR): ν=3494,3215,2932,2918,2849,1613,1526,1503,1480,1470,143 4,1400,1287,1264,1212,1183,1091,1077,1054,1020,1004,967,942,804cm -1 .

[0499] 1 H-NMR(600MHz in DMSO-d6): δ=9.75(1H,s),6.70(2H,dt),4.28(1H,t),3.92(2H,t),3.35(2H,m),1.65(2H,m),1.32-1.42(4H,m),1.20-1.32(12H,m)ppm.

[0500] 19 F-NMR (565MHz in DMSO-d6): δ=-158.1~-157.9(1F,m),-159.3~-159.1(1F,m)ppm.

[0501] [Synthetic Examples 1-4] Synthesis of Capping Agent 4

[0502] [Chemistry 72]

[0503]

[0504] [Synthetic Example 1-4-1] Synthesis of Bromobenzene 4

[0505] Bromophenol 1 was replaced with bromophenol 4, and otherwise bromobenzene 4 was obtained by the same method as in [Synthesis Example 1-1-1] (yield 72%).

[0506] Boiling point: 53℃ / 15Pa.

[0507] [Synthetic Example 1-4-2] Synthesis of intermediate phenol 4

[0508] Bromobenzene 1 was replaced with bromobenzene 4, and otherwise intermediate phenol 4 was obtained by the same method as in [Synthetic Example 1-1-2] (yield 64%).

[0509] 1 H-NMR (600MHz in DMSO-d6): δ=9.99(1H,s),6.44(2H,m),1.62(2H,m),1.15(6H,s),0.94(3H,t)ppm.

[0510] 19 F-NMR (565MHz in DMSO-d6): δ=-122.9(2F,s)ppm.

[0511] [Synthetic Example 1-4-3] Synthesis of Protected Phenol 4

[0512] Intermediate phenol 1 was replaced with intermediate phenol 4. Otherwise, protected phenol 4 was obtained by the same method as in [Synthetic Example 1-1-3] (yield 89%).

[0513] [Synthetic Example 1-4-4] Synthesis of Capping Agent 4

[0514] Protecting phenol 1 was replaced with protecting phenol 4. Otherwise, capping agent 4 was obtained in the same manner as in [Synthetic Example 1-1-4] (yield 73%).

[0515] IR(D-ATR): ν=3532,3101,2922,2853,2801,1649,1613,1530,1468,1457, 1426,1397,1268,1254,1239,1200,1156,1046,1036,1018,855,817,804cm -1 .

[0516] 1 H-NMR(600MHz in DMSO-d6): δ=9.38(1H,s),6.63(2H,m),4.30(1H,s),3.85(2H,t),3.36(2H,t),1.63(2H,m),1.32-1.42(4H,m),1.20-1.32(12H,m)ppm.

[0517] 19 F-NMR (565MHz in DMSO-d6): δ=-158.1(1F,m)ppm.

[0518] [Synthetic Examples 1-5] Synthesis of Capping Agent 5

[0519] [Chemistry 73]

[0520]

[0521] [Synthetic Example 1-5-1] Synthesis of Bromobenzene 5

[0522] By replacing fluorobenzene 1 with fluorobenzene 2, bromobenzene 5 was obtained using the same method as in [Synthesis Example 1-2-1] (yield 94%).

[0523] Boiling point: 82-84℃ / 300Pa.

[0524] [Synthetic Example 1-5-2] Synthesis of intermediate phenol 5

[0525] Bromobenzene 1 was replaced with bromobenzene 5, and otherwise intermediate phenol 5 was obtained by the same method as in [Synthetic Example 1-1-2] (yield 62%).

[0526] [Synthetic Example 1-5-3] Synthesis of Protected Phenol 5

[0527] Intermediate phenol 1 was replaced with intermediate phenol 5. Otherwise, protected phenol 5 was obtained by the same method as in [Synthetic Example 1-1-3] (yield 81%).

[0528] [Synthetic Example 1-5-4] Synthesis of Capping Agent 5

[0529] Protecting phenol 1 was replaced with protecting phenol 5. Otherwise, capping agent 5 was obtained in the same manner as in [Synthetic Example 1-1-4] (yield 77%).

[0530] [Synthetic Examples 1-6] Synthesis of Capping Agent 6

[0531] [Chemistry 74]

[0532]

[0533] [Synthetic Example 1-6-1] Synthesis of Bromobenzene 6

[0534] By replacing fluorobenzene 1 with fluorobenzene 3, bromobenzene 6 was obtained using the same method as in [Synthesis Example 1-2-1] (yield 77%).

[0535] Boiling point: 99-100℃ / 1KPa.

[0536] [Synthetic Example 1-6-2] Synthesis of intermediate phenol 6

[0537] Bromobenzene 1 was replaced with bromobenzene 6, and otherwise intermediate phenol 6 was obtained by the same method as in [Synthetic Example 1-1-2] (yield 68%).

[0538] [Synthetic Example 1-6-3] Synthesis of Protected Phenol 6

[0539] The intermediate phenol 1 was replaced with the intermediate phenol 6. Otherwise, the protected phenol 6 was obtained by the same method as in [Synthetic Example 1-1-3] (yield 86%).

[0540] [Synthetic Example 1-6-4] Synthesis of End-Capping Agent 6

[0541] Protecting phenol 1 was replaced with protecting phenol 6. Otherwise, capping agent 6 was obtained in the same manner as in [Synthetic Example 1-1-4] (yield 86%).

[0542] [Synthetic Examples 1-7] Synthesis of Capping Agent 7

[0543] [Chemistry 75]

[0544]

[0545] [Synthetic Example 1-7-1] Synthesis of Capping Agent 7

[0546] Under nitrogen atmosphere, etherifying agent 2 (19.5 g) was added at 60–80 °C to a slurry solution of dihydroxybenzene 1 (55.9 g), potassium carbonate (41.5 g), sodium iodide (100 mg), and dimethylformaldehyde (300 g). After stirring at this temperature for 3 hours, water (400 g) was added dropwise to stop the reaction. A conventional aqueous work-up was performed. Recrystallization was carried out in an ethyl acetate / n-hexane mixed solvent to obtain capping agent 7 (18.6 g, 62% yield).

[0547] [Synthetic Examples 1-8] Synthesis of Capping Agent 8

[0548] [Chemistry 76]

[0549]

[0550] [Synthetic Example 1-8-1] Synthesis of Capping Agent 8

[0551] Dihydroxybenzene 1 was replaced with dihydroxybenzene 2, and etherifying agent 2 was replaced with etherifying agent 1. Otherwise, capping agent 8 was obtained by the same method as in [Synthesis Example 1-7-1] (yield 43%).

[0552] [Synthetic Examples 1-9] Synthesis of Capping Agent 9

[0553] [Chemistry 77]

[0554]

[0555] [Synthetic Example 1-9-1] Synthesis of Capping Agent 9

[0556] Dihydroxybenzene 1 was replaced with dihydroxybenzene 3, and etherifying agent 2 was replaced with etherifying agent 1. Otherwise, capping agent 9 was obtained in the same manner as in [Synthesis Example 1-7-1] (yield 45%).

[0557] [Synthetic Examples 1-10] Synthesis of Capping Agent 10

[0558] [Chemistry 78]

[0559]

[0560] [Synthetic Example 1-10-1] Synthesis of Protected Phenol 10

[0561] Etherifying agent 1 was changed to etherifying agent 3, and otherwise protected phenol 10 was obtained by the same method as in [Synthesis Example 1-1-3] (yield 81%).

[0562] [Synthetic Example 1-10-2] Synthesis of Capping Agent 10

[0563] Protecting phenol 1 was replaced with protecting phenol 10. Otherwise, capping agent 10 was obtained in the same manner as in [Synthetic Example 1-1-4] (yield 86%).

[0564] [Synthetic Examples 1-11] Synthesis of Capping Agent 11

[0565] [Chemistry 79]

[0566]

[0567] [Synthetic Example 1-11-1] Synthesis of Protected Phenol 11

[0568] Etherifying agent 1 was changed to etherifying agent 4, and otherwise protected phenol 11 was obtained by the same method as in [Synthesis Example 1-1-3] (yield 82%).

[0569] [Synthetic Example 1-11-2] Synthesis of End-Capping Agent 11

[0570] Protecting phenol 1 was replaced with protecting phenol 11. Otherwise, capping agent 11 was obtained in the same manner as in [Synthetic Example 1-1-4] (yield 75%).

[0571] IR(D-ATR): ν=3619,3292,2948,2890,1608,1516,1452,1386,1280,1234,11 91,1157,1109,1101,1052,1023,966,945,912,851,841,823,798,756,740cm -1 .

[0572] 1H-NMR (600MHz in DMSO-d6): δ=9.20(2H,s),6.82(2H,t),6.76(2H,dd),6.57(2H,dd),4.55(2H,t),3.85(4H,s),3.54(4H,d)ppm.

[0573] [2] Synthesis of polyols containing weakly acidic functional groups

[0574] [Synthetic Example 2-1] Synthesis of Hexafluorool-containing Chain Extender 1

[0575] [Chemistry 80]

[0576]

[0577] [Synthetic Example 2-1-1] Synthesis of Chain Extender 1

[0578] Under nitrogen atmosphere, trimethylolpropane (1260 g), esterifying agent 1 (1415 g), and a methanol solution of 28% sodium methoxide (60.7 g) were stirred at 100–140 °C. Transesterification was carried out while distilling off methanol. After the reaction was complete, the mixture was cooled to below 50 °C and neutralized with hydrochloric acid. Subsequently, a conventional aqueous work-up was performed, followed by recrystallization in an IPE / n-hexane mixed solvent to obtain 949 g of chain extender 1 (99.1% purity, 46.2% yield).

[0579] Chain extender 1:

[0580] White powder

[0581] 1 H-NMR (DMSO-d6): δ=0.78(3H,t),1.26(2H,q),3.27(4H,m),4.17(2H,s),4.49(2H,t),9.08(1H,s)

[0582] [Synthetic Example 2-2] Synthesis of Hexafluorool-containing Chain Extender 2

[0583] [Chemistry 81]

[0584]

[0585] [Synthetic Example 2-2-1] Synthesis of Chain Extender 2

[0586] The trimethylolpropane raw material was replaced with glycerol, and the chain extender 2 was obtained in the same manner as in [Synthetic Example 2-1-1] (yield 40%).

[0587] [Synthetic Examples 2-3] Synthesis of Hexafluorool-containing Chain Extender 3

[0588] [Chemistry 82]

[0589]

[0590] [Synthetic Example 2-3-1] Synthesis of Intermediate 3

[0591] Oxaloyl chloride (8.7 g) was added to a suspension of carboxylic acid 1 (10.0 g), toluene (50.0 g), and 2 drops of N,N-dimethylformamide under nitrogen atmosphere. After stirring at room temperature for 5 hours, the solvent was removed by vacuum distillation to obtain acyl chloride 1.

[0592] Under nitrogen atmosphere, an acetonitrile solution of acyl chloride 1 was added to a chilled solution of alcohol 3 (15.6 g), triethylamine (7.9 g), and acetonitrile (20 mL), and stirred at room temperature overnight. After the reaction was complete, water was added and routine post-treatment was performed to obtain 19.0 g of intermediate 3 (crude yield 80%).

[0593] [Synthetic Example 2-3-2] Synthesis of Chain Extender 3

[0594] The intermediate 3 (15.0 g), methanol (30 g), and strongly acidic cation exchange resin (1 g) obtained above were heated under reflux. Deprotection was carried out while distilling off acetone. After the reaction was completed, the ion exchange resin was removed and the solvent was distilled off, thereby obtaining 13.3 g of chain extender 3 (crude yield 97%).

[0595] [Synthetic Examples 2-4] Synthesis of hexafluorool-containing chain extender 4

[0596] [Chemistry 83]

[0597]

[0598] [Synthetic Example 2-4-1] Synthesis of Intermediate 4

[0599] Alcohol 3 was replaced with alcohol 4, and otherwise intermediate 4 was obtained by the same method as in [Synthetic Example 2-3-1].

[0600] [Synthetic Example 2-4-2] Synthesis of Chain Extender 4

[0601] Intermediate 3 was changed to intermediate 4, and otherwise chain extender 4 was obtained in the same manner as in [Synthetic Example 2-3-2] (two-step yield 75%).

[0602] [Synthetic Examples 2-5] Synthesis of chain extender 5 containing pentafluorool

[0603] [Chemistry 84]

[0604]

[0605] [Synthetic Example 2-5-1] Synthesis of Intermediate 5

[0606] Alcohol 3 was replaced with alcohol 5, and otherwise intermediate 5 was obtained in the same manner as in [Synthetic Example 2-3-1].

[0607] [Synthetic Example 2-5-2] Synthesis of Chain Extender 5

[0608] Intermediate 3 was replaced with intermediate 5. Otherwise, chain extender 5 was obtained in the same manner as in [Synthetic Example 2-3-2] (two-step yield 75%).

[0609] [Synthetic Examples 2-6] Synthesis of Chain Extender 6 Containing Trifluoromethanesulfonamide

[0610] [Chemistry 85]

[0611]

[0612] [Synthetic Example 2-6-1] Synthesis of Intermediate 6

[0613] Under nitrogen atmosphere, trifluoromethanesulfonic anhydride (32.1 g) was added dropwise at -78°C to a mixed solution of amine 1 (15.0 g), dichloromethane (45.0 g), and triethylamine (12.5 g), and the mixture was stirred at this temperature for 2 hours. After heating to room temperature and stirring for another hour, water was added while cooling to stop the reaction. Subsequently, standard post-processing was performed to obtain 22.7 g of intermediate 6 (78% crude yield).

[0614] [Synthetic Example 2-6-2] Synthesis of Chain Extender 6

[0615] Intermediate 3 was replaced with intermediate 6. Otherwise, chain extender 6 was obtained in the same manner as in [Synthetic Example 2-3-2] (yield 87%).

[0616] [3] Synthetic raw materials of polyurethane containing weakly acidic functional groups

[0617] High molecular weight polyols

[0618] ·NIPPOLLAN 4010 (manufactured by Tosoh Corporation) is a polyester polyol with a number average molecular weight of 2000.

[0619] ·NIPPOLLAN 4009 (manufactured by Tosoh Corporation) is a polyester polyol with a number average molecular weight of 1000.

[0620] KURARAY POLYOL P-2010 (manufactured by KURARAY) is a polyester polyol with a number average molecular weight of 2000.

[0621] KURARAY POLYOL C-2090 (manufactured by KURARAY) is a polycarbonate polyol with a number average molecular weight of 2000.

[0622] PLACEL 210 (manufactured by DAICEL) Polycaprolactone diol, number average molecular weight 1000

[0623] Diisocyanate

[0624] • 2,4-Toluene diisocyanate or 2,6-Toluene diisocyanate and mixtures of their isomers (TDI)

[0625] Isophorone diisocyanate (IPDI)

[0626] Chain extension agent

[0627] [Chemistry 86]

[0628]

[0629] <End-capping agent>

[0630] [Chemistry 87]

[0631]

[0632] Capping agent 12 uses commercially available products.

[0633] <Catalyst>

[0634] XK-640 (manufactured by King Industries)

[0635] [Synthesis example 3]

[0636] Under nitrogen atmosphere, 445.8 g of a 40% by mass BCA solution of NIPPOLLAN 4009 was added dropwise to 86.0 g of TDI, 134.2 g of diethylene glycol monobutyl ether acetate (BCA), and 0.36 g of XK-640 (manufactured by King Industries), and stirred for 1 hour to obtain a prepolymer. 232.9 g of a 50% by mass BCA solution of chain extender 1 was added dropwise to the prepolymer solution heated to 90°C, and after maturing at this temperature for 10 hours, 91.1 g of a 10% by mass BCA solution of end-capping agent 1 was added, and maturation was continued for 1 hour.

[0637] PU1:

[0638] Mw = 125, 190, Mw / Mn = 3.53

[0639] The types, blending ratios, and amounts of diisocyanate, high molecular weight polyol, chain extender, end-capping agent, and catalyst were changed as shown in Tables 1 and 2. Otherwise, PU2-17 and comparative PU1-3 were synthesized using the same procedure as in [Synthesis Example 3] above.

[0640] [Table 1]

[0641]

[0642] [Table 2]

[0643]

[0644] The synthesis is carried out using phenolic compounds as additives as follows.

[0645] [4] Synthesis of phenolic compounds

[0646] [Synthetic Example 4-1] Synthesis of Phenol 1

[0647] [Chemistry 88]

[0648]

[0649] [Synthetic Example 4-1-1] Synthesis of Protected Phenol 12

[0650] Etherifying agent 1 was changed to etherifying agent 5, and otherwise protected phenol 12 was obtained by the same method as in [Synthesis Example 1-1-3] (yield 85%).

[0651] [Synthetic Example 4-1-2] Synthesis of Phenol 1

[0652] The protected phenol 1 was replaced with the protected phenol 12. Otherwise, phenol 1 was obtained by the same method as in [Synthetic Example 1-1-4] (yield 84%).

[0653] IR(D-ATR): ν=3402,2953,2942,2920,2870,2854,1607,1516,1479,1471,1460,1398,1313,1275,1255,1205,1158,1111,1028,840,788cm -1 .

[0654] 1 H-NMR (600MHz in DMSO-d6): δ=9.18(1H,s),6.82(1H,t),6.72(1H,dd),6.54(1H,dd),3.82(2H,t),1.62(2H,m),1.14-1.38(18H,m),0.83(3H,t)ppm.

[0655] 19 F-NMR (565MHz in DMSO-d6): δ=-133.7(1F,t)ppm.

[0656] [Synthetic Example 4-2] Synthesis of Phenol 2

[0657] [Chemistry 89]

[0658]

[0659] [Synthetic Example 4-2-1] Synthesis of Protected Phenol 13

[0660] Intermediate phenol 1 was replaced with intermediate phenol 5. Otherwise, protected phenol 13 was obtained by the same method as in [Synthetic Example 4-1-1] (yield 88%).

[0661] [Synthetic Example 4-2-2] Synthesis of Phenol 2

[0662] Protected phenol 1 was replaced with protected phenol 13. Otherwise, phenol 2 was obtained by the same method as in [Synthetic Example 1-1-4] (yield 72%).

[0663] IR(D-ATR): ν=3423,2954,2942,2920,2853,1639,1616,1531,1478,1472, 1379,1400,1379,1244,1214,1152,1054,1032,1020,828,822,809,789cm -1 .

[0664] 1 1H-NMR (major isomer only, 600 MHz in DMSO-d6): δ = 10.32 (1H, s), 6.38 (1H, m), 6.27 (1H, m), 3.82 (2H, t), 1.63 (2H, m), 1.16–1.40 (18H, m), 0.82 (3H, t) ppm.

[0665] 19 F-NMR (major isomer only, 565 MHz in DMSO-d6): δ = -137.4 (1F, m), -171.7 (1F, m) ppm.

[0666] [Synthetic Example 4-3] Synthesis of Phenol 3

[0667] [Chemistry 90]

[0668]

[0669] [Synthetic Example 4-3-1] Synthesis of Protected Phenol 14

[0670] Intermediate phenol 1 was replaced with intermediate phenol 6. Otherwise, protected phenol 14 was obtained by the same method as in [Synthetic Example 4-1-1] (yield 90%).

[0671] [Synthetic Example 4-3-2] Synthesis of Phenol 3

[0672] Protected phenol 1 was replaced with protected phenol 14. Otherwise, phenol 3 was obtained by the same method as in [Synthetic Example 1-1-4] (yield 81%).

[0673] IR(D-ATR): ν=3591,3446,2926,2855,1605,1507,1468,1391,1254,1204,1172,1026,983,912,836,792cm -1 .

[0674] 1 H-NMR (600MHz in DMSO-d6): δ=10.06(1H,s),7.08(1H,d),6.49(1H,d),6.34(1H,dd),3.86(2H,t),1.64(2H,m),1.15-1.38(18H,m),0.83(3H,t)ppm.

[0675] 19 F-NMR (565MHz in DMSO-d6): δ=-57.5(3F,t)ppm.

[0676] [Synthetic Example 4-4] Synthesis of Phenol 4

[0677] [Chemistry 91]

[0678]

[0679] [Synthetic Example 4-4-1] Synthesis of Protected Phenol 15

[0680] Intermediate phenol 1 was replaced with intermediate phenol 3. Otherwise, protected phenol 15 was obtained by the same method as in [Synthetic Example 4-1-1] (yield 91%).

[0681] [Synthetic Example 4-4-2] Synthesis of Phenol 4

[0682] Protected phenol 1 was replaced with protected phenol 15. Otherwise, phenol 4 was obtained by the same method as in [Synthetic Example 1-1-4] (yield 76%).

[0683] IR(D-ATR): ν=3290,2956,2918,2873,2849,1615,1526,1502,1470,1420,139 8,1284,1265,1216,1180,1089,1062,1053,1042,1030,1016,975,945,802cm -1 .

[0684] 1 H-NMR (600MHz in DMSO-d6): δ=9.74(1H,s),6.70(2H,dt),3.91(2H,t),1.64(2H,m),1.32-1.39(2H,m),1.16-1.32(16H,m),0.82(3H,t)ppm.

[0685] 19 F-NMR (565MHz in DMSO-d6): δ=-158.1~-157.9(1F,m),-159.3~-159.1(1F,m)ppm.

[0686] [Synthetic Examples 4-5] Synthesis of Phenol 5

[0687] [Chemistry 92]

[0688]

[0689] [Synthetic Example 4-5-1] Synthesis of Phenol 5

[0690] The dihydroxybenzene 1 was replaced with hydroquinone, and the etherifying agent 2 was replaced with etherifying agent 6. Otherwise, phenol 5 was obtained by the same method as in [Synthetic Example 1-7-1] (yield 59%).

[0691] [Synthetic Examples 4-6] Synthesis of Phenol 6

[0692] [Chemistry 93]

[0693]

[0694] [Synthetic Example 4-6-1] Synthesis of Protected Phenol 16

[0695] Etherifying agent 1 was changed to etherifying agent 6, and otherwise protected phenol 16 was obtained by the same method as in [Synthesis Example 1-1-3] (yield 94%).

[0696] [Synthetic Example 4-6-2] Synthesis of Phenol 6

[0697] The protected phenol 1 was replaced with the protected phenol 16. Otherwise, phenol 6 was obtained by the same method as in [Synthetic Example 1-1-4] (yield 90%).

[0698] IR(D-ATR): ν=3380,2944,2869,1642,1606,1516,1477,1446,1394,1368,1317,1263,1242,1195,1162,1109,1023,969,956,867,838,796cm -1 .

[0699] 1 H-NMR (600MHz in DMSO-d6): δ=9.19(2H,s),6.82(2H,t),6.75(2H,dd),6.55(2H,dd),3.85(4H,t),1.66(4H,quin),1.42(4H,m)ppm.

[0700] 19 F-NMR (565MHz in DMSO-d6): δ=-133.6(2F,t)ppm.

[0701] [Synthetic Examples 4-7] Synthesis of Phenol 7

[0702] [Chemistry 94]

[0703]

[0704] [Synthetic Example 4-7-1] Synthesis of Protected Phenol 17

[0705] Etherifying agent 1 was changed to etherifying agent 7, and otherwise protected phenol 17 was obtained by the same method as in [Synthesis Example 1-1-3] (yield 92%).

[0706] [Synthetic Example 4-7-2] Synthesis of Phenol 7

[0707] Protected phenol 1 was replaced with protected phenol 17. Otherwise, phenol 7 was obtained by the same method as in [Synthetic Example 1-1-4] (yield 87%).

[0708] IR(D-ATR): ν=3385,2941,2923,2856,1608,1514,1479,1468,1455,1288,1 276,1253,1203,1156,1110,1042,1022,988,956,842,818,802,787,748cm -1 .

[0709] 1H-NMR (600MHz in DMSO-d6): δ=9.18(2H,s),6.82(2H,t),6.74(2H,dd),6.55(2H,dd),3.83(4H,t),1.66(4H,quin),1.20-1.41(12H,m)ppm.

[0710] 19 F-NMR (565MHz in DMSO-d6): δ=-133.7(2F,t)ppm.

[0711] [Synthetic Examples 4-8] Synthesis of Phenol 8

[0712] [Chemistry 95]

[0713]

[0714] [Synthetic Example 4-8-1] Synthesis of Protected Phenol 18

[0715] Intermediate phenol 1 was changed to intermediate phenol 4, and etherifying agent 1 was changed to etherifying agent 7. Otherwise, protected phenol 18 was obtained by the same method as in [Synthesis Example 1-1-3] (yield 88%).

[0716] [Synthetic Example 4-8-2] Synthesis of Phenol 8

[0717] The protected phenol 1 was replaced with the protected phenol 18. Otherwise, phenol 8 was obtained by the same method as in [Synthetic Example 1-1-4] (yield 84%).

[0718] IR (D-ATR): ν=3401,2942,2923,2856,1648,1616,1528,1479,1469,1459,1378,1247,1202,1148,1045,1023,1017,823,802cm -1 .

[0719] 1 H-NMR (600MHz in DMSO-d6): δ=9.38(2H,s),6.64(4H,m),3.85(4H,t),3.36(2H,t),1.64(4H,m),1.32-1.42(4H,m),1.18-1.40(12H,m)ppm.

[0720] 19 F-NMR (565MHz in DMSO-d6): δ=-131.0(4F,d)ppm.

[0721] [Synthetic Examples 4-9] Synthesis of Phenol 9

[0722] [Chemistry 96]

[0723]

[0724] In the formula, Ms represents methanesulfonyl group.

[0725] [Synthetic Example 4-9-1] Synthesis of Protected Phenol 19

[0726] Etherifying agent 1 was changed to etherifying agent 8, and otherwise protected phenol 19 was obtained by the same method as in [Synthesis Example 1-1-3] (yield 85%).

[0727] [Synthetic Example 4-9-2] Synthesis of Phenol 9

[0728] Protected phenol 1 was replaced with protected phenol 19. Otherwise, phenol 9 was obtained by the same method as in [Synthetic Example 1-1-4] (yield 81%).

[0729] 1 H-NMR (600MHz in DMSO-d6): δ=9.22(2H,s),6.83(2H,dd),6.78(2H,dd),6.57(2H,ddd),3.95~3.98(4H,m),3.65~3.70(4H,m),3.50~3.56(8H,m)ppm.

[0730] 19 F-NMR (565MHz in DMSO-d6): δ=-136.8(2F,t)ppm.

[0731] [Synthetic Examples 4-10] Synthesis of Phenol 10

[0732] [Chemistry 97]

[0733]

[0734] [Synthetic Example 4-10-1] Synthesis of Etherifying Agent 9

[0735] Under a nitrogen atmosphere, geraniol reagent, prepared prior with silane 1 (30.7 g), magnesium (6.7 g), and tetrahydrofuran 120 mL, was added dropwise to a solution of dibromosol 1 (75.0 g), copper iodide (I) (0.52 g), triethyl phosphite (0.96 g), and tetrahydrofuran (100 mL) at an internal temperature of 10–30 °C. The reaction was maintained at this temperature and stirred continuously for 20 hours. Subsequently, a saturated ammonium chloride aqueous solution (200 g) was added at an internal temperature below 30 °C, and the reaction was stopped. Following standard post-treatment methods, etherifying agent 9 (43.3 g, yield 62%) was obtained.

[0736] Boiling point: 72℃ / 20Pa.

[0737] [Synthetic Example 4-10-2] Synthesis of Protected Phenol 20

[0738] Etherifying agent 1 was changed to etherifying agent 9, and otherwise protected phenol 20 was obtained by the same method as in [Synthesis Example 1-1-3] (yield 85%).

[0739] [Synthetic Example 4-10-3] Synthesis of Phenol 10

[0740] Protected phenol 1 was replaced with protected phenol 20. Otherwise, phenol 10 was obtained by the same method as in [Synthetic Example 1-1-4] (yield 93%).

[0741] 1 H-NMR(500MHz in DMSO-d6): δ=9.18(1H,s),6.81(1H,t),6.72(1H,dd),6.53(1H,dd),3.82(2H,t),1.63(2H,m),1.19-1.40(12H,m),0.44(2H,m),-0.06(9H,s)ppm.

[0742] 19 F-NMR (470MHz in DMSO-d6): δ=-133.7(1F,t)ppm.

[0743] [Examples 1-26, Comparative Examples 1-5]

[0744] <Preparation of Conductive Paste Composition>

[0745] The polyurethanes used to prepare conductive paste compositions are PU1-17, comparative PU1-3, and the following resins as listed in Tables 1 and 2.

[0746] Fluororubber (Daikin Manufacturing, G801)

[0747] • Polyester (manufactured by UNITIKA, UE-9200)

[0748] For conductive fillers, prepare the following silver powders A to E and copper powder A.

[0749] • Silver powder A: Average particle size (D) L50 The value is 2.1 μm.

[0750] • Silver powder B: Average particle size (D) L50 The value is 5.3 μm.

[0751] • Silver powder C: Average particle size (D) L50 ) is 1.2μm

[0752] • Silver powder D: Average particle size (DL50 The value is 0.67μm.

[0753] Silver powder E: Average particle size (D) L50 The value is 1.72μm.

[0754] Copper powder A: Average particle size (D) L50 ) is 1.30μm

[0755] The average particle size is determined by using a laser diffraction particle size distribution device to measure the particle size distribution and calculating the particle size of the cumulative 50% as the average particle size.

[0756] The phenolic compounds used in the additives are phenols 1 to 13 as described below. Here, phenol 11 is the same as capping agent 1, phenol 12 is the same as capping agent 4, and phenol 13 is the same as capping agent 11.

[0757] [Chem. 98]

[0758]

[0759] The polymer, conductive filler, phenolic compound and solvent (BCA) were mixed according to the composition described in Table 3 to prepare a conductive paste composition.

[0760] [Table 3]

[0761]

[0762] BCA: Diethylene glycol monobutyl ether acetate [Evaluation of the elasticity of conductive wiring]

[0763] <Evaluation Sample Creation>

[0764] Using a Micro-tec MT-320TVC screen printing machine, a conductive paste composition is coated onto a polyurethane film, followed by heat treatment in a hot air dryer to form a stretchable conductive wire with a line width of 10 mm, a length of 70 mm, and a film thickness of 10 μm.

[0765] <Determination of initial resistance in the non-elongated state>

[0766] The resistance between the two ends of a stretchable conductive wire formed on a polyurethane film was measured using a four-terminal resistance measurement method. The resistance was measured using a National Instruments PXIe-4136SMU resistance measuring apparatus.

[0767] Resistance (Ω) R = V / I (V: voltage, I: current)

[0768] The results of the initial resistance (resistance in the non-elongated state) measurement are shown in Table 4.

[0769] <Determination of maximum resistance at 20% elongation>

[0770] The polyurethane film with stretchable conductive wiring was fixed in a state where it was stretched by 20% from a non-stretched state (0%) without deflection, and the resistance was measured by a 4-terminal resistance measurement method.

[0771] The polyurethane film with stretchable conductive wiring is formed by stretching it at a speed of 300 mm / min along the longitudinal direction of the stretchable conductive wiring (rectangle) using a precision universal testing machine manufactured by Shimadzu Corporation AG-Xplus HS.

[0772] • Change in resistance at 20% elongation = [Resistance at 20% elongation (Ω)] ÷ [Initial resistance (Ω)] × 100

[0773] The resistance change at 20% elongation is shown in Table 4.

[0774] <Determination of maximum resistance at 300% elongation>

[0775] A polyurethane film with stretchable conductive wiring was fixed in a state where it was stretched by 300% from a non-stretched state (0%), and its resistance was measured.

[0776] The polyurethane film with stretchable conductive wiring is formed by stretching it at a speed of 300 mm / min along the longitudinal direction of the stretchable conductive wiring (rectangle) using a precision universal testing machine manufactured by Shimadzu Corporation AG-Xplus HS.

[0777] • Change in resistance at 300% elongation = [Resistance at 300% elongation (Ω)] ÷ [Initial resistance (Ω)] × 100

[0778] The resistance change at 300% elongation is shown in Table 4.

[0779] <Determination of maximum resistance value during repeated expansion and contraction from 0% to 20%>

[0780] For a polyurethane film with stretchable conductive wiring, a 20% stretching was repeated 1000 times from a non-stretched state (0%) without flexure, and the change in resistance of the conductive wiring over time was measured.

[0781] The repeated stretching test was conducted by stretching a polyurethane film at a stretching speed of 300 mm / min along the longitudinal direction of the stretchable conductive wiring (rectangle) using a precision universal testing machine manufactured by Shimadzu Corporation, AG-XplusHS.

[0782] Furthermore, the resistance was measured by placing the electrodes inside the sample clamp of the tensile testing machine (the aforementioned precision universal testing machine AG-Xplus HS), using a National Instruments PXIe-4136SMU resistance measuring device, and employing the four-terminal resistance measurement method.

[0783] • The maximum resistance change during 1000 repeated stretching and contraction cycles with an elongation of 0–20% = [maximum resistance (Ω) in repeated stretching and contraction tests] ÷ [initial resistance (Ω)] × 100

[0784] The maximum resistance change during 1000 cycles of expansion and contraction with an elongation of 0–20% is shown in Table 4.

[0785] [Table 4]

[0786]

[0787] -: Not measured

[0788] As shown in Table 4, when using a conductive paste composition incorporating polyurethane containing phenolic hydroxyl groups, even with a short-term calcination at 120°C for 30 minutes, the increase in resistance due to wire elongation is still small, resulting in conductive wiring with excellent conductivity stability during repeated stretching and contraction (Examples 1-26). Furthermore, by adding phenolic compounds as additives, the degradation caused by wire elongation can be suppressed (Examples 7-26). On the other hand, the polyurethanes (Comparative Examples 1-3) and resins (Comparative Examples 4-5) without phenolic hydroxyl groups in the comparative examples showed a significant increase in resistance due to wire elongation and repeated stretching and contraction.

[0789] Furthermore, the present invention is not limited to the embodiments described above. The embodiments described above are illustrative, and those having substantially the same structure and performing the same effects as the technical concept described in the claims of the present invention are all included within the technical scope of the present invention.

Claims

1. A polyurethane, characterized in that it contains phenolic hydroxyl groups as represented by the following general formula (1B); In the formula, Az' represents a straight-chain, branched, or cyclic (ka+2) valence hydrocarbon group or a fluorinated hydrocarbon group with 1 to 19 carbon atoms, and the -CH2- constituting the (ka+2) valence hydrocarbon group can also be replaced by -O- or -NR. 4 -、-C(=O-、or-Si(R) 2 R 3 )-;R 2 R 3 It is a straight-chain, branched, or cyclic alkyl or phenyl group having 1 to 6 carbon atoms, R 4 It consists of hydrogen atoms, or straight-chain or branched alkyl groups with 1 to 4 carbon atoms; ka represents an integer from 0 to 2; kb, kc, kd, and ke represent 1 or 2; the dashed line represents an atomic bond.

2. The polyurethane according to claim 1, wherein, The polyurethane further contains one or more weakly acidic functional groups represented by the following general formulas (1a) to (1c); In the formula, R represents a hydrogen atom, a fluorine atom, or a straight-chain, branched, or cyclic hydrocarbon group with 1 to 10 carbon atoms that can also be fluorinated; Rf represents a fluorine atom or a straight-chain, branched, or cyclic fluorinated hydrocarbon group with 1 to 10 carbon atoms; n is an integer of 1 or 2; and the dashed line represents an atomic bond.

3. The polyurethane according to claim 1 or 2, wherein, The polyurethane further contains one or more structures represented by the following general formulas (2a) to (2c); In the formula, R 1 A is a hydrogen atom or a monovalent hydrocarbon group having 1 to 3 carbon atoms. a It represents a single bond, or a straight-chain, branched, or cyclic divalent hydrocarbon group with 1 to 20 carbon atoms, and the -CH2- group can also be substituted with -O-, -C(=O)-, -C(=O)O-, or -C6H4-, and can also be -NR. 4 -C(=O)-;A b and A c Each can be independently represented by -O-, -OC (=O)-NR 4 -、-NR 4 Any one of the following groups: - or -C(=O)O-; n 1 n 2 n 4 n is an integer between 0 and 10. 3 R is an integer that is either 0 or 1; 4 As mentioned above, dashed lines represent atomic bonds.

4. A method for manufacturing polyurethane, comprising the method for manufacturing polyurethane according to claim 1, characterized in that: After the chain extension reaction, the phenolic hydroxyl group is introduced into the polyurethane using an alcohol or amine represented by the following general formula (1C); In the formula, "Az" represents a straight-chain, branched, or cyclic (ka+2) valence hydrocarbon group or a fluorinated hydrocarbon group with 1 to 19 carbon atoms, and the -CH2- constituting the (ka+2) valence hydrocarbon group can also be substituted with -O-, -C(=O)-, or -Si(R 2 R 3 )-; X represents an oxygen atom or NR 4 ; ka represents an integer from 0 to 2; kb, kc, kd, ke represent 1 or 2; R 2 R 3 R 4 Same as above.

5. The method for manufacturing polyurethane according to claim 4, wherein one or more alcohols represented by the following general formulas (3a) to (3c) are used as chain extenders to introduce weakly acidic functional groups into the polyurethane. In the formula, R 1 A is a hydrogen atom or a monovalent hydrocarbon group having 1 to 3 carbon atoms. a It represents a single bond, or a straight-chain, branched, or cyclic divalent hydrocarbon group with 1 to 20 carbon atoms, and the -CH2- group can also be substituted with -O-, -C(=O)-, -C(=O)O-, or -C6H4-, and can also be -NR. 4 -C(=O)-;R 4 It consists of hydrogen atoms, or straight-chain or branched alkyl groups having 1 to 4 carbon atoms; n 1 n 2 n 4 Integers from 0 to 10.

6. A conductive paste composition, characterized by containing: (A) Conductive filler, (B) The polyurethane according to any one of claims 1 to 3, and (C) Solvent.

7. The conductive paste composition according to claim 6, wherein, This conductive paste composition also contains (D) phenolic compounds.

8. The conductive paste composition according to claim 7, wherein, The phenolic compound of component (D) contains the structure represented by the following general formula (2A); In the formula, R 6 Represents a hydrogen atom, halogen atom, cyano group, or hydroxyl group; Ay represents a straight-chain, branched, or cyclic (ka+2) valence hydrocarbon group or a fluorinated hydrocarbon group having 1 to 20 carbon atoms, and the -CH2- constituting the (ka+2) valence hydrocarbon group can also be substituted with -O-, -C(=O)-, or -Si(R)-. 2 R 3 )-;R 2 R 3 It is a straight-chain, branched, or cyclic alkyl or phenyl group with 1 to 6 carbon atoms; Z represents a single bond or an oxygen atom; Xf independently represents a hydrogen atom, a halogen atom, a straight-chain, branched, or cyclic monovalent hydrocarbon group with 1 to 10 carbon atoms that can be substituted with fluorine atoms, an alkoxy group with 1 to 10 carbon atoms that can be substituted with fluorine atoms, or an electron-withdrawing group; ring ZZ independently represents an aromatic monocyclic or polycyclic ring with 5 to 20 carbon atoms; the carbon atoms of the ring ZZ can also be substituted with nitrogen atoms, oxygen atoms, or sulfur atoms; ka represents an integer from 0 to 2; kb and kd represent 1 or 2; kc and ke represent integers from 0 to 2.

9. The conductive paste composition according to claim 8, wherein, The phenolic compound of component (D) contains the structure represented by the following general formula (2B); In the formula, Ay' represents a straight-chain, branched, or cyclic (ka+2) valence hydrocarbon group or a fluorinated hydrocarbon group with 1 to 19 carbon atoms, and the -CH2- constituting the (ka+2) valence hydrocarbon group can also be substituted with -O-, -C(=O)-, or -Si(R 2 R 3 )-; ka represents an integer from 0 to 2; kb, kc, kd, ke represent 1 or 2; R 2 R 3 R 6 Same as above.

10. The conductive paste composition according to any one of claims 6 to 9, wherein the conductive filler of component (A) is contained in a proportion of more than 70 parts by mass relative to a total of 100 parts by mass of component (A) and component (B).

11. The conductive paste composition according to any one of claims 6 to 9, wherein, The conductive filler of component (A) is a powder selected from gold, silver, silver chloride, platinum, copper, tin, iron, magnesium, titanium, nickel, palladium, aluminum, tungsten, molybdenum, ruthenium, chromium, indium, solder, and carbon, or a combination thereof.

12. The conductive paste composition according to claim 11, wherein, The conductive filler in component (A) is silver powder.

13. The conductive paste composition according to any one of claims 6 to 9, wherein, The average particle size of the conductive filler of component (A) is 5 nm to 10 μm.

14. A conductive wiring, characterized in that: It is formed on a substrate and consists of a calcined product of the conductive paste composition according to any one of claims 6 to 13.

15. The conductive wiring according to claim 14, wherein, The substrate is elastic.

16. The conductive wiring according to claim 15, wherein, The substrate is thermoplastic polyurethane.

17. The conductive wiring according to claim 15 or 16, wherein the resistance at 20% elongation is less than 500% of the resistance before elongation.

18. The conductive wiring according to claim 15 or 16, wherein the maximum resistance when repeatedly stretched and contracted 1000 times with an elongation of 20% is less than 5000% of the resistance before stretching and contraction.

19. A method for manufacturing a conductive wire, comprising forming the conductive wire on a substrate using a conductive paste composition according to any one of claims 6 to 13, characterized in that: The calcination temperature for forming the conductive wiring is set to 60–160°C.

20. A method for manufacturing a conductive wiring, characterized by: Conductive wiring is formed on a substrate by printing the conductive paste composition according to any one of claims 6 to 13.

Images