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

Abstract

The present invention is a polyurethane characterized by containing a phenolic hydroxyl group represented by the following general formula (1A). By doing so, a conductive paste composition for forming a flexible conductive wiring with minimal change in conductivity during stretching and a polyurethane that imparts the composition are provided.

Description

Technology Field

[0001] The present invention relates to polyurethane, a method for manufacturing polyurethane, a conductive paste composition, conductive wiring, and a method for manufacturing conductive wiring. Background Technology

[0002] With the recent proliferation of the Internet of Things (IoT), the development of wearable devices that can be attached to the human body is underway. In particular, their use is expected in the fields of medical care, health management, and care, as well as sports. It is being considered to monitor biometric and exercise data in real time, or to detect diseases early or manage physical condition through body movement sensing.

[0003] Wearable devices that continuously measure biometric information come in various forms, including accessory types such as watches, glasses, and earphones, clothing types, and patch types that are attached directly to the body. To reliably measure accurate biometric information, it is necessary to use them fitted to the body surface. In particular, clothing and patch-type devices require high flexibility to follow body movements, elasticity, and durability against repeated stretching. Therefore, the development of technologies and materials to impart elasticity to wiring and sensors is becoming important.

[0004] For example, the wearable device described in Patent Document 1 uses a flexible silver wire in the form of a corrugated box covered with a flexible urethane film, and even if the metal wire itself is not flexible, conductivity is secured by making it similarly flexible through the design of the wire.

[0005] In addition, a method of making elastic by weaving conductive threads to form a knit (Patent Document 2) and a method of using an elastic conductive composite yarn in which conductive fibers are wrapped around elastic fibers (Patent Document 3) have also been reported.

[0006] However, in the method of weaving conductive threads, problems can be cited such as the low degree of freedom of pattern shape and low throughput compared to pattern formation by printing. In addition, since the method of Patent Document 1 also has limitations on the pattern shape and makes it difficult to design a compact wiring, the development of flexible conductive pastes or inks to form wiring that can maintain conductivity even when stretched by printing is actively underway.

[0007] For example, there are many proposals and applications, such as a flexible wiring using galinstan containing gallium-indium-tin or a liquid metal containing gallium-indium, a flexible wiring mixed with silver nanowires as a metal additive (Patent Document 4), a flexible wiring that generates silver nanoparticles during annealing by combining fluororubber, a surfactant, and a silver filler (Patent Document 5), a flexible wiring using silver flakes with appropriate tap density and average particle size (Patent Document 6), and a flexible wiring using silver powder with appropriate particle size, particle size distribution, and porosity (Patent Document 7). Prior art literature

[0008] [Patent Document 1] Japanese Patent No. 3923861 [Patent Document 2] Japanese Patent No. 6657525 [Patent Document 3] Japanese Patent Publication No. 2019-076214 [Patent Document 4] International Publication No. 2017 / 217509 [Patent Document 5] International Publication No. 2018 / 110632 [Patent Document 6] Japanese Patent Publication No. 2019-110093 [Patent Document 7] International Publication No. 2018 / 235734 The problem to be solved

[0009] The present invention is made to solve the above problem and aims to provide a conductive paste composition for forming a flexible conductive wiring with minimal change in conductivity upon stretching, and a polyurethane that imparts the said composition. means of solving the problem

[0010] In order to solve the above problem, the present invention provides a polyurethane containing a phenolic hydroxyl group represented by the following general formula (1A).

[0011]

[0012] (In the formula, Az represents a straight-chain, branched, or cyclic (ka+2) valent hydrocarbon group or a fluorinated hydrocarbon group having 1 to 20 carbon atoms, and the -CH2- constituting the (ka+2) valent hydrocarbon group is -O-, -NR 4 -, -C(=O)- or -Si(R 2 R 3 It may be replaced with )-. R 2 , R 3 is a straight-chain, branched, or cyclic alkyl group having 1 to 6 carbon atoms, or a phenyl group, and R 4 is 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 represents, respectively, a straight-chain, branched, or cyclic monovalent hydrocarbon group that may be independently substituted with a hydrogen atom, a halogen atom, a fluorine atom having 1 to 10 carbon atoms, an alkoxy group that may be substituted with a fluorine atom having 1 to 10 carbon atoms, or an electron-occulting group. Ring ZZ represents, respectively, an aromatic monocyclic or polycyclic group having 5 to 20 carbon atoms. The carbon atoms of the above ring ZZ may 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, and dashed lines represent bond losses.)

[0013] If it is such a polyurethane, a conductive paste composition is provided to form a flexible conductive wiring with minimal change in conductivity during stretching.

[0014] In addition, in the present invention, it is preferable that the polyurethane contains a phenolic hydroxyl group represented by the following general formula (1B).

[0015]

[0016] (In the formula, Az' represents a straight-chain, branched, or cyclic (ka+2) hydrocarbon group having 1 to 19 carbon atoms, or a fluorinated hydrocarbon group, and the -CH2- constituting the (ka+2) hydrocarbon group is -O-, -NR 4 -, -C(=O)- or -Si(R 2 R 3 It may be substituted with ). ka represents an integer from 0 to 2. kb, kc, kd, and ke represent 1 or 2. R 2 , R 3 , R 4 ...is the same as above, and the dashed line indicates the joining loss.)

[0017] If such a polyurethane is used as a conductive paste composition for forming flexible conductive wiring, the change in conductivity during stretching can be made smaller.

[0018] In addition, in the present invention, it is preferable that the polyurethane further comprises one or more weakly acidic functional groups represented by the following general formulas (1a) to (1c).

[0019]

[0020] (In the formula, R represents a hydrogen atom, a fluorine atom, or a straight-chain, branched, or cyclic hydrocarbon group having 1 to 10 carbon atoms that may be fluorinated, and Rf represents a fluorine atom or a straight-chain, branched, or cyclic fluorinated hydrocarbon group having 1 to 10 carbon atoms. n is an integer of 1 or 2, and dashed lines represent bond losses.)

[0021] If such a polyurethane is used as a conductive paste composition for forming flexible conductive wiring, the change in conductivity during stretching can be made even smaller.

[0022] In addition, in the present invention, it is preferable that the polyurethane further comprises one or more structures represented by the following general formulas (2a) to (2c).

[0023]

[0024] (during food, R 1 is a hydrogen atom or a monovalent hydrocarbon group having 1 to 3 carbon atoms, and A a represents a single bond, or a straight-chain, branched, or cyclic divalent hydrocarbon group having 1 to 20 carbon atoms, and the constituent -CH2- may be substituted with -O-, -C(=O)-, -C(=O)O-, or -C6H4-, and -NR 4 Even if it's -C(=O)- it's fine. A b and A c -O-, -OC(=O)-NR respectively, independently 4 -, -NR 4 Represents one of the groups selected from -, -C(=O)O-. n 1 , n 2 , n 4 is an integer from 0 to 10, and n 3 is an integer of 0 or 1. R 4 ...is the same as above, and the dashed line indicates the joining loss.)

[0025] If such a polyurethane is included in a conductive paste composition for forming a flexible conductive wiring, the change in conductivity during stretching can be made even smaller.

[0026] In addition, the present invention provides a method for manufacturing the polyurethane, characterized by introducing the phenolic hydroxyl group into the polyurethane using an alcohol or amine represented by the following general formula (1C) after a chain extension reaction.

[0027]

[0028] (In the formula, Az" represents a straight-chain, branched, or cyclic (ka+2) hydrocarbon group having 1 to 19 carbon atoms, or a fluorinated hydrocarbon group, and the -CH2- constituting the (ka+2) hydrocarbon group is -O-, -C(=O)-, or -Si(R 2 R 3 It may be substituted with ). X is an oxygen atom or NR 4 Represents. ka represents an integer from 0 to 2. kb, kc, kd, and ke represent 1 or 2. R 2 , R 3 , R 4 is the same as above.)

[0029] With such a method for manufacturing polyurethane, the polyurethane can be easily synthesized.

[0030] At this time, it is preferable to introduce a weakly acidic functional group into the polyurethane by using one or more alcohols represented by the following general formulas (3a) to (3c) as chain extenders.

[0031]

[0032] (during food, R 1 is a hydrogen atom or a monovalent hydrocarbon group having 1 to 3 carbon atoms, and A a represents a single bond, or a straight-chain, branched, or cyclic divalent hydrocarbon group having 1 to 20 carbon atoms, and the constituent -CH2- may be substituted with -O-, -C(=O)-, -C(=O)O-, or -C6H4-, and -NR 4 Even if it's -C(=O)-, it's fine. R 4 is a hydrogen atom, or a straight-chain or branched alkyl group having 1 to 4 carbon atoms. 1 , n 2 , n 4 is an integer between 0 and 10.)

[0033] With this method of manufacturing polyurethane, weakly acidic functional groups can be easily introduced into the polyurethane.

[0034] In addition, the present invention provides a conductive paste composition characterized by comprising (A) a conductive filler, (B) the polyurethane, and (C) a solvent.

[0035] With such a conductive paste composition, it is possible to form a flexible conductive wiring with minimal change in conductivity during stretching.

[0036] In addition, in the present invention, it is preferable that the conductive paste composition further comprises (D) a phenol compound.

[0037] With such a conductive paste composition, it is possible to form a flexible conductive wiring with less change in conductivity during stretching.

[0038] Furthermore, in the present invention, it is preferable that the phenol compound of the above (D) component comprises a structure represented by the following general formula (2A).

[0039]

[0040] (during food, R 6 represents a hydrogen atom, a halogen atom, a cyano group, or a hydroxyl group. Ay represents a straight-chain, branched, or cyclic (ka+2) hydrocarbon group having 1 to 20 carbon atoms, or a fluorinated hydrocarbon group, wherein the -CH2- constituting the (ka+2) hydrocarbon group is -O-, -C(=O)-, or -Si(R 2 R 3 It may be substituted with ). 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 is the same as above.)

[0041] With such a conductive paste composition, it is possible to form a flexible conductive wiring with less change in conductivity during stretching.

[0042] In addition, in the present invention, it is preferable that the phenol compound of the above (D) component includes a structure represented by the following general formula (2B).

[0043]

[0044] (In the formula, Ay' represents a straight-chain, branched, or cyclic (ka+2) hydrocarbon group having 1 to 19 carbon atoms, or a fluorinated hydrocarbon group, and the -CH2- constituting the (ka+2) hydrocarbon group is -O-, -C(=O)-, or -Si(R 2 R 3 It may be substituted with ). ka represents an integer from 0 to 2. kb, kc, kd, and ke represent 1 or 2. R 2 , R 3 , R 6 is the same as above.)

[0045] With such a conductive paste composition, it is possible to form a flexible conductive wiring with less change in conductivity during stretching.

[0046] In this case, it is preferable that the conductive filler of component (A) is contained in a ratio of more than 70 parts by mass to 100 parts by mass of the total of components (A) and (B).

[0047] With such a conductive paste composition, it is possible to form a flexible conductive wiring that has sufficient conductivity and also has less change in conductivity when stretched.

[0048] In addition, in the present invention, it is preferable that 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 composite thereof.

[0049] With such a conductive paste composition, it is possible to form flexible conductive wiring with enhanced electrical conductivity.

[0050] At this time, it is particularly preferable that the conductive filler of the above (A) component is silver powder.

[0051] These conductive fillers are comprehensively suitable in terms of conductivity and price.

[0052] In addition, in the present invention, it is preferable that the average particle size of the conductive filler of component (A) is 5 nm to 10 μm.

[0053] It is suitable to incorporate such conductive fillers into a conductive paste composition.

[0054] In addition, the present invention provides a conductive wiring comprising a fired product of the conductive paste composition described above, formed on a substrate.

[0055] With such conductive wiring, the change in conductivity during expansion is minimal.

[0056] In this case, it is desirable that the above description has elasticity.

[0057] Such a material is suitable for the conductive wiring of the present invention.

[0058] At this time, it is preferable that the above material is a thermoplastic polyurethane.

[0059] Such a material is more suitable for the conductive wiring of the present invention.

[0060] In addition, in the conductive wiring of the present invention, it is preferable that the electrical resistance at 20% elongation is 500% or less of the electrical resistance before elongation.

[0061] With such conductive wiring, the change in conductivity during expansion is minimal, allowing it to be fitted to the body surface for use.

[0062] In addition, in the conductive wiring of the present invention, it is preferable that the maximum electrical resistance when stretched 1,000 times at an elongation rate of 20% is 5,000% or less of the electrical resistance before stretching.

[0063] If such conductive wiring is used, it is suitable for conductive stability during repeated stretching.

[0064] In addition, the present invention provides a method for manufacturing conductive wiring by forming conductive wiring on a substrate using the conductive paste composition described above, characterized in that the firing temperature when forming the conductive wiring is 60 to 160°C.

[0065] With this method of manufacturing conductive wiring, it is possible to form conductive wiring on a substrate with low heat resistance, and also reliably obtain conductive wiring with minimal change in conductivity during expansion.

[0066] In addition, in the present invention, conductive wiring may be formed on a substrate by printing the above-described conductive paste composition.

[0067] By forming wiring patterns through printing, the designability and productivity of the wiring can be improved. Effects of the invention

[0068] As described above, if the conductive paste composition containing polyurethane of the present invention is used, it is possible to form a conductive wiring that has minimal change in conductivity upon stretching, can efficiently transmit electrical signals to a device (i.e., has excellent conductivity), is lightweight, and can be manufactured at a low cost.

[0069] In addition, since the conductive stability during repeated stretching is excellent, it is possible to form conductive wiring suitable for wearable devices that are deformed by the movement of the human body. Specific details for implementing the invention

[0070] In conventional technology, conductive wiring using a conductive paste in which metal fillers are mixed with resin contains insulating components, resulting in higher electrical resistance compared to metal wiring. Furthermore, it is impossible to avoid resistance increases accompanying elongation or degradation caused by repeated stretching, and in some cases, the wiring may even break. Additionally, there is concern that changes in conductivity accompanying stretching may affect the operation of the device. Therefore, there has been a demand for the development of conductive material compositions that exhibit higher conductivity and minimal changes in conductivity during stretching.

[0071] The inventors, as a result of repeated careful consideration to solve the above problem, found that by using a conductive paste composition containing (A) a conductive filler, (B) a polyurethane containing a phenolic hydroxyl group represented by the following general formula (1A), and (C) a solvent, a conductive wiring with low resistance, a small decrease in conductivity during stretching, and excellent conductivity stability during repeated stretching can be obtained.

[0072] In particular, polyurethanes containing phenolic hydroxyl groups represented by the following general formula (1A) are not conventionally known.

[0073] That is, the present invention is a polyurethane characterized by containing a phenolic hydroxyl group represented by the following general formula (1A).

[0074]

[0075] (In the formula, Az represents a straight-chain, branched, or cyclic (ka+2) hydrocarbon group having 1 to 20 carbon atoms, or a fluorinated hydrocarbon group, and the -CH2- constituting the (ka+2) hydrocarbon group is -O-, -NR 4 -, -C(=O)- or -Si(R 2 R 3 It may be replaced with )-. R 2 , R 3is a straight-chain, branched, or cyclic alkyl group having 1 to 6 carbon atoms, or a phenyl group, and R 4 is 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 represents, respectively, a straight-chain, branched, or cyclic monovalent hydrocarbon group that may be independently substituted with a hydrogen atom, a halogen atom, a fluorine atom having 1 to 10 carbon atoms, an alkoxy group that may be substituted with a fluorine atom having 1 to 10 carbon atoms, or an electron-occulting group. Ring ZZ represents, respectively, an aromatic monocyclic or polycyclic group having 5 to 20 carbon atoms. The carbon atoms of the above ring ZZ may 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, and dashed lines represent bond losses.)

[0076] The present invention will be described in detail below, but the present invention is not limited thereto. In addition, in the following description, depending on the structure represented by the chemical formula, a non-carbon may be present, and enantiomers or diastereomers may be present, but in such cases, these isomers are represented by a single formula. These isomers may be used individually or as a mixture.

[0077] [Polyurethane]

[0078] The polyurethane of the present invention contains a phenolic hydroxyl group represented by the following general formula (1A).

[0079]

[0080] (In the formula, Az represents a straight-chain, branched, or cyclic (ka+2) hydrocarbon group having 1 to 20 carbon atoms, or a fluorinated hydrocarbon group, and the -CH2- constituting the (ka+2) hydrocarbon group is -O-, -NR 4-, -C(=O)- or -Si(R 2 R 3 It may be replaced with )-. R 2 , R 3 is a straight-chain, branched, or cyclic alkyl group having 1 to 6 carbon atoms, or a phenyl group, and R 4 is 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 represents, respectively, a straight-chain, branched, or cyclic monovalent hydrocarbon group that may be independently substituted with a hydrogen atom, a halogen atom, a fluorine atom having 1 to 10 carbon atoms, an alkoxy group that may be substituted with a fluorine atom having 1 to 10 carbon atoms, or an electron-occulting group. Ring ZZ represents, respectively, an aromatic monocyclic or polycyclic group having 5 to 20 carbon atoms. The carbon atoms of the above ring ZZ may 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, and dashed lines represent bond losses.)

[0081] Specifically, the following can be exemplified as straight-chain, branched, or cyclic (ka+2) hydrocarbon groups having 1 to 20 carbon atoms of the above Az.

[0082]

[0083] (In the formula, dashed lines indicate joint loss.)

[0084]

[0085] (In the formula, dashed lines indicate joint loss.)

[0086]

[0087] (In the formula, dashed lines indicate joint loss.)

[0088] Specifically, examples of straight, branched, or cyclic (ka+2) fluorinated hydrocarbon groups of Az having 1 to 20 carbon atoms can be given, in which some or all of the hydrogen atoms in the above hydrocarbon groups are substituted with fluorine atoms.

[0089] The -CH2- constituting the above (ka+2) hydrocarbon group is -O-, -NR 4 -, -C(=O)- or -Si(R 2 R 3 It may be replaced with )-.

[0090] R 2 , R 3 Specific examples of straight-chain, branched, or cyclic alkyl groups having 1 to 6 carbon atoms include methyl groups, ethyl groups, propyl groups, isopropyl groups, n-butyl groups, sec-butyl groups, tert-butyl groups, n-pentyl groups, n-hexyl groups, cyclopropyl groups, cyclobutyl groups, cyclopentyl groups, cyclohexyl groups, etc.

[0091] R 4 Specific examples of straight-chain or branched alkyl groups having 1 to 4 carbon atoms include methyl groups, ethyl groups, propyl groups, isopropyl groups, etc.

[0092] Z represents a single bond or an oxygen atom, and an oxygen atom is preferred.

[0093] Specific examples of halogen atoms in Xf include fluorine atoms, chlorine atoms, and bromine atoms.

[0094] Specific examples of straight-chain, branched, or cyclic monovalent hydrocarbon groups that may be substituted with fluorine atoms having 1 to 10 carbon atoms of Xf include alkyl groups such as methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, cyclopropyl, and cyclobutyl groups, trifluoromethyl, 2,2,2-trifluoroethyl groups, etc.

[0095] Specific examples of alkoxy groups that may be substituted with fluorine atoms having 1 to 10 carbon atoms of Xf include methoxy groups, ethoxy groups, propoxy groups, isopropoxy groups, n-butoxy groups, sec-butoxy groups, tert-butoxy groups, cyclopropoxy groups, trifluoromethoxy groups, 2,2,2-trifluoroethoxy groups, etc.

[0096] Specific examples of the electron-attracting groups of Xf include carbonyl groups, alkoxycarbonyl groups, cyano groups, nitro groups, sulfo groups, formyl groups, sulfonic acid ester groups, amide groups, -OC(=O)-G-(G is a sulfur atom or NH), etc.

[0097] The following are examples of aromatic monocyclic or polycyclic rings having 5 to 20 carbon atoms of ring ZZ. As shown below, ring ZZ may have additional substituents.

[0098]

[0099] 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.

[0100] As a specific example of a polyurethane containing a phenolic hydroxyl group represented by (1A), a polyurethane obtained by reacting the following polyisocyanate, high molecular weight polyol, and chain extender may be used. The polyisocyanate, high molecular weight polyol, and chain extender may each be used individually, or two or more types may be used in combination.

[0101] As 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, butene diisocyanate, 1,3-butadiene-1,4-diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, 1,6,11-undecamethylene diisocyanate, 1,3,6-hexamethylene diisocyanate, 1,8-Diisocyanate-4-Isocyanatomethyloctane, 2,5,7-Trimethyl-1,8-Diisocyanate-5-Isocyanatomethyloctane, Bis(isocyanatoethyl)carbonate, Bis(isocyanatoethyl)ether, 1,4-Butyleneglycoldipropylether-ω,ω'-Diisocyanate, Lysine isocyanatomethyl ester, Lysine triisocyanate, 2-Isocyanatoethyl-2,6-Diisocyanatehexanoate, 2-Isocyanatopropyl-2,6-Diisocyanatehexanoate, Bis(4-Isocyanate-n-butylidene)pentaerythritol, 2,6-Diisocyanatemethylcaproate, Isophorone diisocyanate (IPDI), 1,3-Cyclohexyl diisocyanate, 1,4-cyclohexyl diisocyanate, 1,3-bis(isocyanatomethyl)cyclohexane, 1,4-bis(isocyanatomethyl)cyclohexane, 1,3-bis(isocyanatoethyl)cyclohexane, 1,4-bis(isocyanatoethyl)cyclohexane, methylcyclohexane diisocyanate, 2,2'-dimethyldicyclohexylmethane diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, dimer acid diisocyanate, 2,5-diisocyanatomethylbicyclo[2,2,1]-heptane, 2,6-diisocyanatomethylbicyclo[2,2,1]-heptane, 2-isocyanatomethyl2-(3-isocyanatopropyl)-5-isocyanatomethylbicyclo[2,2,1]-heptane, 2-isocyanatomethyl-2-(3-isocyanatopropyl)-6-isocyanatomethylbicyclo[2,2,1]-heptane,Aliphatic and alicyclic polyisocyanates such as 2-isocyanatomethyl 3-(3-isocyanatopropyl)-5-(2-isocyanatoethyl)-bicyclo[2,2,1]-heptane, 2-isocyanatomethyl 3-(3-isocyanatopropyl)-6-(2-isocyanatoethyl)-bicyclo[2,2,1]-heptane, 2-isocyanatomethyl 2-(3-isocyanatopropyl)-5-(2-isocyanatoethyl)-bicyclo[2,2,1]-heptane, 2-isocyanatomethyl 2-(3-isocyanatopropyl)-6-(2-isocyanatoethyl)-bicyclo[2,2,1]-heptane, 2,4-tolylene diisocyanate or 2,6-tolylene diisocyanate and mixtures of isomers thereof (TDI), Examples include 4,4'-diphenylmethane diisocyanate or 2,4'-diphenylmethane diisocyanate and mixtures of their isomers (MDI), aromatic polyisocyanates such as toluidine diisocyanate (TODI), paraphenylene diisocyanate, naphthalene diisocyanate (NDI), and 4,4'-dibenzyl diisocyanate, aromatic aliphatic polyisocyanates such as orthoxylylene diisocyanate, methaxylylene diisocyanate, paraxylylene diisocyanate, 1,3-tetramethylxylylene diisocyanate, and 1,4-tetramethylxylylene diisocyanate, and also urethane modified versions thereof such as polymers, biuret modified versions, carbodiimide modified versions, uretonimine modified versions, uretodione modified versions, isocyanurate modified versions, allofanate modified versions, etc.

[0102] Examples of high molecular weight polyols include polyoxypropylene glycols, polyoxyethylene glycols, polyoxytetramethylene glycols, and copolymers thereof such as polyether polyols, polyester polyols, polyester-amide polyols, polycarbonate polyols, acrylic polyols, terminally hydroxylated polyolefins, silicone polyols, and vegetable oil-based polyols.

[0103] Specific examples of polyoxypropylene glycols and polyoxyethylene glycols 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-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, Dihydric alcohols such as cyclohexane-1,3-dimethanol, cyclohexane-1,4-dimethanol, 1,3-adamantanedimethanol, dimersandiol, 1,2-benzenediol, 1,3-benzenediol, 1,4-benzenediol, hydroquinone di(2-hydroxyethyl ether), bisphenol A, bis(β-hydroxyethyl)benzene, and xylylene glycol, trihydric alcohols such as glycerin, trimethylolpropane, and triisopropanolamine, tetrahydric alcohols such as pentaerythritol, α-methylglycoside, and diglycerin, or low molecular weight polyols such as polyhydric alcohols such as sorbitol and sucrose, low molecular weight amino alcohols such as monoethanolamine, dimethanolamine, and triethanolamine, ethylenediamine, propylenediamine, butanediamine, and pentamethylenediamine, Examples include addition polymers of ethylene oxide, propylene oxide, and butylene oxide initiators using low molecular weight polyamines such as hexamethylenediamine, isophoronediamine, piperazine, toluenediamine, metaphenylenediamine, diphenylmethanediamine, xylylenediamine, dimethylthiotoluenediamine, and 4,4-methylenebis-o-chloroaniline. Additionally, the alkylene oxide constituent of the polyester polyol may be used alone or in combination of two or more types, and the polyoxyalkylene polyol using two or more types in combination may have a block type or a random type structure.

[0104] Specific examples of polyoxytetramethylene glycol include crystalline polyoxytetramethylene glycol, alkyl-substituted tetrahydrofuran such as 3-methyltetrahydrofuran in THF, and amorphous polyoxytetramethylene glycol copolymerized with the aforementioned dihydric alcohol.

[0105] As a polyester polyol, the above-mentioned low molecular weight polyol and polycarboxylic acids such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, souveric acid, glutaconic 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, muconic acid, α-hydromuconic acid, β-hydromuconic acid, phthalic acid, orthophthalic acid, terephthalic acid, isophthalic acid, toluenedicarboxylic acid, naphthalenedicarboxylic acid, hetic acid, dimer acid, hydrogenated dimer acid, and derivatives thereof, acid anhydrides, acid halides, and the above-mentioned low molecular weight polyol Examples of 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, used as initiators. In addition, low molecular weight polyols, polycarboxylic acids, oligomeric acids, lactones, or lactides that are components of polyester polyols may each be used individually or two or more types may be used in combination.

[0106] As polyester-amide polyols, examples include a portion of the low molecular weight polyol of the polyester polyol that is obtained as a polymer condensate instead of the low molecular weight polyamine or amino alcohol described above.

[0107] Specific examples of polycarbonate polyols include polycondensates of the aforementioned low molecular weight polyol and carbonate compounds such as dimethyl carbonate, diethyl carbonate, ethylene carbonate, propylene carbonate, diphenyl carbonate, dinaphthyl carbonate, dianthryl carbonate, diphenanthryl carbonate, diindanyl carbonate, and tetrahydronaphthyl carbonate. Additionally, the low molecular weight polyol or carbonate compound constituting the polycarbonate polyol may each be used individually or in combination of two or more types.

[0108] Specific examples of acrylic polyols include hydroxyl group-containing (meth)acrylates such as 2-hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, 3-hydroxy-2,2-dimethylpropyl acrylate, 2,2-dihydroxymethylbutyl (meth)acrylate, pentaerythritol tri(meth)acrylate, polyhydroxyalkyl maleate, and polyhydroxyalkyl fumarate, and methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, s-butyl (meth)acrylate, t-butyl (meth)acrylate, and pentyl (meth)acrylate. (Meth)acrylic acid esters such as isopentyl (meth)acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, octyl (meth)acrylate, nonyl (meth)acrylate, isononyl (meth)acrylate, decyl (meth)acrylate, dodecyl (meth)acrylate, cyclohexyl (meth)acrylate, phenyl (meth)acrylate, benzyl (meth)acrylate, allyl (meth)acrylate, ethylene glycol di(meth)acrylate), butylene glycol di(meth)acrylate, hexanediol di(meth)acrylate, oligoethylene glycol di(meth)acrylate, etc., aromatic vinyl monomers such as styrene, vinyltoluene, α-methylstyrene, vinyl cyanide monomers such as (meth)acrylonitrile, fumaric acid, maleic acid, Examples include copolymers obtained by copolymerizing vinyl monomers such as carboxyl group-containing vinyl monomers or their alkyl esters, vinyl monomers containing isocyanate groups such as 3-(2-isocyanate-2-propyl)-α-methylstyrene, vinyl monomers containing fluorine such as tetrafluoroethylene, chlorotrifluoroethylene, trichlorofluoroethylene, hexafluoropropylene, vinylidene fluoride, vinyl fluoride, trifluoromethyltrifluoroethylene, and silicon monomers such as γ-(meth)acryloxypropyltrimethoxysilane.In addition, the (meth)acrylate or vinyl monomer, which are components of the acrylic polyol, may each be used individually or two or more types may be used in combination.

[0109] Specific examples of terminally hydroxylated polyolefins include compounds in which the terminals of a polymer obtained by polymerizing one or more types of olefins, such as ethylene, propylene, butadiene, isoprene, styrene, acrylonitrile, vinyl ether, vinyl acetate, and olefins in which a part of their structure is substituted with a halogen such as fluorine, chlorine, or bromine, are hydroxylated.

[0110] Specific examples of silicone polyols include vinyl group-containing silicone compounds obtained by polymerizing γ-methacryloxypropyltrimethoxysilane, etc., and polysiloxanes such as α,ω-dihydroxypolydimethylsiloxane and α,ω-dihydroxypolydiphenylsiloxane having at least one terminal hydroxyl group in the molecule.

[0111] Specific examples of vegetable oil-based polyols include ester-modified castor oil polyols obtained by the reaction of castor oil fatty acids with polyols, such as hydroxyl group-containing vegetable oils like castor oil and palm oil, dehydrated castor oil, partially dehydrated castor oil, and hydrogenated castor oil.

[0112] As chain extenders, 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-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-dimethanol, Dihydric alcohols such as cyclohexane-1,4-dimethanol, 1,3-adamantan dimethanol, dimersandiol, 1,2-benzenediol, 1,3-benzenediol, 1,4-benzenediol, hydroquinone di(2-hydroxyethyl ether), bisphenol A, bis(β-hydroxyethyl)benzene, xylylene glycol, ethanolamine, dimethanolamine, triethanolamine, ethylenediamine, propylenediamine, butanediamine, pentamethylenediamine, hexamethylenediamine, isophoronediamine, piperazine, toluenediamine, metaphenylenediamine, diphenylmethanediamine, xylylenediamine, dimethylthiotoluenediamine, 4,4-methylenebis-o-chloroaniline, etc. are used.

[0113] Additionally, the following chain extenders containing weakly acidic functional groups may be cited.

[0114]

[0115] (during food, R 1 , R 4 , R 7 , R 8 is the same as above.)

[0116]

[0117]

[0118] (during food, R 1 is the same as above.)

[0119] Additionally, the following chain extenders containing phenol may be cited.

[0120]

[0121] As a specific example of a polyurethane containing a phenolic hydroxyl group represented by (1A), a polyurethane obtained by reacting the polyisocyanate, high molecular weight polyol, and chain extender can be cited.

[0122] In addition, a polyurethane obtained by reacting the following capping agent with the aforementioned polyisocyanate, high molecular weight polyol, and chain extender may be cited.

[0123]

[0124] (In the formula, X is an oxygen atom or NR 4 Represents, and R 4 is the same as above.)

[0125]

[0126] (In the formula, X is an oxygen atom or NR 4 Represents, and R 4 is the same as above.)

[0127] As an example of the above, the following polyurethane can be cited.

[0128]

[0129] (In the formula, la is an integer from 7 to 30, lb is an integer from 2 to 30, lc is an integer from 3 to 30, ld is an integer from 1 to 5, and le is an integer from 2 to 20.)

[0130] As for the polyurethane containing a phenolic hydroxyl group represented by the above general formula (1A), it is particularly desirable to include a phenolic hydroxyl group represented by the following general formula (1B).

[0131]

[0132] (In the formula, Az' represents a straight-chain, branched, or cyclic (ka+2) hydrocarbon group having 1 to 19 carbon atoms, or a fluorinated hydrocarbon group, and the -CH2- constituting the (ka+2) hydrocarbon group is -O-, -NR 4 -, -C(=O)- or -Si(R2 R 3 It may be substituted with ). ka represents an integer from 0 to 2. kb, kc, kd, and ke represent 1 or 2. R 2 , R 3 , R 4 ...is the same as above, and the dashed line indicates the joining loss.)

[0133] Az' represents a straight-chain, branched, or cyclic (ka+2) hydrocarbon group or a fluorinated hydrocarbon group having 1 to 19 carbon atoms, and the -CH2- constituting the (ka+2) hydrocarbon group is -O-, -NR 4 -, -C(=O)- or -Si(R 2 R 3 It may be replaced with )-.

[0134] ka represents an integer from 0 to 2, and kb, kc, kd, and ke represent 1 or 2.

[0135] Specifically, the following can be exemplified as a substructure represented by the above general formulas (1A) and (1B).

[0136]

[0137] (In the formula, X is an oxygen atom or NR 4 It represents, and the dashed line represents the coupling loss. R 4 is the same as above.)

[0138]

[0139] (In the formula, X is an oxygen atom or NR 4 It represents, and the dashed line represents the coupling loss. R 4 is the same as above.)

[0140]

[0141] (In the formula, X is an oxygen atom or NR 4 It represents, and the dashed line represents the coupling loss. R 4 is the same as above.)

[0142]

[0143] (In the formula, X is an oxygen atom or NR 4 It represents, and the dashed line represents the coupling loss. R 4 is the same as above.)

[0144]

[0145] (In the formula, X is an oxygen atom or NR 4 It represents, and the dashed line represents the coupling loss. R 4 is the same as above.)

[0146]

[0147] (In the formula, X is an oxygen atom or NR 4 It represents, and the dashed line represents the coupling loss. R 4 is the same as above.)

[0148] In addition, in the present invention, it is preferable that the polyurethane described above further comprises one or more weakly acidic functional groups represented by the following general formulas (1a) to (1c).

[0149]

[0150] (In the formula, R represents a hydrogen atom, a fluorine atom, or a straight-chain, branched, or cyclic hydrocarbon group having 1 to 10 carbon atoms that may be fluorinated, and Rf represents a fluorine atom or a straight-chain, branched, or cyclic fluorinated hydrocarbon group having 1 to 10 carbon atoms. n is an integer of 1 or 2, and dashed lines represent bond losses.)

[0151] R represents a hydrogen atom, a fluorine atom, or a straight, branched, or cyclic hydrocarbon group having 1 to 10 carbon atoms that may be fluorinated, and specific examples thereof include a hydrogen atom, a fluorine atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a difluoromethyl group, a trifluoromethyl group, a 2,2,2-trifluoroethyl group, etc.

[0152] Rf represents a fluorine atom or a straight-chain, branched, or cyclic fluorinated hydrocarbon group having 1 to 10 carbon atoms, and specific examples thereof include a fluorine atom, a difluoromethyl group, a trifluoromethyl group, a 2,2,2-trifluoroethyl group, etc.

[0153] n is an integer of 1 or 2.

[0154] Specific examples of the weak acidic functional group (1a) include the fluoroalcohol-containing group shown below.

[0155]

[0156] (during food, R 7 , R 8 Each independently represents a hydrogen atom, a straight-chain, branched, or cyclic hydrocarbon group having 1 to 6 carbon atoms, and R 7 and R 8 They may bond with each other to form non-aromatic rings having 3 to 8 carbon atoms together with the carbon atoms to which they bond. Dashed lines indicate bond losses.

[0157] Specific examples of the weak acidic functional group (1b) include the cyclic fluoroalcohol-containing group shown below.

[0158]

[0159] (during food, R 1 It is a hydrogen atom or a monovalent hydrocarbon group having 1 to 3 carbon atoms. The dashed lines indicate bond loss.

[0160] Specific examples of the weakly acidic functional group (1c) include the sulfonamide-containing group shown below.

[0161]

[0162] The polyurethane of the present invention is further preferably composed of one or more structures represented by the following general formulas (2a) to (2c).

[0163]

[0164] (during food, R 1 is a hydrogen atom, or a monovalent hydrocarbon group having 1 to 3 carbon atoms, and A a represents a single bond, or a straight-chain, branched, or cyclic divalent hydrocarbon group having 1 to 20 carbon atoms, and the constituent -CH2- may be substituted with -O-, -C(=O)-, -C(=O)O-, or -C6H4-, and -NR 4 Even if it's -C(=O)- it's fine. A b and A c -O-, -OC(=O)-NR respectively, independently 4 -, -NR 4 Represents one of the groups selected from -, -C(=O)O-. n 1 , n 2 , n 4 is an integer from 0 to 10, and n 3 is an integer of 0 or 1. R 4 ...is the same as above, and the dashed line indicates the joining loss.)

[0165] R 1 It is a hydrogen atom or a monovalent hydrocarbon group having 1 to 3 carbon atoms, and a hydrogen atom, a methyl group, or an ethyl group is preferred.

[0166] [Method for manufacturing polyurethane]

[0167] The above polyurethane is obtained by reacting a polyisocyanate with a polyol, polyamine, or polycarboxylic acid, etc., by a known method such as the one-shot method or the prepolymer method, and preferably the prepolymer method is used.

[0168] In the prepolymer method, polyurethane is synthesized by a process of (a) reacting a diisocyanate with a high molecular weight polyol in excess of isocyanate groups to obtain a reaction mixture containing a prepolymer with isocyanate group ends, and (b) reacting the prepolymer with a low molecular weight diol, diamine, or dicarboxylic acid (chain extender) to increase the molecular weight of the prepolymer. Furthermore, a polyurethane having a cross-linked structure may be obtained by adding a polyisocyanate with three or more reaction groups, or a polyol, polyamine, or polycarboxylic acid with three or more reaction groups.

[0169] In addition, after performing the polymerization of (b) above with an excess of isocyanate groups, a capping agent having a reactive group (hydroxyl group, amino group, carboxyl group, etc.) capable of reacting with the isocyanate groups may be added to introduce a functional group derived from the capping agent to the urethane terminal.

[0170] The polyurethane containing phenolic hydroxyl groups according to the present invention can be synthesized by substituting at least one or part of the high molecular weight polyol, chain extender, and capping agent in the reactions of (a) and (b) with a compound containing phenolic hydroxyl groups, but a method of introducing phenolic hydroxyl groups as a capping agent after the chain extension reaction, that is, a method of introducing said phenolic hydroxyl groups into the polyurethane using an alcohol or amine represented by the following general formula (1C) after the chain extension reaction is more preferred.

[0171]

[0172] (In the formula, Az" represents a straight-chain, branched, or cyclic (ka+2) hydrocarbon group having 1 to 19 carbon atoms, or a fluorinated hydrocarbon group, and the -CH2- constituting the (ka+2) hydrocarbon group is -O-, -C(=O)-, or -Si(R 2 R 3 It may be substituted with ). X is an oxygen atom or NR 4Represents. ka represents an integer from 0 to 2. kb, kc, kd, and ke represent 1 or 2. R 2 , R 3 , R 4 is the same as above.)

[0173] Az" represents a straight-chain, branched, or cyclic (ka+2) hydrocarbon group having 1 to 19 carbon atoms, and the -CH2- constituting the (ka+2) hydrocarbon group is -O-, -C(=O)-, or -Si(R 2 R 3 It may be replaced with )-.

[0174] X is an oxygen atom or NR 4 It represents.

[0175] ka represents an integer from 0 to 2, and kb, kc, kd, and ke represent 1 or 2.

[0176] R 2 , R 3 , R 4 It is the same as above.

[0177] In addition, since phenolic hydroxyl groups can react with isocyanates, when introducing phenolic hydroxyl groups into high molecular weight polyols or chain extenders, it is preferable to perform polyurethane while protected with a suitable protecting group and then deprotect.

[0178] In addition, in the reactions of (a) and (b), a polyurethane containing phenolic hydroxyl groups and weak acidic functional groups can be synthesized by substituting at least one whole or part of the high molecular weight polyol, chain extender, and capping agent with a compound containing weak acidic functional groups.

[0179] [Polyisocyanate]

[0180] As polyisocyanates that are components of polyurethane, 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, butene diisocyanate, 1,3-butadiene-1,4-diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, 1,6,11-undecamethylene diisocyanate, 1,3,6-hexamethylene triisocyanate, 1,8-diisocyanate-4-isocyanatomethyloctane, 2,5,7-trimethyl-1,8-diisocyanate-5-isocyanatomethyloctane, bis(isocyanatoethyl)carbonate, bis(isocyanatoethyl)ether, 1,4-butylene glycol dipropyl ether-ω,ω'-diisocyanate, lysine isocyanatomethyl ester, lysine triisocyanate, 2-isocyanatoethyl-2,6-diisocyanate hexanoate, 2-isocyanatopropyl-2,6-diisocyanate hexanoate, bis(4-isocyanate-n-butylidene)pentaerythritol, 2,6-diisocyanate methylcaproate, Isophorone diisocyanate (IPDI), 1,3-cyclohexyl diisocyanate, 1,4-cyclohexyl diisocyanate, 1,3-bis(isocyanatomethyl)cyclohexane, 1,4-bis(isocyanatomethyl)cyclohexane, 1,3-bis(isocyanatoethyl)cyclohexane, 1,4-bis(isocyanatoethyl)cyclohexane, methylcyclohexane diisocyanate, 2,2'-dimethyldicyclohexylmethane diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, dimer acid diisocyanate, 2,5-diisocyanatomethylbicyclo[2,2,1]-heptane, 2,6-diisocyanatomethylbicyclo[2,2,1]-heptane, 2-isocyanatomethyl2-(3-isocyanatopropyl)-5-isocyanatomethylbicyclo[2,2,1]-heptane,Aliphatic and such as 2-isocyanatomethyl-2-(3-isocyanatopropyl)-6-isocyanatomethylbicyclo[2,2,1]-heptane, 2-isocyanatomethyl3-(3-isocyanatopropyl)-5-(2-isocyanatoethyl)-bicyclo[2,2,1]-heptane, 2-isocyanatomethyl3-(3-isocyanatopropyl)-6-(2-isocyanatoethyl)-bicyclo[2,2,1]-heptane, 2-isocyanatomethyl2-(3-isocyanatopropyl)-5-(2-isocyanatoethyl)-bicyclo[2,2,1]-heptane, 2-isocyanatomethyl2-(3-isocyanatopropyl)-6-(2-isocyanatoethyl)-bicyclo[2,2,1]-heptane Alicyclic polyisocyanates, 2,4-tolylene diisocyanate or 2,6-tolylene diisocyanate and mixtures of isomers thereof (TDI), 4,4'-diphenylmethane diisocyanate or 2,4'-diphenylmethane diisocyanate and mixtures of isomers thereof (MDI), toluidine diisocyanate (TODI), paraphenylene diisocyanate, naphthalene diisocyanate (NDI), aromatic polyisocyanates such as 4,4'-dibenzyl diisocyanate, orthoxylylene diisocyanate, methaxylylene diisocyanate, paraxylylene diisocyanate, 1,3-tetramethylxylylene diisocyanate, 1,4-tetramethylxylylene diisocyanate, aromatic aliphatic polyisocyanates such as orthoxylylene diisocyanate, methaxylylene diisocyanate, paraxylylene diisocyanate, and 1,3-tetramethylxylylene diisocyanate, 1,4-tetramethylxylylene diisocyanate, and also urethane modified forms thereof such as polymers and biuret modified forms, Examples include carbodiimide modifieds, uretonimine modifieds, uretodion modifieds, isocyanurate modifieds, allofanate modifieds, etc.

[0181] The above polyisocyanate may be used alone or in combination of two or more types.

[0182] [High molecular weight polyol]

[0183] As a high molecular weight polyol that is a component of polyurethane, a polyol having two or more hydroxyl groups capable of reacting with isocyanate groups and having a number average molecular weight of 500 to 5,000 can be used. Examples include polyether polyols, polyester polyols, polycarbonate polyols, acrylic polyols, terminally hydroxylated polyolefins, silicone polyols, vegetable oil-based polyols, etc.

[0184] Examples of polyether polyols include polyoxypropylene glycols, polyoxyethylene glycols, polyoxytetramethylene glycols, and copolymers thereof.

[0185] Polyoxypropylene glycols and polyoxyethylene glycols are addition polymers of alkylene oxides initiating low molecular weight polyols, polyamines, or amino alcohols, and as low molecular weight polyols, 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-dimethylolheptane, 2,2,2-trimethylpentanediol, 1,4-dihydroxy-2-butene, 2,6-dimethyl-1-octene-3,8-diol, diethylene glycol, triethylene glycol, Examples include dihydric alcohols such as dipropylene glycol, cyclohexane-1,3-diol, cyclohexane-1,4-diol, cyclohexane-1,3-dimethanol, cyclohexane-1,4-dimethanol, 1,3-adamantan dimethanol, dimersandiol, 1,2-benzenediol, 1,3-benzenediol, 1,4-benzenediol, hydroquinone di(2-hydroxyethyl ether), bisphenol A, bis(β-hydroxyethyl)benzene, xylylene glycol, trihydric alcohols such as glycerin, trimethylolpropane, triisopropanolamine, tetrahydric alcohols such as pentaerythritol, α-methylglucoside, and diglycerin, or polyhydric alcohols such as sorbitol and sucrose. Examples of low molecular weight amino alcohols include monoethanolamine, dimethanolamine, and triethanolamine, and examples of low molecular weight polyamines include ethylenediamine, propylenediamine, butanediamine, pentamethylenediamine, hexamethylenediamine, isophoronediamine, piperazine, toluenediamine, metaphenylenediamine, diphenylmethanediamine, xylylenediamine, dimethylthiotoluenediamine, 4,4-methylenebis-o-chloroaniline, etc. The initiator may be used alone or two or more types may be used in combination.

[0186] Furthermore, by using the low molecular weight polyol containing the aforementioned phenolic hydroxyl group or weak acid functional group, a polyether polyol containing the phenolic hydroxyl group or weak acid functional group may be obtained. Additionally, it is preferable to perform polymerization while protecting the phenolic hydroxyl group and the weak acid functional group, and then deprotect them.

[0187] Examples of alkylene oxides include ethylene oxide, propylene oxide, butylene oxide, etc., and can be used alone or in combination of two or more types. For the polyoxyalkylene polyol using two or more types in combination, either a block type or a random type structure may be used.

[0188] Polyoxytetramethylene glycol is a ring-opening polymer obtained by cationic polymerization of tetrahydrofuran (THF), and examples include crystalline polyoxytetramethylene glycol, alkyl-substituted tetrahydrofuran such as 3-methyltetrahydrofuran in THF, or amorphous polyoxytetramethylene glycol obtained by copolymerizing the aforementioned dihydric alcohol.

[0189] Examples of polyester polyols include polymerization condensates of the aforementioned low molecular weight polyol with polycarboxylic acids or oligomeric acids, or lactones or ring-opening polymers of lactones using the low molecular weight polyol as an initiator.

[0190] Examples of polycarboxylic acids include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, souveric acid, glutaconic 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, muconic acid, α-hydromuconic acid, β-hydromuconic acid, phthalic acid, orthophthalic acid, terephthalic acid, isophthalic acid, toluenedicarboxylic acid, naphthylenedicarboxylic acid, hetic acid, dimer acid, and hydrogenated dimer acid, and derivatives thereof, acid anhydrides, acid halides, etc. may also be used.

[0191] Examples of lactones include β-propiolactone, β-butyrolactone, γ-butyrolactone, γ-valerolactone, δ-valerolactone, ε-caprolactone, etc., and examples of lactides include L-lactide and D-lactide.

[0192] The low molecular weight polyol, polycarboxylic acid, oligomeric acid, lactone, or lactide that are components of the polyester polyol may each be used individually or two or more types may be used in combination.

[0193] Furthermore, some of the low molecular weight polyols of the polyester polyol may be the low molecular weight polyamines described above or polyester-amide polyols obtained instead of amino alcohols.

[0194] As a polycarbonate polyol, a polycondensate of the aforementioned polyol and carbonate compound is exemplified.

[0195] Examples of carbonate compounds include dimethyl carbonate, diethyl carbonate, ethylene carbonate, propylene carbonate, diphenyl carbonate, dinaphthyl carbonate, dianthryl carbonate, diphenanthryl carbonate, diindanyl carbonate, tetrahydronaphthyl carbonate, etc.

[0196] The low molecular weight polyol or carbonate compound that is a component of the polycarbonate polyol may each be used alone or two or more types may be used in combination.

[0197] As an example of an acrylic polyol, a copolymer obtained by copolymerizing a hydroxyl group-containing (meth)acrylate and a vinyl monomer is used.

[0198] Examples of hydroxyl group-containing (meth)acrylates include 2-hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, 3-hydroxy-2,2-dimethylpropylacrylate, 2,2-dihydroxymethylbutyl (meth)acrylate, pentaerythritol tri(meth)acrylate, polyhydroxyalkyl maleate, polyhydroxyalkyl fumarate, etc. The above-mentioned hydroxyl group-containing (meth)acrylates may be used alone or in combination of two or more types.

[0199] As vinyl monomers, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, s-butyl (meth)acrylate, t-butyl (meth)acrylate, pentyl (meth)acrylate, isopentyl (meth)acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, octyl (meth)acrylate, nonyl (meth)acrylate, isononyl (meth)acrylate, decyl (meth)acrylate, dodecyl (meth)acrylate, cyclohexyl (meth)acrylate, phenyl (meth)acrylate, benzyl (meth)acrylate, allyl (meth)acrylate, Examples include (meth)acrylic acid esters such as ethylene glycol di(meth)acrylate, butylene glycol di(meth)acrylate, hexanediol di(meth)acrylate, and oligoethylene glycol di(meth)acrylate; aromatic vinyl monomers such as styrene, vinyltoluene, and α-methylstyrene; vinyl cyanide monomers such as (meth)acrylonitrile; vinyl monomers containing carboxyl groups such as fumaric acid, maleic acid, and itaconic acid, or their alkyl esters; vinyl monomers containing isocyanate groups such as 3-(2-isocyanate-2-propyl)-α-methylstyrene; vinyl monomers containing fluorine such as tetrafluoroethylene, chlorotrifluoroethylene, trichlorofluoroethylene, hexafluoropropylene, vinylidene fluoride, vinyl fluoride, and trifluoromethyltrifluoroethylene; and silicon monomers such as γ-(meth)acryloxypropyltrimethoxysilane. The vinyl monomer described above may be used alone, or two or more types may be used in combination.

[0200] Examples of terminally hydroxylated polyolefins include compounds in which the terminals of one or more olefin polymers are hydroxylated. Examples of olefins include ethylene, propylene, butadiene, isoprene, styrene, acrylonitrile, vinyl ether, and vinyl acetate, and a part of the above structure may also be substituted with a halogen such as fluorine, chlorine, or bromine.

[0201] Examples of silicone polyols include vinyl group-containing silicone compounds obtained by polymerizing γ-methacryloxypropyltrimethoxysilane, etc., and polysiloxanes such as α,ω-dihydroxypolydimethylsiloxane and α,ω-dihydroxypolydiphenylsiloxane having at least one terminal hydroxyl group in the molecule.

[0202] Examples of vegetable oil-based polyols include hydroxyl group-containing vegetable oils such as castor oil and palm oil, ester-modified castor oil polyols obtained by the reaction of castor oil fatty acids with polyols, dehydrated castor oil, partially dehydrated castor oil, hydrogenated castor oil, etc.

[0203] The number average molecular weight of the high molecular weight polyol is preferably in the range of 500 to 5,000, more preferably in the range of 1,000 to 3,000, and even more preferably in the range of 1,000 to 2,000.

[0204] By ensuring that the number-average molecular weight of the high molecular weight polyol is above the lower limit, it is possible to suppress performance degradation, such as an excessive increase in the concentration of urethane groups in the polyurethane and the accompanying increase in hardness and decrease in elasticity. Furthermore, by ensuring that the number-average molecular weight is below the upper limit, an excessive decrease in the concentration of urethane groups is suppressed, thereby preventing a decrease in strength originating from urethane bonds and enabling the coexistence of appropriate strength and elasticity.

[0205] The high molecular weight polyol is preferably a difunctional polyol or a trifunctional polyol, and more preferably a difunctional polyol.

[0206] [Chain extension system]

[0207] As chain extenders, 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-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-dimethanol, Dihydric alcohols such as cyclohexane-1,4-dimethanol, 1,3-adamantan dimethanol, dimersandiol, 1,2-benzenediol, 1,3-benzenediol, 1,4-benzenediol, hydroquinone di(2-hydroxyethyl ether), bisphenol A, bis(β-hydroxyethyl)benzene, xylylene glycol, ethanolamine, dimethanolamine, triethanolamine, ethylenediamine, propylenediamine, butanediamine, pentamethylenediamine, hexamethylenediamine, isophoronediamine, piperazine, toluenediamine, metaphenylenediamine, diphenylmethanediamine, xylylenediamine, dimethylthiotoluenediamine, 4,4-methylenebis-o-chloroaniline, etc. are used.

[0208] Furthermore, a weakly acidic functional group can be introduced into the polyurethane by using one or more alcohols represented by the following general formulas (3a) to (3c) as chain extenders. The chain extender may be the polyol described in (3a) to (3c) used alone, or used in combination with the chain extender described above.

[0209]

[0210] (during food, R 1 is a hydrogen atom or a monovalent hydrocarbon group having 1 to 3 carbon atoms, and A a represents a single bond, or a straight-chain, branched, or cyclic divalent hydrocarbon group having 1 to 20 carbon atoms, and the constituent -CH2- may be substituted with -O-, -C(=O)-, -C(=O)O-, or -C6H4-, and -NR4 Even if it's -C(=O)-, it's fine. R 4 is a hydrogen atom, or a straight-chain or branched alkyl group having 1 to 4 carbon atoms. 1 , n 2 , n 4 is an integer between 0 and 10.)

[0211] By using such a chain extender, a polyurethane having a structure represented by the general formulas (2a) to (2c) described above can be obtained.

[0212] R 1 It is a hydrogen atom or a monovalent hydrocarbon group having 1 to 3 carbon atoms, and a hydrogen atom, a methyl group, or an ethyl group is preferred.

[0213] A a represents a single bond, or a straight-chain, branched, or cyclic divalent hydrocarbon group having 1 to 20 carbon atoms, and the constituent -CH2- may be substituted with -O-, -C(=O)-, -C(=O)O-, or -C6H4-, and -NR 4 -C(=O)- is also fine. The above A a The straight, branched, or cyclic divalent hydrocarbon groups having 1 to 20 carbon atoms can be specifically exemplified as follows.

[0214]

[0215] Additionally, the above A a Any one of the -CH2- groups is -O-, -C(=O)-, -C(=O)O-, -C6H4-, or -NR 4 An example of substitution with -C(=O)- can be provided. R 4 is a hydrogen atom, or a straight-chain or branched alkyl group having 1 to 4 carbon atoms, and n 1 , n 2 , n 4 is an integer from 0 to 10.

[0216] The following are specific examples of polyols represented by the above general formulas (3a) to (3c), but are not limited thereto.

[0217]

[0218] (during food, R 1 , R 4 , R 7 , R 8 is the same as above.)

[0219]

[0220]

[0221] (during food, R 1 is the same as above.)

[0222] The chain extender having the above-mentioned weak acidic functional group is preferably used in an amount of 5 to 50 mass% relative to the total amount of the urethane components, and more preferably in an amount of 20 to 40 mass%.

[0223] [Crosslinking agent]

[0224] As crosslinking agents, trihydric alcohols such as glycerin, trimethylolpropane, and triisopropanolamine, and polyhydric alcohols such as pentaerythritol, α-methylglucoside, and diglycerin are used.

[0225] As for the amount of crosslinking agent added, it is preferable to be in the range of 0 to 5 mass% with respect to the total amount of the urethane components, and more preferable to be 0 to 3 mass%.

[0226] If the amount of crosslinking agent added is below the upper limit, the strength does not increase excessively, and flexibility and elasticity are not compromised, making it suitable for use in the conductive paste composition containing the polyurethane of the present invention.

[0227] [Organic Solvents]

[0228] Polyurethane is synthesized by bulk polymerization or solution polymerization. Organic solvents used for solution polymerization include, for example, toluene, xylene, cumene, 1,2,3-trimethylbenzene, 1,2,4-trimethylbenzene, 1,3,5-trimethylbenzene, styrene, α-methylstyrene, butylbenzene, sec-butylbenzene, isobutylbenzene, cymene, 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-amylbenzene, amylbenzene, 2-tert-butyltoluene, 3-tert-butyltoluene, 4-tert-butyltoluene, 5-isopropyl-m-xylene, Aromatic hydrocarbon solvents such as 3-methylethylbenzene, tert-butyl-3-ethylbenzene, 4-tert-butyl-o-xylene, 5-tert-butyl-m-xylene, tert-butyl-p-xylene, 1,2-diisopropylbenzene, 1,3-diisopropylbenzene, 1,4-diisopropylbenzene, dipropylbenzene, pentamethylbenzene, hexamethylbenzene, hexylbenzene, and 1,3,5-triethylbenzene, n-heptane, isoheptane, n-hexane, octane, 3-methylhexane, 2,3-dimethylpentane, 3-ethylpentane, 1,6-heptadiene, 5-methyl-1-hexine, norbornane, norbornene, dicyclopentadiene, and 1-methyl-1,4-cyclohexadiene, 1-Heptin, 2-Heptin, Cycloheptane, Cycloheptene, 1,3-Dimethylcyclopentane, Ethylcyclopentane, Cyclohexane, 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-octine, 2-octine, 3-octine, 4-octine, 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-Hepten, 2,3-Dimethyl-3-Hepten, 2,4-Dimethyl-1-Hepten, 2,6-Dimethyl-1-Hepten, 2,6-Dimethyl-3-Hepten, 3,5-Dimethyl-3-Hepten, 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, hydroindane, 1,8-nonadiene, 1-nonine, 2-nonine, 3-nonine, 4-nonine, 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-decine, 2-decine, 3-decine, 4-decine, 5-decine, 1,5,9-decatriene, 2,6-dimethyl-2,4,6-octatriene, limonene, myrcene, 1,2,3,4,5-Pentamethylcyclopentadiene, α-Pelendrene, Pinene, Terpinene, Tetrahydrodicyclopentadiene, 5,6-Dihydrodicyclopentadiene, Dicyclopentadiene, 1,4-Decadine, 1,5-Decadine, 1,9-Decadine, 2,8-Decadine, 4,6-Decadine, n-Undecane, Amylcyclohexane, 1-Undecene, 1,10-Undecadiene, 1-Undecine, 3-Undecine, 5-Undecine, Tricyclo[6.2.1.0, 2,7Aliphatic hydrocarbon solvents such as ]undeca-4-ene, n-dodecane, 2-methylundecane, 3-methylundecane, 4-methylundecane, 5-methylundecane, 2,2,4,6,6-pentamethylheptane, 1,3-dimethyladamantan, 1-ethyladamantan, 1,5,9-cyclododecatriene, 1,2,4-trivinylcyclohexane, isoparaffin, etc., cyclohexanone, cyclopentanone, acetone, methyl ethyl ketone, 2-octanone, 2-nonanone, 2-heptanone, 3-heptanone, 4-heptanone, 2-hexanone, 3-hexanone, diisobutyl ketone, methylisobutyl ketone, methylcyclohexanone, methyl n-pentyl ketone, etc., Ethylene glycol dimethyl ether, propylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, diethylene glycol ethylmethyl ether, diethylene glycol butylmethyl ether, diethyl ether, diisopropyl ether, di-n-butyl ether, di-sec-butyl ether, diisobutyl ether, amyl ether, isoamyl ether, di-tert-amyl ether, methylcyclopentyl ether, methylcyclohexyl ether, methyl-tert-butyl ether, di-n-hexyl ether, ether-based solvents such as anisole, dihydroterpinyl acetate, tetrahydrofuran, and dioxane, 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 mono-tert-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, 3-methyl methoxypropionate, 3-ethyl ethoxypropionate, tert-butyl propionate, 3-methoxybutyl acetate,Examples include ester solvents such as ethyl-3-ethoxypropionate, lactone solvents such as γ-butyrolactone, nitrile solvents such as acetonitrile, halogen solvents such as methyl chloride, methylene chloride, chloroform, carbon tetrachloride, 1,2-dichloroethane, and 1,1,2,2-tetrachloroethane, and polar aproton solvents such as N-methylpyrrolidone, N,N'-dimethylformamide, N,N'-dimethylacetamide, dimethyl sulfoxide, and hexamethylphosphoramide.

[0229] In addition, the amount of organic solvent added is preferably in the range of 20 parts by mass or more and 500 parts by mass or less per 100 parts by mass of the total amount of polyurethane components (polyisocyanate, high molecular weight polyol, chain extender, crosslinking agent), and more preferably 25 parts by mass or more and 100 parts by mass or less.

[0230] The organic solvent may be removed after the polymerization reaction by vacuum removal or crystallization, or the polyurethane solution may be applied directly to the conductive paste composition without removal.

[0231] [catalyst]

[0232] In polyurethane synthesis, it is desirable to add a catalyst as needed to promote the urethane bond formation reaction.

[0233] As a urethane catalyst, it can be appropriately selected from known catalysts, and examples include amine-based catalysts, ammonium salt-based catalysts, potassium salt-based catalysts, organometallic catalysts, etc.

[0234] As amine-based catalysts, for example, triethylamine, N,N-dimethylcyclohexylamine, triethylenediamine, 2-methyltriethylenediamine, N,N,N',N'-tetramethylethylenediamine, N,N,N',N'-tetramethylpropylenediamine, N,N,N',N",N"-pentamethyldiethylenetriamine, N,N,N',N",N"-pentamethyl-(3-aminopropyl)ethylenediamine, N,N,N',N",N"-pentamethyldipropylenediamine, N,N,N',N'-tetramethylhexamethylenediamine, bis(2-dimethylaminoethyl)ether, dimethylethanolamine, dimethylisopropanolamine, dimethylaminoethoxyethanol, N,N-dimethylhexanolamine, N,N-dimethyl-N'-(2-hydroxyethyl)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-Methylimidazole, 1,2-Dimethylimidazole, 1-Isobutyl-2-methylimidazole, 1-Dimethylaminopropylimidazole, 1-(2-hydroxyethyl)imidazole, 1-(2-hydroxypropyl)imidazole, 1-(2-hydroxyethyl)-2-methylimidazole, 1-(2-hydroxypropyl)-2-methylimidazole You can lift the back.

[0235] Examples of ammonium salt-based catalysts include quaternary ammonium salts such as tetraethylhydroxylammonium, 1,8-diazabicyclo(5,4,0)-undecene-7 or 1,5-diazabicyclo(4,3,0)-nonene-5, and ammonium salts including octylic acid, oleic acid, p-toluenesulfonic acid, formic acid, phenolic acid, orthophthalic acid, acetic acid, maleic acid, or boric acid.

[0236] Examples of potassium salt-based catalysts include potassium carbonate, potassium acetate, and potassium octylate.

[0237] Examples of organometallic catalysts include organotin compounds such as tin acetate, tin octylate (2-ethylhexanoate), tin oleate, tin laurylate, dibutyltin diacetate, dimethyltin dilaurate, dibutyltin dilaurate, dibutyltin dimercaptide, dibutyltin maleate, dibutyltin dineodecanoate, dioctyltin dimercaptide, dioctyltin dilaurate, and dibutyltin dichloride; organolead compounds such as lead octanoate and lead naphthenate; organonickel compounds such as nickel naphthenate; organocobalt compounds such as cobalt naphthenate; organocopper compounds such as copper octate; and organobismuth compounds such as bismuth octylate and bismuth neodecanoate.

[0238] Since the polyurethane of the present invention contains weakly acidic functional groups, it is possible to inhibit the activity of basic catalysts, so it is preferable to use an organometallic catalyst, and more preferably, an organic bismuth compound can be used.

[0239] These urethane catalysts can be used alone or in combination of two or more types. In addition, the amount of urethane catalyst used is preferably in the range of 0 to 5 parts by mass per 100 parts by mass of the total amount of polyurethane components, and more preferably in the range of 0.1 to 2 parts by mass.

[0240] [Capje]

[0241] The polyurethane according to the present embodiment can introduce functional groups derived from the capping agent to the polyurethane terminals by adding a terminal capping agent after polymerizing with an excess of isocyanate groups.

[0242] For example, urethane acrylate can be synthesized by using the following hydroxyalkyl (meth)acrylate as a capping agent for the polyurethane terminals.

[0243]

[0244] (during food, R 5is a hydrogen atom or a methyl group, Et is an ethyl group, and Ph is a phenyl group. R 1 is the same as above.)

[0245] R 5 is a hydrogen atom or a methyl group.

[0246] Urethane acrylate can be polymerized and cured into a cured product by irradiating it with heat or active energy rays such as ultraviolet light, visible light, laser light, electron beam, X-ray, γ-ray, plasma, or microwave together with a reactive monomer and a polymerization initiator as needed.

[0247] As the above-mentioned reactive monomer, for example, alkyl (meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, t-butyl (meth)acrylate, isobutyl (meth)acrylate, isoamyl (meth)acrylate, lauryl (meth)acrylate, dodecyl (meth)acrylate, stearyl acrylate, cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, adamantyl (meth)acrylate, aryloxyalkyl (meth)acrylates such as phenoxymethyl (meth)acrylate, phenoxyethyl (meth)acrylate, benzyl (meth)acrylate, phenethyl (meth)acrylate, etc., (meth)acrylic acid aralkyl esters such as benzyl (meth)acrylate, phenethyl (meth)acrylate, etc. Single-action (meth)acrylate compounds such as phenyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 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, 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, Tri(meth)acrylates such as 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, and glycerin tri(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol tri(meth)acrylate, ditrimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, and dipentaerythritol penta(meth)acrylate,Multifunctional (meth)acrylate compounds such as ditrimethylolpropane penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, and ditrimethylolpropane hexa(meth)acrylate, or their ethyleneoxy modified, propyleneoxy modified, or lactone modified products, may be used. These may be used alone or in combination of two or more types.

[0248] As the above polymerization initiator, for example, acetophenone, 2,2-diethoxyacetophenone, p-dimethylaminoacetophenone, benzophenone, 2-chlorobenzophenone, 4,4'-bisdiethylaminobenzophenone, benzoin ethyl ether, benzoin-n-propyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin-n-butyl ether, benzoin dimethyl ketal, thioxanthone, p-isopropyl-α-hydroxyisobutylphenone, 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, Examples include 2,4,6-trimethylbenzophenone, 4-methylbenzophenone, (2,4,6-trimethylbenzoyl)-diphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, 2,2-dimethoxy-1,2-diphenylethanolone, but preferably 1-hydroxycyclohexylphenylketone and bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide are used. These may be used alone or in combination of two or more types.

[0249] In addition, the phenolic hydroxyl group may be introduced into the polyurethane using an alcohol or amine represented by the following general formula (1C) after the chain extension reaction.

[0250]

[0251] (In the formula, Az" represents a straight-chain, branched, or cyclic (ka+2) hydrocarbon group having 1 to 19 carbon atoms, or a fluorinated hydrocarbon group, and the -CH2- constituting the (ka+2) hydrocarbon group is -O-, -C(=O)-, or -Si(R2 R 3 It may be substituted with ). X is an oxygen atom or NR 4 Represents. ka represents an integer from 0 to 2. kb, kc, kd, and ke represent 1 or 2. R 2 , R 3 , R 4 is the same as above.)

[0252] Az" represents a straight-chain, branched, or cyclic (ka+2) hydrocarbon group having 1 to 19 carbon atoms, or a fluorinated hydrocarbon group, wherein the -CH2- constituting the (ka+2) hydrocarbon group is -O-, -C(=O)-, or -Si(R 2 R 3 It may be replaced with )-.

[0253] X is an oxygen atom or NR 4 It represents.

[0254] ka represents an integer from 0 to 2, and kb, kc, kd, and ke represent 1 or 2.

[0255] R 2 , R 3 , R 4 It is the same as above.

[0256] The straight, branched, or cyclic (ka+2) hydrocarbon groups of the above Az" having 1 to 19 carbon atoms can be specifically given as the following examples.

[0257]

[0258] (In the formula, dashed lines indicate joint loss.)

[0259]

[0260] (In the formula, dashed lines indicate joint loss.)

[0261]

[0262] (In the formula, dashed lines indicate joint loss.)

[0263] The following are examples of specific examples of alcohols or amines represented by the above general formula (1C), but are not limited to these.

[0264]

[0265] (In the formula, X is an oxygen atom or NR 4 Represents, and R 4 is the same as above.)

[0266]

[0267] (In the formula, X is an oxygen atom or NR 4 Represents, and R 4 is the same as above.)

[0268]

[0269] (In the formula, X is an oxygen atom or NR 4 Represents, and R 4 is the same as above.)

[0270] It is preferable to use the above-mentioned capping agent having a phenolic hydroxyl group in an amount of 1 to 20 mass% relative to the total amount of the urethane components, and more preferable to use an amount of 1 to 5 mass%.

[0271] The reaction temperature during polyurethane synthesis is appropriately changed depending on the type of reaction substrate, but typically 30 to 200°C is preferred, and 40 to 120°C is more preferred.

[0272] The weight average molecular weight of the polyurethane is preferably 10,000 to 500,000, and more preferably 15,000 to 200,000. Even more preferably, it is 20,000 to 150,000. The weight average molecular weight (Mw) is measured as a polystyrene equivalent value by gel permeation chromatography (GPC).

[0273] The polyurethane according to the present embodiment may also include, if necessary, an antioxidant, an antifoaming agent, a UV absorber, etc. as an additive.

[0274] Conductive Paste Composition

[0275] The conductive paste composition of the present invention comprises (A) a conductive filler, (B) a polyurethane containing phenolic hydroxyl groups of the present invention, and (C) a solvent, and additionally preferably comprises (D) a phenolic compound. Each component will be described in more detail below.

[0276] [(A) Conductive Filler]

[0277] As a component (A) for increasing electrical conductivity, metal particles or alloy particles such as gold, silver, platinum, copper, tin, iron, magnesium, titanium, nickel, palladium, aluminum, tungsten, molybdenum, ruthenium, chromium, indium, solder and their silver plating powders, or powders such as carbon, carbon black, carbon nanotubes, silver chloride, zinc oxide, titanium oxide, indium tin oxide, etc. may be used.

[0278] From the perspective of conductivity, gold, silver, and platinum are desirable, and from the perspective of price, silver, copper, tin, iron, titanium, nickel, aluminum, tungsten, molybdenum, ruthenium, chromium, and stainless steel are desirable, and overall, silver (silver powder) is the most desirable.

[0279] Examples of particle shapes for conductive fillers include spherical, granular, angular, tree-branched, flake-shaped, needle-shaped, and irregular shapes, and multiple types of fillers can also be used in combination.

[0280] The average particle size of the conductive filler is not particularly limited, but it is preferably 5 nm to 10 µm.

[0281] The method for measuring the average particle size is not particularly limited, but, for example, it can be measured using a laser diffraction particle size distribution device.

[0282] It is preferable that the amount of conductive filler added be at a ratio of more than 70 parts by mass per 100 parts by mass of the total of (A) conductive filler and (B) polyurethane containing phenolic hydroxyl groups, and more preferably at least 80 parts by mass and no more than 90 parts by mass.

[0283] [(B) Polyurethane containing phenolic hydroxyl groups]

[0284] Examples of polyurethanes containing phenolic hydroxyl groups include those described above.

[0285] Polyurethane containing phenolic hydroxyl groups may be used as a single type or as a mixture of multiple types. In addition, a portion of the polyurethane containing phenolic hydroxyl groups may be replaced with polyurethane that does not contain phenolic hydroxyl groups.

[0286] The content of polyurethane not containing phenolic hydroxyl groups is preferably 0 to 30 mass% with respect to the total amount of polyurethane containing phenolic hydroxyl groups and polyurethane not containing phenolic hydroxyl groups.

[0287] It is preferable that the polyurethane containing the above-mentioned phenolic hydroxyl group additionally includes the weakly acidic functional group described above.

[0288] When the conductive filler is a metal particle or an alloy particle, particularly silver powder, it is presumed that the conductive paste composition of the present invention forms a silver salt through the oxide film of the silver powder and the phenolic hydroxyl group or weak acid functional group in the polyurethane, and that silver nanoparticles are produced by reducing the silver salt by heat. At this time, it is thought that if the functional group exhibits strong acidity, the formed silver salt becomes stable, making it difficult for reduction by heat to proceed, and if the acid is weak, it is difficult to form a silver salt, making it difficult to produce silver nanoparticles. Therefore, it is thought that by using a polyurethane containing a functional group having appropriate acidity, the formation of the silver salt and the reduction of the silver salt become possible even with firing at a relatively low temperature, making it easier to produce silver nanoparticles.

[0289] [(C) Solvent]

[0290] Component (C) is a solvent. By including component (C), the viscosity of the conductive paste composition becomes suitable, thereby improving workability.

[0291] (C) As a solvent of component, specifically, toluene, xylene, cumene, 1,2,3-trimethylbenzene, 1,2,4-trimethylbenzene, 1,3,5-trimethylbenzene, styrene, α-methylstyrene, butylbenzene, sec-butylbenzene, isobutylbenzene, cymene, 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-amylbenzene, amylbenzene, 2-tert-butyltoluene, 3-tert-butyltoluene, 4-tert-butyltoluene, 5-isopropyl-m-xylene, Aromatic hydrocarbon solvents such as 3-methylethylbenzene, tert-butyl-3-ethylbenzene, 4-tert-butyl-o-xylene, 5-tert-butyl-m-xylene, tert-butyl-p-xylene, 1,2-diisopropylbenzene, 1,3-diisopropylbenzene, 1,4-diisopropylbenzene, dipropylbenzene, pentamethylbenzene, hexamethylbenzene, hexylbenzene, and 1,3,5-triethylbenzene, n-heptane, isoheptane, 3-methylhexane, 2,3-dimethylpentane, 3-ethylpentane, 1,6-heptadiene, 5-methyl-1-hexine, norbornane, norbornene, dicyclopentadiene, 1-methyl-1,4-cyclohexadiene, and 1-heptine, 2-Heptine, Cycloheptane, Cyclohepten, 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-Hepten, 2-Hepten, 3-Hepten, 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-octine, 2-octine, 3-octine, 4-octine, 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, hydroindane, 1,8-nonadiene, 1-nonine, 2-nonine, 3-nonine, 4-nonine, 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-decadien, decahydronaphthalene, 1-decine, 2-decine, 3-decine, 4-decine, 5-decine, 1,5,9-decatriene, 2,6-dimethyl-2,4,6-octatriene, limonene, myrcene, 1,2,3,4,5-pentamethylcyclopentadiene, α-phelendrene, pinene, terpinene, tetrahydrodicyclopentadiene, 5,6-Dihydrodicyclopentadiene, dicyclopentadiene, 1,4-decadine, 1,5-decadine, 1,9-decadine, 2,8-decadine, 4,6-decadine, n-undecane, amylcyclohexane, 1-undecene, 1,10-undecadine, 1-undecin, 3-undecin, 5-undecin, tricyclo[6.2.1.0, 2,7Aliphatic hydrocarbon solvents such as ]undeca-4-ene, n-dodecane, 2-methylundecane, 3-methylundecane, 4-methylundecane, 5-methylundecane, 2,2,4,6,6-pentamethylheptane, 1,3-dimethyladamantan, 1-ethyladamantan, 1,5,9-cyclododecatriene, 1,2,4-trivinylcyclohexane, isoparaffin, etc., ketone solvents such as cyclohexanone, cyclopentanone, 2-octanone, 2-nonanone, 2-heptanone, 3-heptanone, 4-heptanone, 2-hexanone, 3-hexanone, diisobutylketone, methylcyclohexanone, methyl n-pentylketone, methylisobutylketone, isophorone, etc., Alcohol-based solvents such as 3-methoxybutanol, 3-methyl-3-methoxybutanol, 1-methoxy-2-propanol, and 1-ethoxy-2-propanol, 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, diisopentyl ether, di-n-pentyl ether, methylcyclopentyl ether, methylcyclohexyl ether, di-n-butyl ether, di-sec-butyl ether, di-sec-pentyl ether, di-tert-amyl ether, Ether-based solvents such as di-n-hexyl ether and anisole, ester-based 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, propylene glycol monotert-butyl ether acetate, lactone-based solvents such as γ-butyrolactone, α-terpineol, α-pinene, and dihydroterpineol,Examples include terpene-based solvents such as dihydroterpinyl acetate. The solvent may be used alone or a mixture of two or more types.

[0292] Diethylene glycol monobutyl ether, diethylene glycol monoethyl ether acetate, and diethylene glycol monobutyl ether acetate are particularly preferred because the solvent is difficult to volatilize during printing and provides a viscosity suitable for printing.

[0293] The amount of solvent (organic solvent) added is preferably in the range of 100 to 1,000 parts by mass per 100 parts by mass of (B) polyurethane.

[0294] [(D) Phenolic Compounds]

[0295] In addition, it is preferable to include a phenol compound having a structure represented by the following general formula (2A) as a phenol compound.

[0296]

[0297] (during food, R 6 represents a hydrogen atom, a halogen atom, a cyano group, or a hydroxyl group. Ay represents a straight-chain, branched, or cyclic (ka+2) hydrocarbon group having 1 to 20 carbon atoms, or a fluorinated hydrocarbon group, wherein the -CH2- constituting the (ka+2) hydrocarbon group is -O-, -C(=O)-, or -Si(R 2 R 3 It may be substituted with ). 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 is the same as above.)

[0298] R 6 It represents a hydrogen atom, a halogen atom, a cyano group, or a hydroxyl group.

[0299] Ay represents a straight-chain, branched, or cyclic (ka+2) hydrocarbon group having 1 to 20 carbon atoms, or a fluorinated hydrocarbon group, wherein the -CH2- constituting the (ka+2) hydrocarbon group is -O-, -C(=O)-, or -Si(R 2 R 3 It may be substituted with )-. Specifically, the following may be exemplified as straight-chain, branched, or cyclic (ka+2) hydrocarbon groups of Ay having 1 to 20 carbon atoms.

[0300]

[0301] (In the formula, dashed lines indicate joint loss.)

[0302]

[0303] (In the formula, dashed lines indicate joint loss.)

[0304]

[0305] (In the formula, dashed lines indicate joint loss.)

[0306] Specifically, examples of straight, branched, or cyclic (ka+2) fluorinated hydrocarbon groups having 1 to 20 carbon atoms of Ay can be given in which some or all of the hydrogen atoms in the above hydrocarbon groups are substituted with fluorine atoms.

[0307] 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.

[0308] Z, Xf, ZZ, R 2 , R 3 It is the same as above.

[0309] As for the phenol compound represented by the above general formula (2A), it is particularly preferable that it be a phenol compound represented by the following general formula (2B).

[0310]

[0311] (In the formula, Ay' represents a straight-chain, branched, or cyclic (ka+2) hydrocarbon group having 1 to 19 carbon atoms, or a fluorinated hydrocarbon group, and the -CH2- constituting the (ka+2) hydrocarbon group is -O-, -C(=O)-, or -Si(R 2 R 3 It may be substituted with ). ka represents an integer from 0 to 2. kb, kc, kd, and ke represent 1 or 2. R 2 , R 3 , R 6 is the same as above.)

[0312] Ay' represents a straight-chain, branched, or cyclic (ka+2) hydrocarbon group having 1 to 19 carbon atoms, or a fluorinated hydrocarbon group, wherein the -CH2- constituting the (ka+2) hydrocarbon group is -O-, -C(=O)-, or -Si(R 2 R 3 It may be replaced with )-.

[0313] ka represents an integer from 0 to 2, and kb, kc, kd, and ke represent 1 or 2.

[0314] R 2 , R 3 , R 6 It is the same as above.

[0315] Specifically, the following compounds represented by the above general formulas (2A) and (2B) can be exemplified.

[0316]

[0317]

[0318]

[0319]

[0320]

[0321]

[0322]

[0323]

[0324]

[0325]

[0326]

[0327]

[0328]

[0329] The synthesis method of phenol compounds represented by the above general formulas (2A) and (2B) is not particularly limited and can be synthesized by selecting the optimal method according to the structure, but for example, in the case of the general formula (2Ba) in which kb and kc in formula (2B) are 1, it can be synthesized by steps i) to v) shown in the reaction scheme below.

[0330]

[0331] (during food, R 6 , Ay', ka, kc, and ke are as described above. Rp represents an acid unstable group. XA represents a halogen atom.)

[0332] Step i) is a process of inducing an intermediate aryl halogenated compound (2Bd) by protecting a halogenated phenol compound (2Bb).

[0333] The reaction of step i) proceeds easily under known conditions, but, for example, when Rp is a tertiary alkyl group such as a t-butyl group, t-amyl group, methylcyclopentyl group, ethylcyclopentyl group, methylcyclohexyl group, ethylcyclohexyl group, methyladamantyl group, ethyladamantyl group, etc., it is preferable to carry out the reaction of the halogenated phenol compound (2Bb) and the olefin corresponding to Rp, such as isobutene, isoamylene, etc., in the presence of an acid catalyst at a reaction temperature of -20 to 50°C in a solvent-free solvent or a solvent such as toluene, hexane, etc. Examples of acid catalysts used include inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, perchloric acid, etc., and organic acids such as methanesulfonic acid, trifluoromethanesulfonic acid, p-toluenesulfonic acid, benzenesulfonic acid, etc.

[0334] Step ii) is a process of inducing an intermediate aryl halide compound (2Bd) by a nucleus substitution reaction of a fluorobenzene compound (2Bc).

[0335] The reaction of step ii) proceeds easily under known conditions, but, for example, when Rp is a tertiary alkyl group such as t-butyl group, t-amyl group, methylcyclopentyl group, ethylcyclopentyl group, methylcyclohexyl group, ethylcyclohexyl group, methyladamantyl group, ethyladamantyl group, etc., it is preferable to carry out the reaction at a reaction temperature of 10 to 80°C in the presence of a base, with the fluorobenzene compound (2Bc) and the alcohol corresponding to Rp, such as t-butyl alcohol, t-amyl alcohol, etc., or the corresponding alkoxide, such as t-butoxypotassium, in a solvent such as tetrahydrofuran, N-methyl-2-pyrrolidone. 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 trithyllithium, trithyl sodium, trithyl 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.

[0336] Step iii) is a process of inducing an intermediate phenol compound (2Be) by oxidizing an aryl halide compound (2Bd).

[0337] The reaction proceeds easily by known methods, but, for example, the method of the following reaction equation can be exemplified.

[0338]

[0339] (In the formula, Rp, ke, and XA are as described above. MA represents Li, MgCl, MgBr, and MgI. R r ...represents a straight, branched, or cyclic monovalent hydrocarbon group having 1 to 6 carbon atoms.

[0340] First, an organometallic reagent (2Bg) is prepared with an aryl halide compound (2Bd) and Li or Mg in a solvent such as tetrahydrofuran or diethyl ether. Subsequently, an arylboronic acid derivative (2Bh) is produced by reaction with a boric acid ester compound (2J), and finally, an intermediate phenol compound (2Be) is obtained using an oxidizing agent such as hydrogen peroxide, performic acid, peracetic acid, or m-chloroperbenzoic acid. This process can be carried out in a single pot without undergoing a conventional purification process.

[0341] Step iv) is a process of inducing an aryl ether compound (2Bf) by etherification of an intermediate phenol compound (2Be).

[0342] The reaction proceeds easily by known methods, but, for example, the method of the following reaction equation can be exemplified.

[0343]

[0344] (In the formula, Rp, ka, ke, and Ay' are as stated above. T 1 Each represents an independent hydroxyl group, halogen atom, alkanesulfonyloxy group, or arenesulfonyloxy group.

[0345] As an etherification method, a method of etherifying by treating an intermediate phenol compound (2Be) and a degreasing compound (2Bi) with a base can be exemplified.

[0346] T 1 Chlorine, bromine, and iodine atoms can be examples of halogen atoms. In addition, T 1 Examples of alkansulfonyloxy groups and arenesulfonyloxy groups include methanesulfonyloxy, trifluoromethanesulfonyloxy, benzenesulfonyloxy, and p-toluenesulfonyloxy.

[0347] Specifically, as bases used, alkoxides such as sodium methoxide, sodium ethoxide, lithium methoxide, lithium ethoxide, lithium tert-butoxide, and potassium tert-butoxide; 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 tetra-n-butylammonium hydroxide; inorganic carbonates such as sodium carbonate, sodium bicarbonate, lithium carbonate, and potassium carbonate; metal hydrides such as boranes, alkylboranes, sodium hydride, lithium hydride, potassium hydride, and calcium hydride; alkyl metal compounds such as trithyllithium, trithyl sodium, trithyl potassium, methyllithium, phenyllithium, sec-butyllithium, tert-butyllithium, methyl magnesium chloride, ethyl magnesium chloride, and ethyl magnesium bromide; and sodium amide. Examples of metal amides include potassium amide, lithium diisopropylamide, potassium diisopropylamide, lithium dicyclohexylamide, potassium dicyclohexylamide, lithium 2,2,6,6-tetramethylpiperidine, lithium bistrimethylsilylamide, sodium bistrimethylsilylamide, potassium bistrimethylsilylamide, lithium isopropylcyclohexylamide, bromomagnesium diisopropylamide, etc. The amount of base used is preferably 0.9 to 10 moles, particularly 1.0 to 5.0 moles, per 1 mole of intermediate phenol compound (2Be).

[0348] As a solvent, 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, isopropyl alcohol, and tert-butyl alcohol; aprotic polar solvents such as dimethyl sulfoxide (DMSO) and N,N-dimethylformamide (DMF); and chlorine-based organic solvents such as methylene chloride, chloroform, and carbon tetrachloride may be selected according to reaction conditions and used alone or in combination. The above-mentioned base itself may also be used as a solvent.

[0349] The reaction temperature and time vary widely depending on the reagents and conditions, but for example, T 1 When carrying out the reaction using potassium carbonate as the base for the bromine atom, the reaction temperature is preferably room temperature to 120°C, preferably 30°C to 90°C, as this allows for rapid completion of the reaction. The reaction time is typically 1 to 60 hours, although it is preferable to complete the reaction by tracking the reaction with gas chromatography (GC) or silica gel thin-layer chromatography (TLC) for yield purposes. An aryl ether compound (2Bf) can be obtained from the reaction mixture by conventional aqueous work-up, and if necessary, it can be purified by conventional methods such as distillation and chromatography.

[0350] Step v) is a process of inducing the phenol compound of the present invention by deprotection reaction of the aryl ether compound (2Bf).

[0351] As a solvent, hydrocarbons such as toluene, xylene, hexane, and heptane; chlorine-based solvents such as methylene chloride, 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; nitriles such as acetonitrile; alcohols such as methanol and ethanol; non-protonic polar solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, and dimethyl sulfoxide; and water may be selected and used alone or in a mixture of two or more. In addition, the reaction may be carried out without a solvent.

[0352] As for the acid, 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, trimethylsilyltriplate, aluminum chloride, magnesium chloride, iron chloride, zinc chloride, and titanium chloride may be used. In addition, the amount of acid used is preferably 0.001 to 5 moles, particularly 0.01 to 0.5 moles, per 1 mole of aryl ether compound (2Bf). If more than 0.001 moles are used, the reaction rate is not slowed down, so it does not become a disadvantage in terms of cost due to increased reaction time, and if 5 moles or less are used, side reactions due to strong acidity do not occur, and the yield does not decrease. In addition, to suppress acidity, bases such as ammonia, triethylamine, pyridine, rutidine, colidine, N,N-dimethylaniline, and amines may be added.

[0353] For the above deprotection reaction, an appropriate reaction temperature can be selected depending on the reaction conditions, but since the reaction may not proceed under low temperature conditions, a temperature of typically 40 to 120°C is preferred. In addition, to improve the yield, it is preferable to determine the reaction time by tracking the progress of the reaction using thin-layer chromatography, gas chromatography, etc., but it is typically about 2 hours to 1 day. The reaction can be carried out by diluting the aryl ether compound (2Bf) with a solvent, adding an acid, and heating and stirring. After the reaction is finished, the phenol compound of the present invention can be obtained by conventional aqueous work-up, and if necessary, it can be purified by conventional methods such as distillation, recrystallization, and chromatography.

[0354] When the above phenol compound is incorporated into the conductive paste composition of the present invention, it is preferable to have a range of more than 0.5 parts by mass per 100 parts by mass of the total of (A) the conductive filler, (B) the polyurethane containing phenolic hydroxyl groups, and (D) the phenol compound, and more preferably 1 part by mass or more and 10 parts by mass or less.

[0355] The above phenolic compound has the same effect as the phenolic hydroxyl group and weak acidic functional group in the polyurethane of the present invention. That is, when the conductive filler is a metal particle or alloy particle, particularly silver powder, it is presumed that a silver salt is formed by the phenolic hydroxyl group of the phenolic compound and the oxide film of the silver powder, and that silver nanoparticles are produced by reducing the silver salt by heat. In particular, it is thought that a phenolic compound having an electron-removing group on the aromatic ring has improved acidity compared to a non-functional phenol, making it easier to form a silver salt, and thus making it easier to produce silver nanoparticles even at low temperatures. Then, when the phenolic compound is a phenolic compound of the above general formula (2B), it has a fluorine atom on the aromatic ring, and it is presumed that a nucleus substitution reaction proceeds by the silver salt, and that silver nanoparticles are produced by reducing the silver fluoride produced as a byproduct in the process by heat, etc.

[0356] <Challenge Wiring>

[0357] In addition, the present invention provides a conductive wiring comprising a sintered product of the conductive paste composition formed on a substrate. If the substrate has elasticity, an elastic conductive wiring is provided.

[0358] The conductive wiring of the present invention will be described below, but the present invention is not limited to these.

[0359] Examples of substrates for forming conductive wiring include polyurethane, polyester, silicone, nitrile rubber, butadiene rubber, polyethylene, polypropylene, polyolefin, PTFE, PFA, etc. It is preferable for the substrate to have elasticity, and it is more preferable for an elastic sheet or film to be elastic, and even more preferably for an elastic polyurethane substrate, and particularly preferably for a thermoplastic polyurethane substrate. The surface of the sheet may be flat, but it may also have irregularities. If irregularities are present, a corrugated box structure of elastic wiring can be formed in a direction perpendicular to the substrate, and changes in conductivity during stretching can be suppressed. In addition, a non-woven fabric or a cloth containing elastic fibers may be used.

[0360] It is desirable for the elastic material to have a maximum elasticity of 1000%. The elongation of the skin in response to human movement is considered to be 10% above bones such as the chest, 20% above the abdomen, and 50% at joints, and the elasticity required for conductive wiring varies depending on the part that adheres to the skin.

[0361] The following description applies to cases where a flexible material (flexible material) is used, but the same applies to materials that do not have flexibility and is not limited to the following.

[0362] Conductive wiring is formed on a flexible substrate using the conductive paste composition of the present invention. The method of forming conductive wiring on the flexible substrate is not particularly limited, but methods such as dip coating, spray coating, spin coating, roll coating, flow coating, doctor coating, screen printing, flexographic printing, gravure printing, and inkjet printing are suitable. In particular, by forming a wiring pattern by printing, productivity can be improved, and a free design including the wiring width becomes possible.

[0363] The film thickness of the conductive wiring is preferably in the range of 10 nm to 1000 μm. More preferably, it is 5 to 50 μm.

[0364] A conductive paste composition is applied to a flexible substrate by printing, and then fired. That is, conductive wiring is formed on the substrate by printing the conductive paste composition. When forming the conductive wiring, the firing temperature is in the range of 60 to 160°C, preferably 120°C to 150°C, and the time is from 1 second to 10 hours, preferably 10 minutes to 5 hours. Firing can be performed in a hot plate or oven, but it can also be performed in a short time at a higher temperature than the above temperature by flash annealing, or firing can be performed by irradiation with infrared light.

[0365] Conductivity can be evaluated by forming a flexible conductive wire on a substrate and measuring the electrical resistance between the two ends of the wire. A flexible conductive wire can be described as superior if the change in electrical resistance before and during stretching of the substrate, and the deterioration in conductivity when the stretched substrate is shrunk back to its original state, is minimal. Furthermore, it is desirable to have a small change in electrical resistance without wire breakage when subjected to repeated stretching.

[0366] In addition, the conductive wiring of the present invention preferably has an electrical resistance of 500% or less of the electrical resistance before stretching when stretched by 20%, and regarding the lower limit, it is not particularly limited and is preferably lower, but for example, it can be 150% or more. It is also preferable that the maximum electrical resistance when stretched 1,000 times repeatedly at a stretching rate of 20% is 5,000% or less of the electrical resistance before stretching, and regarding the lower limit, it is not particularly limited and is preferably lower, but for example, it can be 300% or more. The above electrical resistance can be obtained by the measurement method described later.

[0367] Furthermore, a cover film may be installed to cover the conductive wiring. By installing the cover film, water resistance or mechanical strength can be improved. Since both the substrate and the conductive wiring have elasticity, the cover film also needs to have elasticity. The material of the cover film can be selected from polyurethane, urethane acrylate, polyester, silicone, nitrile rubber, butadiene rubber, polyethylene, polypropylene, polyolefin, PTFE, PFA, etc., just like the substrate. The thickness of the cover film is preferably in the range of 10 nm to 1 mm.

[0368] A conductive wiring formed using the conductive paste composition of the present invention, particularly when it contains silver powder, exhibits high conductivity as silver nanoparticles generated during the firing process of the wiring are dispersed within the insulating polymer between the silver powder bodies. Furthermore, even when the wiring is extended and the distance between the silver powder bodies widens, the conductive path is difficult to cut due to the silver nanoparticles dispersed between the silver powder bodies, so it is difficult for the wire to break and the change in conductivity is reduced.

[0369] Examples

[0370] The present invention will be specifically described below using synthetic examples, examples, and comparative examples, but the present invention is not limited thereto. In addition, the weight average molecular weight (Mw) and number average molecular weight (Mn) were measured as polystyrene equivalent values ​​by gel permeation chromatography (GPC). The measurement conditions for GPC are as follows.

[0371] Column: TSKgel G4000H XL , TSKgel G3000H XL , TSKgel G2000H XL 2 pieces

[0372] Mobile phase: Tetrahydrofuran

[0373] Column oven temperature: 40℃

[0374] Sample concentration: 0.20 mass%

[0375] Sample injection volume: 100 μL

[0376] Flow rate: 1 mL / min

[0377] Polyurethane containing phenolic hydroxyl groups was synthesized as follows.

[0378] [1] Synthesis of phenolic hydroxyl group-containing caps

[0379] [Synthesization Example 1-1] Synthesis of Cap 1

[0380]

[0381] [Synthesization Example 1-1-1] Synthesis of Bromobenzene 1

[0382] Under a nitrogen atmosphere, methanesulfonic acid (4.8 g) was added to a toluene (10 g) solution of bromophenol 1 (76.4 g) and isoamylene (112.2 g) at -20 to -10°C. After stirring at the same temperature for 3 hours, triethylamine (10.1 g) was added dropwise, followed by 25 mass% caustic soda water (32.0 g), to stop the reaction. Conventional aqueous work-up was performed. Bromobenzene 1 (84.6 g, yield 81%) was obtained by vacuum distillation.

[0383] Boiling point: 67℃ / 10 Pa.

[0384] [Synthesization Example 1-1-2] Synthesis of Intermediate Phenol 1

[0385] Under a nitrogen atmosphere, a Grignard reagent prepared in advance using bromobenzene 1 (52.2 g), magnesium (5.1 g), and 140 mL of tetrahydrofuran was added dropwise to a solution of trimethyl borate (22.9 g) and tetrahydrofuran (310 mL) at an internal temperature of -5°C or lower. Stirring was continued for 3 hours at a reaction temperature of 5°C. Subsequently, acetic acid (18.0 g) and 35% hydrogen peroxide (25.3 g) were added at an internal temperature of 30°C or lower. Stirring was continued for 3 hours at room temperature, followed by a standard post-treatment method, and recrystallization was performed from a toluene / n-hexane mixed solvent to obtain the intermediate phenol 1 (29.7 g, yield 75%).

[0386] 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, 816 cm -1 .

[0387] 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.

[0388] 19 F-NMR (565MHz in DMSO-d6): δ=-126.6(1F, s) ppm.

[0389] [Synthesization Example 1-1-3] Synthesis of Protected Phenol 1

[0390] Under a nitrogen atmosphere, etherifying agent 1 (36.9 g) was added to a slurry solution of intermediate phenol 1 (29.5 g), potassium carbonate (20.5 g), sodium iodide (40 mg), and dimethylformaldehyde (74 g) at 60–80°C. After stirring at the same temperature for 20 hours, water (160 g) was added dropwise to stop the reaction. A normal aqueous work-up was performed to obtain protected phenol 1 (53.2 g, crude yield 91%).

[0391] [Synthesization Example 1-1-4] Synthesis of Cap 1

[0392] The solution of the above-mentioned protected phenol 1 (53.2 g), p-toluenesulfonic acid monohydrate (0.2 g), and toluene (140 g) was heated and stirred for 3 hours at an internal temperature of 70 to 100°C. Afterward, 50 g of water was added at an internal temperature of 30°C or lower to stop the reaction. Subsequently, a normal aqueous work-up was performed, and recrystallization was carried out using an ethyl acetate / n-hexane mixed solvent to obtain capping agent 1 (31.6 g, 2 process yield 71%).

[0393] 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, 788 cm -1 .

[0394] 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.

[0395] 19F-NMR (565MHz in DMSO-d6): δ=-133.7(1F, t) ppm.

[0396] [Synthesization Example 1-2] Synthesis of Cap 2

[0397]

[0398] [Synthesization Example 1-2-1] Synthesis of Bromobenzene 2

[0399] Under a nitrogen atmosphere, fluorobenzene 1 (100 g) was added dropwise at 0–10°C to a solution of t-butoxypotassium (63.9 g) dissolved in THF (360 g). After stirring at the same temperature for 10 hours, water (150 g) was added dropwise to stop the reaction. Conventional aqueous work-up was performed. Bromobenzene 2 (98.6 g, yield 77%) was obtained by vacuum distillation.

[0400] Boiling point: 97-100℃ / 700 Pa.

[0401] [Synthesization Example 1-2-2] Synthesis of Intermediate Phenol 2

[0402] Intermediate phenol 2 was obtained by the same method as in [Synthesization Example 1-1-2], except that bromobenzene 1 was changed to bromobenzene 2 (yield 77%).

[0403] [Synthesization Example 1-2-3] Synthesis of Protected Phenol 2

[0404] Protected phenol 2 was obtained by the same method as in [Synthesization Example 1-1-3], except that intermediate phenol 1 was changed to intermediate phenol 2 (yield 92%).

[0405] [Synthesization Example 1-2-4] Synthesis of Cap 2

[0406] Cap 2 was obtained in the same manner as [Synthetic Example 1-1-4], except that protected phenol 1 was changed to protected phenol 2 (yield 78%).

[0407] [Synthesized Example 1-3] Synthesis of Cap 3

[0408]

[0409] [Synthesization Example 1-3-1] Synthesis of Bromobenzene 3

[0410] Bromobenzene 3 was obtained in the same manner as [Synthesization Example 1-1-1], except that bromophenol 1 was changed to bromophenol 3 (yield 77%).

[0411] Boiling point: 66℃ / 6 ​​Pa.

[0412] [Synthesization Example 1-3-2] Synthesis of Intermediate Phenol 3

[0413] Intermediate phenol 3 was obtained in the same manner as in [Synthetic Example 1-1-2], except that bromobenzene 1 was changed to bromobenzene 3 (yield 62%).

[0414] [Synthesization Example 1-3-3] Synthesis of Protected Phenol 3

[0415] Protected phenol 3 was obtained by the same method as in [Synthesization Example 1-1-3], except that intermediate phenol 1 was changed to intermediate phenol 3 (yield 82%).

[0416] [Synthesization Example 1-3-4] Synthesis of Cap 3

[0417] Except for changing protected phenol 1 to protected phenol 3, cap 3 was obtained in the same manner as [Synthetic Example 1-1-4] (yield 92%).

[0418] IR(D-ATR): ν=3494, 3215, 2932, 2918, 2849, 1613, 1526, 1503, 1480, 1470, 1434, 1400, 1287, 1264, 1212, 1183, 1091, 1077, 1054, 1020, 1004, 967, 942, 804 cm -1 .

[0419] 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.

[0420] 19 F-NMR (565MHz in DMSO-d6): δ=-158.1∼-157.9(1F, m), -159.3∼-159.1(1F, m) ppm.

[0421] [Synthesization Example 1-4] Synthesis of Cap 4

[0422]

[0423] [Synthesization Example 1-4-1] Synthesis of Bromobenzene 4

[0424] Bromobenzene 4 was obtained by the same method as in [Synthesization Example 1-1-1], except that bromophenol 1 was changed to bromophenol 4 (yield 72%).

[0425] Boiling point: 53℃ / 15 Pa.

[0426] [Synthesization Example 1-4-2] Synthesis of Intermediate Phenol 4

[0427] Intermediate phenol 4 was obtained by the same method as in [Synthetic Example 1-1-2], except that bromobenzene 1 was changed to bromobenzene 4 (yield 64%).

[0428] 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.

[0429] 19 F-NMR (565MHz in DMSO-d6): δ=-122.9(2F, s) ppm.

[0430] [Synthesization Example 1-4-3] Synthesis of Protected Phenol 4

[0431] Protected phenol 4 was obtained in the same manner as in [Synthesization Example 1-1-3], except that intermediate phenol 1 was changed to intermediate phenol 4 (yield 89%).

[0432] [Synthesization Example 1-4-4] Synthesis of Cap 4

[0433] Cap 4 was obtained in the same manner as [Synthetic Example 1-1-4], except that protected phenol 1 was changed to protected phenol 4 (yield 73%).

[0434] 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, 804 cm -1 .

[0435] 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.

[0436] 19 F-NMR (565MHz in DMSO-d6): δ=-158.1(1F, m) ppm.

[0437] [Synthesization Example 1-5] Synthesis of Cap 5

[0438]

[0439] [Synthesization Example 1-5-1] Synthesis of Bromobenzene 5

[0440] Bromobenzene 5 was obtained in the same manner as [Synthesization Example 1-2-1], except that fluorobenzene 1 was changed to fluorobenzene 2 (yield 94%).

[0441] Boiling point: 82-84℃ / 300 Pa.

[0442] [Synthesization Example 1-5-2] Synthesis of Intermediate Phenol 5

[0443] Intermediate phenol 5 was obtained in the same manner as in [Synthetic Example 1-1-2], except that bromobenzene 1 was changed to bromobenzene 5 (yield 62%).

[0444] [Synthesization Example 1-5-3] Synthesis of Protected Phenol 5

[0445] Except for changing intermediate phenol 1 to intermediate phenol 5, protected phenol 5 was obtained by the same method as in [Synthetic Example 1-1-3] (yield 81%).

[0446] [Synthesization Example 1-5-4] Synthesis of Capsule 5

[0447] Except for changing protected phenol 1 to protected phenol 5, cap 5 was obtained in the same manner as [Synthetic Example 1-1-4] (yield 77%).

[0448] [Synthesization Example 1-6] Synthesis of Cap 6

[0449]

[0450] [Synthesization Example 1-6-1] Synthesis of Bromobenzene 6

[0451] Bromobenzene 6 was obtained in the same manner as in [Synthesization Example 1-2-1], except that fluorobenzene 1 was changed to fluorobenzene 3 (yield 77%).

[0452] Boiling point: 99-100℃ / 1 KPa.

[0453] [Synthesization Example 1-6-2] Synthesis of Intermediate Phenol 6

[0454] Intermediate phenol 6 was obtained by the same method as in [Synthesization Example 1-1-2], except that bromobenzene 1 was changed to bromobenzene 6 (yield 68%).

[0455] [Synthesization Example 1-6-3] Synthesis of Protected Phenol 6

[0456] Protected phenol 6 was obtained by the same method as in [Synthesization Example 1-1-3], except that intermediate phenol 1 was changed to intermediate phenol 6 (yield 86%).

[0457] [Synthesization Example 1-6-4] Synthesis of Cap 6

[0458] Cap 6 was obtained in the same manner as [Synthetic Example 1-1-4], except that protected phenol 1 was changed to protected phenol 6 (yield 86%).

[0459] [Synthesization Example 1-7] Synthesis of Cap 7

[0460]

[0461] [Synthesization Example 1-7-1] Synthesis of Cap 7

[0462] Under a nitrogen atmosphere, etherifying agent 2 (19.5 g) was added to a slurry solution of dihydroxybenzene 1 (55.9 g), potassium carbonate (41.5 g), sodium iodide (100 mg), and dimethylformaldehyde (300 g) at 60–80°C. After stirring at the same temperature for 3 hours, water (400 g) was added dropwise to stop the reaction. Conventional aqueous work-up was performed. Recrystallization was carried out using an ethyl acetate / n-hexane mixed solvent to obtain capping agent 7 (18.6 g, yield 62%).

[0463] [Synthesized Example 1-8] Synthesis of Cap 8

[0464]

[0465] [Synthesization Example 1-8-1] Synthesis of Cap 8

[0466] Cap 8 was obtained in the same manner as in [Synthetic Example 1-7-1], except that dihydroxybenzene 1 was changed to dihydroxybenzene 2 and etherifying agent 2 was changed to etherifying agent 1 (yield 43%).

[0467] [Synthesized Example 1-9] Synthesis of Cap 9

[0468]

[0469] [Synthesization Example 1-9-1] Synthesis of Cap 9

[0470] Cap 9 was obtained in the same manner as in [Synthetic Example 1-7-1], except that dihydroxybenzene 1 was changed to dihydroxybenzene 3 and etherifying agent 2 was changed to etherifying agent 1 (yield 45%).

[0471] [Synthesization Example 1-10] Synthesis of Capsule 10

[0472]

[0473] [Synthesization Example 1-10-1] Synthesis of Protected Phenol 10

[0474] Protected phenol 10 was obtained in the same manner as [Synthesizing Example 1-1-3], except that etherifying agent 1 was changed to etherifying agent 3 (yield 81%).

[0475] [Synthesization Example 1-10-2] Synthesis of Capsule 10

[0476] Except for changing protected phenol 1 to protected phenol 10, cap 10 was obtained in the same manner as [Synthetic Example 1-1-4] (yield 86%).

[0477] [Synthesized Example 1-11] Synthesis of Cap 11

[0478]

[0479] [Synthesization Example 1-11-1] Synthesis of Protected Phenol 11

[0480] Protected phenol 11 was obtained in the same manner as in [Synthetic Example 1-1-3], except that etherifying agent 1 was changed to etherifying agent 4 (yield 82%).

[0481] [Synthesization Example 1-11-2] Synthesis of Cap 11

[0482] Cap 11 was obtained in the same manner as [Synthetic Example 1-1-4], except that protected phenol 1 was changed to protected phenol 11 (yield 75%).

[0483] IR(D-ATR): ν=3619, 3292, 2948, 2890, 1608, 1516, 1452, 1386, 1280, 1234, 1191, 1157, 1109, 1101, 1052, 1023, 966, 945, 912, 851, 841, 823, 798, 756, 740 cm -1 .

[0484] 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.

[0485] [2] Synthesis of polyols containing weakly acidic functional groups

[0486] [Synthesization Example 2-1] Synthesis of Hexafluoroalcohol-containing Chain Extender 1

[0487]

[0488] [Synthesization Example 2-1-1] Synthesis of Chain Extender 1

[0489] Under a nitrogen atmosphere, trimethylolpropane (1260 g), esterifying agent 1 (1415 g), and a methanol solution (60.7 g) of 28 mass% sodium methoxide were stirred at 100–140°C. Ester exchange was performed while draining the methanol, and after the reaction was completed, the mixture was cooled to 50°C or lower and neutralized with hydrochloric acid. Subsequently, a normal aqueous work-up was performed, and recrystallization was carried out using an IPE / n-hexane mixed solvent to obtain 949 g of chain extender 1 (purity 99.1%, yield 46.2%).

[0490] Chain Extension System 1:

[0491] white powder

[0492] 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)

[0493] [Synthesization Example 2-2] Synthesis of Hexafluoroalcohol-containing Chain Extender 2

[0494]

[0495] [Synthesization Example 2-2-1] Synthesis of Chain Extender 2

[0496] Chain extender 2 was obtained in the same manner as [Synthetic Example 2-1-1], except that the raw material trimethylolpropane was changed to glycerol (yield 40%).

[0497] [Synthesization Example 2-3] Synthesis of Hexafluoroalcohol-containing Chain Extender 3

[0498]

[0499] [Synthesization Example 2-3-1] Synthesis of Intermediate 3

[0500] Under a nitrogen atmosphere, oxalyl chloride (8.7 g) was added to a suspension of carboxylic acid 1 (10.0 g), toluene (50.0 g), and two drops of N,N-dimethylformamide. After stirring at room temperature for 5 hours, the solvent was removed under reduced pressure to obtain chloride 1.

[0501] Under a nitrogen atmosphere, an acetonitrile solution of chloride 1 was added to an ice-cold solution of alcohol 3 (15.6 g), triethylamine (7.9 g), and acetonitrile (20 mL), and stirred overnight at room temperature. After the reaction was complete, water was added and normal post-treatment was performed to obtain 19.0 g of intermediate 3 (crude yield 80%).

[0502] [Synthesization Example 2-3-2] Synthesis of Chain Extender 3

[0503] The intermediate 3 (15.0 g) obtained above, methanol (30 g), and strong acidic cation exchange resin (1 g) were heated and refluxed. Deprotection was performed while removing acetone, and after the reaction was completed, the ion exchange resin was removed and the solvent was removed to obtain 13.3 g of chain extender 3 (crude yield 97%).

[0504] [Synthesization Example 2-4] Synthesis of Hexafluoroalcohol-containing Chain Extender 4

[0505]

[0506] [Synthesization Example 2-4-1] Synthesis of Intermediate 4

[0507] Intermediate 4 was obtained in the same manner as in [Synthetic Example 2-3-1], except that alcohol 3 was changed to alcohol 4.

[0508] [Synthesization Example 2-4-2] Synthesis of Chain Extender 4

[0509] Chain extender 4 was obtained in the same manner as in [Synthetic Example 2-3-2], except that intermediate 3 was changed to intermediate 4 (process yield 75%).

[0510] [Synthesization Example 2-5] Synthesis of Pentafluoroalcohol-containing Chain Extender 5

[0511]

[0512] [Synthesization Example 2-5-1] Synthesis of Intermediate 5

[0513] Intermediate 5 was obtained in the same manner as in [Synthetic Example 2-3-1], except that alcohol 3 was changed to alcohol 5.

[0514] [Synthesization Example 2-5-2] Synthesis of Chain Extender 5

[0515] Chain extender 5 was obtained in the same manner as in [Synthetic Example 2-3-2], except that intermediate 3 was changed to intermediate 5 (process yield 75%).

[0516] [Synthesization Example 2-6] Synthesis of Trifluoromethanesulfonamide-Containing Chain Extender 6

[0517]

[0518] [Synthesization Example 2-6-1] Synthesis of Intermediate 6

[0519] Under a nitrogen atmosphere, trifluoromethanesulfonic acid 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 stirred at the same temperature for 2 hours. After raising the temperature to room temperature and stirring for another 1 hour, the reaction was stopped by adding water while cooling on ice. Subsequently, 22.7 g of intermediate 6 (crude yield 78%) was obtained by performing normal post-treatment.

[0520] [Synthesization Example 2-6-2] Synthesis of Chain Extender 6

[0521] Chain extender 6 was obtained in the same manner as in [Synthetic Example 2-3-2], except that intermediate 3 was changed to intermediate 6 (yield 87%).

[0522] [3] Synthesis of polyurethane containing weakly acidic functional groups

[0523] raw material

[0524] High molecular weight polyols

[0525] · Nippo-ran 4010 (Manufactured by Tosho Co.) Polyester polyol, number average molecular weight 2000

[0526] · Nippo-ran 4009 (Manufactured by Tosho Co.) Polyester polyol, number average molecular weight 1,000

[0527] · Curare Polyol P-2010 (Manufactured by Curare) Polyester Polyol, Number Average Molecular Weight 2000

[0528] · Curare Polyol C-2090 (Manufactured by Curare) Polycarbonate Polyol, Number Average Molecular Weight 2000

[0529] · Fraxel 210 (manufactured by Daicel) Polycaprolactone diol, number average molecular weight 1,000

[0530] Diisocyanate

[0531] · 2,4-tolylene diisocyanate or 2,6-tolylene diisocyanate and mixtures of their isomers (TDI)

[0532] · Isophorone diisocyanate (IPDI)

[0533] Chain extension system

[0534]

[0535] <Capje>

[0536]

[0537] Cap 12 used a commercially available product.

[0538] Catalyst

[0539] · XK-640 (Manufactured by KING INDUSTRIES)

[0540] [Synthesized Example 3]

[0541] Under a nitrogen atmosphere, 445.8 g of a 40 mass% BCA solution of Nipporan 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 prepare a prepolymer. 232.9 g of a 50 mass% BCA solution of chain extender 1 was added dropwise to the prepolymer solution heated to 90°C, and after aging at the same temperature for 10 hours, 91.1 g of a 10 mass% BCA solution of capping agent 1 was added and aged for 1 hour.

[0542] PU 1:

[0543] Mw=125,190, Mw / Mn=3.53

[0544] PU 2 to 17 and comparative PU 1 to 3 were synthesized by the same procedure as in [Synthesization Example 3] above, except that the type, formulation ratio, and amount of diisocyanate, high molecular weight polyol, chain extender, and capping agent, as well as the amount of catalyst used, were changed as described in Tables 1 and 2.

[0545]

[0546]

[0547] The phenol compound used as an additive was synthesized as follows.

[0548] [4] Synthesis of phenol compounds

[0549] [Synthesization Example 4-1] Synthesis of Phenol 1

[0550]

[0551] [Synthesization Example 4-1-1] Synthesis of Protected Phenol 12

[0552] Protected phenol 12 was obtained in the same manner as in [Synthesizing Example 1-1-3], except that etherifying agent 1 was changed to etherifying agent 5 (yield 85%).

[0553] [Synthesization Example 4-1-2] Synthesis of Phenol 1

[0554] Phenol 1 was obtained by the same method as in [Synthesization Example 1-1-4], except that protected phenol 1 was changed to protected phenol 12 (yield 84%).

[0555] IR(D-ATR): ν=3402, 2953, 2942, 2920, 2870, 2854, 1607, 1516, 1479, 1471, 1460, 1398, 1313, 1275, 1255, 1205, 1158, 1111, 1028, 840, 788 cm -1 .

[0556] 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.

[0557] 19 F-NMR (565MHz in DMSO-d6): δ=-133.7(1F, t) ppm.

[0558] [Synthesization Example 4-2] Synthesis of Phenol 2

[0559]

[0560] [Synthesization Example 4-2-1] Synthesis of Protected Phenol 13

[0561] Protected phenol 13 was obtained in the same manner as in [Synthesization Example 4-1-1], except that intermediate phenol 1 was changed to intermediate phenol 5 (yield 88%).

[0562] [Synthesization Example 4-2-2] Synthesis of Phenol 2

[0563] Phenol 2 was obtained by the same method as in [Synthesization Example 1-1-4], except that protected phenol 1 was changed to protected phenol 13 (yield 72%).

[0564] 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, 789 cm -1 .

[0565] 1 H-NMR (major isomers 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.

[0566] 19 F-NMR (major isomers only, 565 MHz in DMSO-d6): δ=-137.4(1F, m), -171.7(1F, m) ppm.

[0567] [Synthesization Example 4-3] Synthesis of Phenol 3

[0568]

[0569] [Synthesization Example 4-3-1] Synthesis of Protected Phenol 14

[0570] Protected phenol 14 was obtained in the same manner as in [Synthesization Example 4-1-1], except that intermediate phenol 1 was changed to intermediate phenol 6 (yield 90%).

[0571] [Synthesization Example 4-3-2] Synthesis of Phenol 3

[0572] Phenol 3 was obtained by the same method as in [Synthesization Example 1-1-4], except that protected phenol 1 was changed to protected phenol 14 (yield 81%).

[0573] IR(D-ATR): ν=3591, 3446, 2926, 2855, 1605, 1507, 1468, 1391, 1254, 1204, 1172, 1026, 983, 912, 836, 792 cm -1 .

[0574] 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.

[0575] 19 F-NMR (565MHz in DMSO-d6): δ=-57.5(3F, t) ppm.

[0576] [Synthesization Example 4-4] Synthesis of Phenol 4

[0577]

[0578] [Synthesization Example 4-4-1] Synthesis of Protected Phenol 15

[0579] Protected phenol 15 was obtained by the same method as in [Synthesization Example 4-1-1], except that intermediate phenol 1 was changed to intermediate phenol 3 (yield 91%).

[0580] [Synthesization Example 4-4-2] Synthesis of Phenol 4

[0581] Phenol 4 was obtained by the same method as in [Synthesization Example 1-1-4], except that protected phenol 1 was changed to protected phenol 15 (yield 76%).

[0582] IR(D-ATR): ν=3290, 2956, 2918, 2873, 2849, 1615, 1526, 1502, 1470, 1420, 1398, 1284, 1265, 1216, 1180, 1089, 1062, 1053, 1042, 1030, 1016, 975, 945, 802 cm -1 .

[0583] 1H-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.

[0584] 19 F-NMR (565MHz in DMSO-d6): δ=-158.1∼-157.9(1F, m), -159.3∼-159.1(1F, m) ppm.

[0585] [Synthesization Example 4-5] Synthesis of Phenol 5

[0586]

[0587] [Synthesization Example 4-5-1] Synthesis of Phenol 5

[0588] Phenol 5 was obtained by the same method as in [Synthesizing Example 1-7-1], except that dihydroxybenzene 1 was changed to hydroquinone and etherifying agent 2 was changed to etherifying agent 6 (yield 59%).

[0589] [Synthesization Example 4-6] Synthesis of Phenol 6

[0590]

[0591] [Synthesization Example 4-6-1] Synthesis of Protected Phenol 16

[0592] Protected phenol 16 was obtained in the same manner as in [Synthetic Example 1-1-3], except that etherifying agent 1 was changed to etherifying agent 6 (yield 94%).

[0593] [Synthesization Example 4-6-2] Synthesis of Phenol 6

[0594] Phenol 6 was obtained by the same method as in [Synthesization Example 1-1-4], except that protected phenol 1 was changed to protected phenol 16 (yield 90%).

[0595] 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 .

[0596] 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.

[0597] 19 F-NMR (565MHz in DMSO-d6): δ=-133.6(2F, t) ppm.

[0598] [Synthesization Example 4-7] Synthesis of Phenol 7

[0599]

[0600] [Synthesization Example 4-7-1] Synthesis of Protected Phenol 17

[0601] Protected phenol 17 was obtained in the same manner as in [Synthetic Example 1-1-3], except that etherifying agent 1 was changed to etherifying agent 7 (yield 92%).

[0602] [Synthesization Example 4-7-2] Synthesis of Phenol 7

[0603] Phenol 7 was obtained by the same method as in [Synthesization Example 1-1-4], except that protected phenol 1 was changed to protected phenol 17 (yield 87%).

[0604] IR(D-ATR): ν=3385, 2941, 2923, 2856, 1608, 1514, 1479, 1468, 1455, 1288, 1276, 1253, 1203, 1156, 1110, 1042, 1022, 988, 956, 842, 818, 802, 787, 748 cm -1 .

[0605] 1 H-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.

[0606] 19 F-NMR (565MHz in DMSO-d6): δ=-133.7(2F, t) ppm.

[0607] [Synthesization Example 4-8] Synthesis of Phenol 8

[0608]

[0609] [Synthesization Example 4-8-1] Synthesis of Protected Phenol 18

[0610] Protected phenol 18 was obtained in the same manner as in [Synthesizing Example 1-1-3], except that intermediate phenol 1 was changed to intermediate phenol 4 and etherifying agent 1 was changed to etherifying agent 7 (yield 88%).

[0611] [Synthesization Example 4-8-2] Synthesis of Phenol 8

[0612] Phenol 8 was obtained by the same method as in [Synthesization Example 1-1-4], except that protected phenol 1 was changed to protected phenol 18 (yield 84%).

[0613] IR(D-ATR): ν=3401, 2942, 2923, 2856, 1648, 1616, 1528, 1479, 1469, 1459, 1378, 1247, 1202, 1148, 1045, 1023, 1017, 823, 802cm -1 .

[0614] 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.

[0615] 19F-NMR (565MHz in DMSO-d6): δ=-131.0(4F, d) ppm.

[0616] [Synthesization Example 4-9] Synthesis of Phenol 9

[0617]

[0618] (In the food, Ms indicates plum flavor.)

[0619] [Synthesization Example 4-9-1] Synthesis of Protected Phenol 19

[0620] Protected phenol 19 was obtained in the same manner as in [Synthetic Example 1-1-3], except that etherifying agent 1 was changed to etherifying agent 8 (yield 85%).

[0621] [Synthesization Example 4-9-2] Synthesis of Phenol 9

[0622] Phenol 9 was obtained by the same method as in [Synthesization Example 1-1-4], except that protected phenol 1 was changed to protected phenol 19 (yield 81%).

[0623] 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.

[0624] 19 F-NMR (565MHz in DMSO-d6): δ=-136.8(2F, t) ppm.

[0625] [Synthesization Example 4-10] Synthesis of Phenol 10

[0626]

[0627] [Synthesizing Example 4-10-1] Synthesis of Etherizing Agent 9

[0628] Under a nitrogen atmosphere, Grignard reagent prepared in advance using silane 1 (30.7 g), magnesium (6.7 g), and 120 mL of tetrahydrofuran was added dropwise to a solution of dibromosite 1 (75.0 g), cuprous iodide (0.52 g), triethyl phosphite (0.96 g), and tetrahydrofuran (100 mL) at an internal temperature of 10 to 30°C. Stirring was continued for 20 hours at the reaction temperature. Afterward, a saturated aqueous ammonium chloride solution (200 g) was added at an internal temperature of 30°C or lower to stop the reaction. After performing a normal post-treatment method, etherifying agent 9 (43.3 g, yield 62%) was obtained.

[0629] Boiling point: 72℃ / 20 Pa.

[0630] [Synthesization Example 4-10-2] Synthesis of Protected Phenol 20

[0631] Protected phenol 20 was obtained in the same manner as in [Synthetic Example 1-1-3], except that etherifying agent 1 was changed to etherifying agent 9 (yield 85%).

[0632] [Synthesization Example 4-10-3] Synthesis of Phenol 10

[0633] Phenol 10 was obtained by the same method as in [Synthesization Example 1-1-4], except that protected phenol 1 was changed to protected phenol 20 (yield 93%).

[0634] 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.

[0635] 19 F-NMR (470MHz in DMSO-d6): δ=-133.7(1F, t) ppm.

[0636] [Examples 1–26, Comparative Examples 1–5]

[0637] <Preparation of a conductive paste composition>

[0638] As polyurethanes for preparing a conductive paste composition, PU 1 to 17 listed in Tables 1 and 2, comparative PU 1 to 3, and the following resins were used.

[0639] · Fluororubber (Manufactured by Daikin, G801)

[0640] · Polyester (Manufactured by Unichika, UE-9200)

[0641] Conductive fillers were prepared using the following silver powders A to E and copper powder A.

[0642] · Silver powder A: Average particle size (DL) 50 ) is 2.1 µm

[0643] · Silver powder B: Average particle size (DL) 50 ) is 5.3 µm

[0644] · Silver powder C: Average particle size (DL) 50 ) is 1.2 µm

[0645] · Silver powder D: Average particle size (DL) 50 ) is 0.67 µm

[0646] · Silver powder E: Average particle size (DL) 50 ) is 1.72 µm

[0647] · Copper powder A: Average particle size (DL) 50 ) is 1.30 µm

[0648] The average particle size was measured by using a laser diffraction particle size distribution device to measure the particle size distribution, and the particle size at 50% of the accumulated value was determined as the average particle size.

[0649] The following phenols 1 to 13 were used as the phenol compounds of the additive. Here, phenol 11 is the same as cap 1, phenol 12 is the same as cap 4, and phenol 13 is the same as cap 11.

[0650]

[0651] A conductive paste composition was prepared by stirring and mixing a polymer, a conductive filler, a phenolic compound, and a solvent (BCA) according to the composition listed in Table 3.

[0652]

[0653] BCA: Diethylene glycol monobutyl ether acetate

[0654] [Evaluation of Flexible Conductive Wiring]

[0655] <Production of Evaluation Samples>

[0656] A flexible conductive wiring with a line width of 10 mm, a length of 70 mm, and a film thickness of 10 μm was formed by applying a conductive paste composition onto a polyurethane film using a screen printing machine MT-320TVC manufactured by Microtech Co., Ltd., and then heat-treating it with a hot air dryer.

[0657] Measurement of Initial Electrical Resistance in Non-Extended State

[0658] The electrical resistance at both ends of the flexible conductive wiring formed on the polyurethane film was measured using the four-terminal resistance measurement method. The electrical resistance was measured using a PXIe-4136SMU resistance measuring device manufactured by National Instruments Co., Ltd.

[0659] · Electric resistance (Ω) R = V / I (V: voltage, I: current)

[0660] The measurement results of the initial electrical resistance (electrical resistance in the non-stretched state) are shown in Table 4.

[0661] <Measurement of maximum electrical resistance at 20% extension>

[0662] A polyurethane film with elastic conductive wiring formed thereon was fixed from a non-stretched state (0%) to a state stretched by 20%, and the electrical resistance was measured using the 4-terminal resistance measurement method.

[0663] The polyurethane film with the formed elastic conductive wiring was stretched at a speed of 300 mm / min in the longitudinal direction of the elastic conductive wiring (rectangular) using the precision universal testing machine AG-Xplus HS manufactured by Shimadzu Corporation.

[0664] · Change in electrical resistance at 20% extension = [Electrical resistance at 20% extension (Ω)] ÷ [Initial electrical resistance (Ω)] × 100

[0665] The change in electrical resistance at 20% elongation is shown in Table 4.

[0666] <Measurement of maximum electrical resistance at 300% extension>

[0667] The electrical resistance of a polyurethane film with elastic conductive wiring formed thereon was measured by fixing it from a non-stretched state of 0% to a state of 300% stretch.

[0668] The polyurethane film with the formed elastic conductive wiring was stretched at a speed of 300 mm / min in the longitudinal direction of the elastic conductive wiring (rectangular) using the precision universal testing machine AG-Xplus HS manufactured by Shimadzu Corporation.

[0669] · Change in electrical resistance at 300% extension = [Electrical resistance at 300% extension (Ω)] ÷ [Initial electrical resistance (Ω)] × 100

[0670] The change in electrical resistance at 300% elongation is shown in Table 4.

[0671] <Measurement of maximum resistance value during 0–20% repeated stretching>

[0672] For a polyurethane film with a flexible conductive wire formed thereon, the change in the electrical resistance of the conductive wire over time was measured by repeating the stretching from a non-stretched state (0%) to 20% 1000 times.

[0673] The repeated stretching test was performed by stretching a polyurethane film in the longitudinal direction of a stretchable conductive wire (rectangular) at a tensile speed of 300 mm / min using the precision universal testing machine AG-Xplus HS manufactured by Shimadzu Corporation.

[0674] In addition, electrical resistance was measured by the 4-terminal resistance measurement method using a PXIe-4136SMU resistance measuring device manufactured by National Instruments Co., Ltd., by installing electrodes on the inner side of the sample fixing jig of the tensile testing machine (the above-mentioned precision universal testing machine AG-Xplus HS).

[0675] · Change in maximum electrical resistance when stretched 1,000 times at an elongation rate of 0–20% = [Maximum electrical resistance during repeated stretching test (Ω)] ÷ [Initial electrical resistance (Ω)] × 100

[0676] Table 4 shows the change in maximum electrical resistance when stretched 1,000 times with an elongation rate of 0 to 20%.

[0677]

[0678] -: Unmeasured

[0679] As shown in Table 4, it can be seen that when a conductive paste composition containing a polyurethane with phenolic hydroxyl groups is used, a conductive wiring with excellent conductivity stability during repeated stretching and a small increase in electrical resistance due to wiring elongation can be obtained even during low-temperature short-time firing at 120°C for 30 minutes (Examples 1 to 26). In addition, by adding a phenolic compound as an additive, deterioration due to wiring elongation can be suppressed (Examples 7 to 26). On the other hand, the polyurethane (Comparative Examples 1 to 3) or resin (Comparative Examples 4 to 5) that do not have phenolic hydroxyl groups in the comparative examples showed a significant increase in electrical resistance due to wiring elongation or repeated stretching.

[0680] Furthermore, the present invention is not limited to the above embodiments. The above embodiments are examples, and any configuration substantially identical to the technical concept described in the claims of the present invention and exhibiting the same functional effect is included within the technical scope of the present invention.

Claims

Claim 1 Polyurethane characterized by containing a phenolic hydroxyl group represented by the following general formula (1B). (In the formula, Az' represents a straight-chain, branched, or cyclic (ka+2) hydrocarbon group having 1 to 19 carbon atoms, or a fluorinated hydrocarbon group, and the -CH2- constituting the (ka+2) hydrocarbon group is -O-, -NR 4 -, -C(=O)- or -Si(R 2 R 3 It may be substituted with ). ka represents an integer from 0 to 2. kb, kc, kd, and ke represent 1 or 2. R 2 , R 3 is a straight-chain, branched, or cyclic alkyl group having 1 to 6 carbon atoms, or a phenyl group, and R 4 is a hydrogen atom, or a straight-chain or branched alkyl group having 1 to 4 carbon atoms. Dashed lines indicate bond losses. Claim 2 delete Claim 3 A polyurethane according to claim 1, characterized in that the polyurethane further comprises 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 having 1 to 10 carbon atoms that may be fluorinated, and Rf represents a fluorine atom or a straight-chain, branched, or cyclic fluorinated hydrocarbon group having 1 to 10 carbon atoms. n is an integer of 1 or 2, and dashed lines represent bond losses.) Claim 4 A polyurethane according to claim 1, characterized in that the polyurethane further comprises one or more structures represented by the following general formulas (2a) to (2c). (during food, R 1 is a hydrogen atom or a monovalent hydrocarbon group having 1 to 3 carbon atoms, and A a represents a single bond, or a straight-chain, branched, or cyclic divalent hydrocarbon group having 1 to 20 carbon atoms, and the constituent -CH2- may be substituted with -O-, -C(=O)-, -C(=O)O-, or -C6H4-, and -NR 4 Even if it's -C(=O)- it's fine. A b and A c -O-, -OC(=O)-NR respectively, independently 4 -, -NR 4 Represents one of the groups selected from -, -C(=O)O-. n 1 , n 2 , n 4 is an integer from 0 to 10, and n 3 is an integer of 0 or 1. R 4 ...is the same as above, and the dashed line indicates the joining loss.) Claim 5 A method for manufacturing a polyurethane as described in claim 1, characterized by introducing the phenolic hydroxyl group into the polyurethane using an alcohol or amine represented by the following general formula (1C) after a chain extension reaction. (In the formula, Az" represents a straight-chain, branched, or cyclic (ka+2) hydrocarbon group having 1 to 19 carbon atoms, or a fluorinated hydrocarbon group, and the -CH2- constituting the (ka+2) hydrocarbon group is -O-, -C(=O)-, or -Si(R 2 R 3 It may be substituted with ). X is an oxygen atom or NR 4 Represents. ka represents an integer from 0 to 2. kb, kc, kd, and ke represent 1 or 2. R 2 , R 3 , R 4 is the same as above.) Claim 6 A method for manufacturing a polyurethane according to claim 5, characterized by introducing a weakly acidic functional group into the polyurethane using one or more alcohols represented by the following general formulas (3a) to (3c) as chain extenders. (during food, R 1 is a hydrogen atom or a monovalent hydrocarbon group having 1 to 3 carbon atoms, and A a represents a single bond, or a straight-chain, branched, or cyclic divalent hydrocarbon group having 1 to 20 carbon atoms, and the constituent -CH2- may be substituted with -O-, -C(=O)-, -C(=O)O-, or -C6H4-, and -NR 4 Even if it's -C(=O)-, it's fine. R 4 is a hydrogen atom, or a straight-chain or branched alkyl group having 1 to 4 carbon atoms. 1 , n 2 , n 4 is an integer between 0 and 10.) Claim 7 A conductive paste composition characterized by comprising (A) a conductive filler, (B) a polyurethane as described in any one of claims 1, 3 and 4, and (C) a solvent. Claim 8 A conductive paste composition according to claim 7, characterized in that the conductive paste composition further comprises (D) a phenolic compound. Claim 9 A conductive paste composition according to claim 8, characterized in that the phenol compound of component (D) comprises a structure represented by the following general formula (2A). (during food, R 6 represents a hydrogen atom, a halogen atom, a cyano group, or a hydroxyl group. Ay represents a straight-chain, branched, or cyclic (ka+2) hydrocarbon group having 1 to 20 carbon atoms, or a fluorinated hydrocarbon group, wherein the -CH2- constituting the (ka+2) hydrocarbon group is -O-, -C(=O)-, or -Si(R 2 R 3 It may be substituted with ). 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 represents a single bond or an oxygen atom. Xf represents, respectively, a linear, branched, or cyclic monovalent hydrocarbon group that may be independently substituted with a hydrogen atom, a halogen atom, a fluorine atom having 1 to 10 carbon atoms, an alkoxy group that may be substituted with a fluorine atom having 1 to 10 carbon atoms, or an electron-occlusive group. Ring ZZ represents, respectively, an aromatic monocyclic or polycyclic ring having 5 to 20 carbon atoms. The carbon atoms of the above ring ZZ may be substituted with nitrogen atoms, oxygen atoms, or sulfur atoms. R 2 , R 3 is the same as above.) Claim 10 A conductive paste composition according to claim 9, characterized in that the phenol compound of component (D) comprises a structure represented by the following general formula (2B). (In the formula, Ay' represents a straight-chain, branched, or cyclic (ka+2) hydrocarbon group having 1 to 19 carbon atoms, or a fluorinated hydrocarbon group, and the -CH2- constituting the (ka+2) hydrocarbon group is -O-, -C(=O)-, or -Si(R 2 R 3 It may be substituted with ). ka represents an integer from 0 to 2. kb, kc, kd, and ke represent 1 or 2. R 2 , R 3 , R 6 is the same as above.) Claim 11 A conductive paste composition according to claim 7, characterized in that the conductive filler of component (A) is contained in a ratio of more than 70 parts by mass relative to 100 parts by mass of the total of component (A) and component (B). Claim 12 A conductive paste composition according to claim 7, characterized in that 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 composite thereof. Claim 13 A conductive paste composition according to claim 12, characterized in that the conductive filler of component (A) is silver powder. Claim 14 A conductive paste composition according to claim 7, characterized in that the average particle size of the conductive filler of component (A) is 5 nm to 10 μm. Claim 15 A conductive wiring formed on a substrate and characterized by including a fired product of the conductive paste composition described in claim 7. Claim 16 In claim 15, the conductive wiring is characterized in that the above description has elasticity. Claim 17 In claim 16, the conductive wiring is characterized in that the above-mentioned material is thermoplastic polyurethane. Claim 18 In claim 16, a conductive wiring characterized in that the electrical resistance at 20% elongation is 500% or less of the electrical resistance before elongation. Claim 19 In claim 16, the conductive wiring is characterized in that the maximum electrical resistance when stretched 1,000 times at an elongation rate of 20% is 5,000% or less of the electrical resistance before stretching. Claim 20 A method for manufacturing conductive wiring by forming conductive wiring on a substrate using a conductive paste composition described in claim 7, characterized in that the firing temperature when forming the conductive wiring is 60 to 160°C. Claim 21 A method for manufacturing conductive wiring characterized by forming conductive wiring on a substrate by printing the conductive paste composition described in claim 7.

Images