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  • C07C39/11—Alkylated hydroxy benzenes containing also acyclically bound hydroxy groups, e.g. saligenol
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  • C07C39/12—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring polycyclic with no unsaturation outside the aromatic rings
  • C07C39/15—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring polycyclic with no unsaturation outside the aromatic rings with all hydroxy groups on non-condensed rings, e.g. phenylphenol
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  • C07C39/15—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring polycyclic with no unsaturation outside the aromatic rings with all hydroxy groups on non-condensed rings, e.g. phenylphenol
  • C07C39/16—Bis-(hydroxyphenyl) alkanes; Tris-(hydroxyphenyl)alkanes
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  • C07C39/18—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring monocyclic with unsaturation outside the aromatic ring
  • C07C39/19—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring monocyclic with unsaturation outside the aromatic ring containing carbon-to-carbon double bonds but no carbon-to-carbon triple bonds
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  • C07C69/708—Ethers
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  • C07C69/92—Esters of carboxylic acids having a carboxyl group bound to a carbon atom of a six-membered aromatic ring of monocyclic hydroxy carboxylic acids, the hydroxy groups and the carboxyl groups of which are bound to carbon atoms of a six-membered aromatic ring with etherified hydroxyl groups
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  • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
  • H01B1/20—Conductive material dispersed in non-conductive organic material
  • H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
  • H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
  • H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
  • H01B13/0016—Apparatus or processes specially adapted for manufacturing conductors or cables for heat treatment
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
  • H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
  • H01B13/0026—Apparatus for manufacturing conducting or semi-conducting layers, e.g. deposition of metal
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
  • H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
  • H01B5/14—Non-insulated conductors or conductive bodies characterised by their form comprising conductive layers or films on insulating-supports
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
  • H01B7/00—Insulated conductors or cables characterised by their form
  • H01B7/06—Extensible conductors or cables, e.g. self-coiling cords
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C2601/00—Systems containing only non-condensed rings
  • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
  • C07C2601/14—The ring being saturated
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C2603/00—Systems containing at least three condensed rings
  • C07C2603/56—Ring systems containing bridged rings
  • C07C2603/58—Ring systems containing bridged rings containing three rings
  • C07C2603/70—Ring systems containing bridged rings containing three rings containing only six-membered rings
  • C07C2603/74—Adamantanes
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/02—Elements
  • C08K3/08—Metals
  • C08K2003/0806—Silver
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K2201/00—Specific properties of additives
  • C08K2201/001—Conductive additives
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K2201/00—Specific properties of additives
  • C08K2201/002—Physical properties
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K2201/00—Specific properties of additives
  • C08K2201/002—Physical properties
  • C08K2201/005—Additives being defined by their particle size in general

Definitions

• the present invention relates to a conductive paste composition capable of producing a highly conductive and stretchable conductive wiring, and a phenol compound contained in the composition.
• wearable devices In recent years, in the field of sports or healthcare, research on the development of wearable devices aimed at acquiring vital signs such as heart rate and respiratory rate by wearing them on the human body has become active.
• Such wearable devices usually consist of bioelectrodes for detecting electrical signals from the body, wiring for sending electrical signals to sensors, semiconductor chips serving as sensors, and batteries.
• the desired stretching performance is said to be about 50%, with the maximum elongation of clothes worn by humans in the exercise state at the knees and elbows.
• Even if the wiring itself is not elastic, conductivity can be ensured even if it is stretched by using a bellows wiring with horseshoes lined up or by using a board with wrinkles.
• the wiring area will be more compact, the design will be beautiful, and the cost will be low. Furthermore, the higher the conductivity, the more the wiring can be made thinner to ensure continuity, and the invisible ultra-fine wiring makes the design flexible so that the existence of the wiring is not felt. It has a cool impression. For this reason, highly conductive and stretchable conductive pastes and conductive inks are being actively developed.
• Patent Document 1 proposes a paste in which a metal powder is contained in an elastomer binder containing a sulfur atom or a nitrile group to give the conductor flexibility and stretchability.
• Patent Document 2 proposes an elastic conductor having a conductivity of more than 100 S / cm at the time of expansion and contraction of about 200% by optimizing the blending amount of conductive particles, fluororubber, and an aqueous solution of a fluorine surfactant. There is.
• Patent No. 6319085 International Publication No. 2015/11927
• the conductivity may be sharply lowered or the wire may be broken in the repeated expansion and contraction, and the expansion and contraction may be repeated.
• a conductive paste composition capable of obtaining a conductor having excellent conductive stability.
• the present invention has been made in view of the above circumstances, and is a phenol compound as an additive for a conductive paste composition having little decrease in conductivity due to repeated expansion and contraction and excellent printability, and a conductive paste containing the additive. It is an object of the present invention to provide a composition and a conductive wiring using the conductive paste composition.
• the present invention provides a phenol compound represented by the following general formula (1A).
• R 1 represents a hydrogen atom, a halogen atom, a cyano group or a hydroxyl group.
• Az is a linear, branched or cyclic (ka + 2) -valent hydrocarbon group or fluorinated hydrocarbon having 1 to 20 carbon atoms.
• R 2 and R 3 are linear, branched, or cyclic alkyl groups or phenyl groups having 1 to 6 carbon atoms.
• Xf is a hydrogen atom, a halogen atom, and a fluorine atom having 1 to 10 carbon atoms, respectively.
• Z indicates a single bond or an oxygen atom.
• Each ring ZZ independently represents an aromatic monocyclic or polycyclic ring having 5 to 20 carbon atoms. The carbon atom of the ring ZZ may be substituted with a nitrogen atom, an oxygen atom or a sulfur atom.
• Ka indicates an integer of 0 to 2.
• kb and kd indicate 1 or 2.
• kc and ke indicate an integer of 0 to 2.
• Such a phenol compound can be an additive for a conductive paste composition having little decrease in conductivity due to repeated expansion and contraction and having excellent printability.
• a phenol compound represented by the following general formula (1B) is preferable.
• Az' represents a linear, branched or cyclic (ka + 2) -valent hydrocarbon group or fluorinated hydrocarbon group having 1 to 19 carbon atoms, and constitutes the above-mentioned (ka + 2) -valent hydrocarbon group.
• ka indicates 0 or 1.
• R 1 , R 2 , and R 3 are the same as above.
• Such a phenol compound is more suitable as an additive for a conductive paste composition, which has less decrease in conductivity due to repeated expansion and contraction and has excellent printability.
• the conductive paste composition containing (A) a conductive filler, (B) a phenol compound, (C) an elastomer resin and (D) a solvent, and the phenol compound of the component (B) is described below.
• the present invention provides a conductive paste composition which is a phenol compound according to the above.
• R 1 represents a hydrogen atom, a halogen atom, a cyano group or a hydroxyl group.
• Az is a linear, branched or cyclic (ka + 2) -valent hydrocarbon group or fluorinated hydrocarbon having 1 to 20 carbon atoms.
• R 2 and R 3 are linear, branched, or cyclic alkyl groups or phenyl groups having 1 to 6 carbon atoms.
• Xf is a hydrogen atom, a halogen atom, and a fluorine atom having 1 to 10 carbon atoms, respectively.
• a linear, branched or cyclic monovalent hydrocarbon group which may be substituted with, an alkoxy group or an electron-withdrawing group which may be substituted with a fluorine atom having 1 to 10 carbon atoms.
• Each ring ZZ independently represents an aromatic monocyclic or polycyclic ring having 5 to 20 carbon atoms.
• the carbon atom of the ring ZZ may be substituted with a nitrogen atom, an oxygen atom or a sulfur atom.
• .Ka indicates an integer of 0 to 2.
• kb and kd indicate 1 or 2.
• kc and ke indicate an integer of 0 to 2.
• Az' represents a linear, branched or cyclic (ka + 2) -valent hydrocarbon group or fluorinated hydrocarbon group having 1 to 19 carbon atoms, and constitutes the above-mentioned (ka + 2) -valent hydrocarbon group.
• ka indicates 0 or 1.
• R 1 , R 2 , and R 3 are the same as above.
• a conductive paste composition in which the elastomer resin of the component (C) is polyurethane is preferable.
• a conductive paste composition in which the elastomer resin of the component (C) is a polyurethane containing the structures represented by the following general formulas (1a) to (1c) is preferable.
• R represents a hydrogen atom, a fluorine atom or a linear, branched or cyclic hydrocarbon group having 1 to 10 carbon atoms
• R f is a fluorine atom or 1 carbon atom.
• n is an integer of 1 or 2 and the broken line indicates a bond.
• a conductive paste composition in which the elastomer resin of the component (C) is a polyurethane containing the structures represented by the following general formulas (2a) to (2c) is preferable.
• R4 is a hydrogen atom or a monovalent hydrocarbon group having 1 to 3 carbon atoms
• Aa is a single bond or a linear, branched or cyclic divalent having 1 to 20 carbon atoms.
• R 8 is a hydrogen atom or a linear or branched alkyl group having 1 to 4 carbon atoms.
• N 2 , n 4 are integers from 0 to 10
• n 3 is an integer of 0 or 1, and the broken line indicates a bond.
• Such a conductive paste composition is even more suitable as a conductive paste composition having little decrease in conductivity due to repeated expansion and contraction and having excellent printability.
• the conductive filler of the component (A) is contained in a ratio of more than 70 parts by mass with respect to a total of 100 parts by mass of the component (A) and the component (C).
• the conductive filler of the component (A) is gold, silver, silver chloride, platinum, copper, tin, iron, titanium, nickel, palladium, aluminum, tungsten, molybdenum, ruthenium, chromium, indium, and solder. , And a conductive paste composition selected from carbon or a composite thereof.
• a conductive paste composition in which the conductive filler of the component (A) is a silver powder having an average particle size of 5 nm to 10 ⁇ m is preferable.
• the elastomer of the component (C) is a polyurethane containing the structures shown in the above (2a) to (2c), which is a method for producing a conductive paste composition of the component (C).
• the above polyurethane can be easily synthesized.
• the present invention provides a conductive wiring formed on a base material and made of a fired product of a conductive paste composition.
• conductive wiring in which the base material has elasticity is preferable.
• Such a base material is suitable for the conductive wiring of the present invention.
• conductive wiring in which the base material is thermoplastic polyurethane is preferable.
• Such a base material is more suitable for the conductive wiring of the present invention.
• conductive wiring having a resistance change of 500% or less at the time of 20% elongation is preferable.
• conductive wiring in which the maximum resistance value when repeatedly expanded and contracted 1000 times at an elongation rate of 20% is 5000% or less of the resistance value before expansion and contraction is preferable.
• Such conductive wiring is suitable for conductive stability in repeated expansion and contraction.
• the present invention is a method for manufacturing a conductive wiring for forming a conductive wiring on a base material using the above conductive paste composition, and the firing temperature at the time of forming the conductive wiring is 60 to 160 ° C.
• a method for manufacturing a conductive wiring is provided.
• the conductive wiring can be formed on the base material by printing the above conductive paste composition.
• productivity can be improved by forming a wiring pattern by printing.
• the conductive paste composition of the present invention has less decrease in conductivity due to repeated expansion and contraction, can efficiently transmit an electric signal to a device (that is, has excellent conductivity), has excellent print processability, and is lightweight. It is possible to form a conductive wiring that can be manufactured at low cost. Further, since it is excellent in conductive stability in repeated expansion and contraction, it is possible to form conductive wiring suitable for a wearable device in which strain is generated by the movement of the human body. Further, the present invention provides a phenol compound suitable as an additive to be blended in the conductive paste composition.
• a phenol compound as an additive for a conductive paste composition having little decrease in conductivity due to repeated expansion and contraction and having excellent printability a conductive paste composition containing the additive, and the conductivity.
• the development of conductive wiring using a paste composition has been required.
• the present inventor can obtain a phenol compound represented by the following general formula (1A) extremely easily, and further, a conductive paste using this phenol compound as an additive. It has been found that the composition provides a conductive wiring having low resistance, little decrease in conductivity during elongation, and excellent conductivity stability in repeated expansion and contraction.
• the present invention is a phenol compound represented by the following general formula (1A).
• R 1 represents a hydrogen atom, a halogen atom, a cyano group or a hydroxyl group.
• Az is a linear, branched or cyclic (ka + 2) -valent hydrocarbon group or fluorinated hydrocarbon having 1 to 20 carbon atoms.
• R 2 and R 3 are linear, branched, or cyclic alkyl groups or phenyl groups having 1 to 6 carbon atoms.
• Xf is a hydrogen atom, a halogen atom, and a fluorine atom having 1 to 10 carbon atoms, respectively.
• Z indicates a single bond or an oxygen atom.
• Each ring ZZ independently represents an aromatic monocyclic or polycyclic ring having 5 to 20 carbon atoms.
• the carbon atom of the ring ZZ may be substituted with a nitrogen atom, an oxygen atom or a sulfur atom.
• .Ka indicates an integer of 0 to 2.
• kb and kd indicate 1 or 2.
• kc and ke indicate an integer of 0 to 2.
• an asymmetric carbon may be present, and an enantiomer or a diastereomer may be present. In that case, one The formula represents those isomers. These isomers may be used alone or as a mixture.
• the phenol compound of the present invention is represented by the following general formula (1A) and is blended as an additive for a conductive paste composition.
• R 1 represents a hydrogen atom, a halogen atom, a cyano group or a hydroxyl group.
• Az is a linear, branched or cyclic (ka + 2) -valent hydrocarbon group or fluorinated hydrocarbon having 1 to 20 carbon atoms.
• R 2 and R 3 are linear, branched, or cyclic alkyl groups or phenyl groups having 1 to 6 carbon atoms.
• Xf is a hydrogen atom, a halogen atom, and a fluorine atom having 1 to 10 carbon atoms, respectively.
• Z indicates a single bond or an oxygen atom.
• Each ring ZZ independently represents an aromatic monocyclic or polycyclic ring having 5 to 20 carbon atoms.
• the carbon atom of the ring ZZ may be substituted with a nitrogen atom, an oxygen atom or a sulfur atom.
• .Ka indicates an integer of 0 to 2.
• kb and kd indicate 1 or 2.
• kc and ke indicate an integer of 0 to 2.
• linear, branched or cyclic (ka + 2) -valent hydrocarbon group having 1 to 20 carbon atoms of Az include the following. (In the formula, the broken line indicates the bond.)
• linear, branched or cyclic (ka + 2) -valent fluorinated hydrocarbon group having 1 to 20 carbon atoms of Az specifically, a part or all of the hydrogen atoms in the above-mentioned hydrocarbon group may be used. Examples thereof include those substituted with a fluorine atom.
• linear, branched, and cyclic alkyl groups having 1 to 6 carbon atoms of R 2 and R 3 include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, and a sec-butyl group. , Tart-butyl group, n-pentyl group, n-hexyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group and the like.
• linear, branched or cyclic monovalent hydrocarbon group which may be substituted with a fluorine atom having 1 to 10 carbon atoms of Xf include a methyl group, an ethyl group, a propyl group, an isopropyl group and n-butyl.
• alkyl group such as a group, a sec-butyl group, a tert-butyl group, a cyclopropyl group and a cyclobutyl group, a trifluoromethyl group, and a 2,2,2-trifluoroethyl group.
• alkoxy group that may be substituted with a fluorine atom having 1 to 10 carbon atoms in Xf include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, an n-butoxy group, a sec-butoxy group, and a tert-butoxy group. , Cyclopropoxy group, trifluoromethoxy group, 2,2,2-trifluoroethoxy group and the like.
• G is a sulfur atom or NH
• Z represents a single bond or an oxygen atom.
• aromatic monocyclic or polycyclic ring having 5 to 20 carbon atoms in the ring ZZ include the following.
• Ring ZZ may further have a substituent as described below.
• the additive contained in the conductive paste composition of the present invention is a phenol compound represented by the above general formula (1A).
• the phenol compound represented by the general formula (1A) is particularly preferably a phenol compound represented by the following general formula (1B).
• Az' represents a linear, branched or cyclic (ka + 2) -valent hydrocarbon group or fluorinated hydrocarbon group having 1 to 19 carbon atoms, and constitutes the above-mentioned (ka + 2) -valent hydrocarbon group.
• ka indicates 0 or 1.
• R 1 , R 2 , and R 3 are the same as above.
• the method for synthesizing the phenol compound represented by the general formulas (1A) and (1B) is not particularly limited, and the optimum method can be selected and synthesized according to the structure.
• the general formula (1B) In the case of the general formula (1Ba) in which kb and kc are 1, it can be synthesized by steps i) to v) shown in the following reaction formula. (In the formula, R 1 , Az', ka, kc and ke are as described above. Rp indicates an acid unstable group. XA indicates a halogen atom.)
• Step i) is a step of protecting the halogenated phenol compound (1Bb) to lead to the intermediate halogenated aryl compound (1Bd).
• step i) proceeds easily under known conditions, and for example, Rp is a t-butyl group, a t-amyl group, a methylcyclopentyl group, an ethylcyclopentyl group, a methylcyclohexyl group, an ethylcyclohexyl group, a methyladamantyl group, and the like.
• a tertiary alkyl group such as an ethyladamantyl group
• an acid catalyst using a halogenated phenol compound (1Bb) and an olefin corresponding to Rp such as isobutene and isoamylene
• a solvent-free or solvent such as toluene and hexane. It is preferable to carry out the reaction at a reaction temperature of ⁇ 20 to 50 ° C.
• Examples of the acid catalyst used include inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid and perchloric acid, and organic acids such as methanesulfonic acid, trifluoromethanesulfonic acid, p-toluenesulfonic acid and benzenesulfonic acid.
• 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.
• Step ii) is a step of nucleophilic substitution of the fluorobenzene compound (1Bc) to lead to the intermediate aryl halide compound (1Bd).
• step ii) proceeds easily under known conditions, and for example, Rp is a t-butyl group, a t-amyl group, a methylcyclopentyl group, an ethylcyclopentyl group, a methylcyclohexyl group, an ethylcyclohexyl group, a methyladamantyl group, and the like.
• an alcohol corresponding to Rp such as a fluorobenzene compound (1Bc) and t-butyl alcohol and t-amyl alcohol in a solvent such as tetrahydrofuran and N-methyl-2-pyrrolidone.
• a reaction temperature 10 to 80 ° C. in the presence of a base using a corresponding alkoxide such as t-butoxypotassium.
• Examples of the base used include metal hydrides such as borane, alkylborane, sodium hydride, lithium hydride, potassium hydride, calcium hydride, trityl lithium, trityl sodium, trityl potassium, methyl lithium, phenyl lithium, n-.
• Alkyl metal compounds such as butyl lithium, sec-butyl lithium, tert-butyl lithium and ethyl magnesium bromide, metals such as sodium methoxyd, sodium ethoxydo, lithium methoxyd, lithium ethoxydo, lithium tert-butoxide and potassium tert-butoxide. Alkoxide can be mentioned.
• Step iii) is a step of oxidizing the aryl halide compound (1Bd) to the intermediate phenol compound (1Be).
• reaction easily proceeds by a known method, and for example, the method of the following reaction formula can be exemplified.
• Rp, ke and XA are as described above.
• MA represents Li, MgCl, MgBr and MgI .
• Rr is a linear, branched or cyclic monovalent hydrocarbon having 1 to 6 carbon atoms. Indicates a hydrogen group.
• an organometallic reagent (1Bg) is prepared from an aryl halide compound (1Bd) and Li or Mg in a solvent such as tetrahydrofuran or diethyl ether. Subsequently, the reaction with the boric acid ester compound (1J) leads to an arylboronic acid derivative (1Bh), and finally, an oxidizing agent such as hydrogen peroxide, performic acid, peracetic acid, or m-chloroperbenzoic acid is used in the middle. The body phenol compound (1Be) is obtained. This step can usually proceed in one pot without going through a purification step.
• Step iv) is a step of leading to an aryl ether compound (1Bf) by etherifying the intermediate phenol compound (1Be).
• reaction easily proceeds by a known method, and for example, the method of the following reaction formula can be exemplified.
• Rp, ka, ke and Az'are as described above.
• T 1 independently represents a hydroxyl group, a halogen atom, an alkane sulfonyl oxy group, or an arene sulfonyl oxy group.
• Examples of the halogen atom of T 1 include a chlorine atom, a bromine atom, and an iodine atom.
• Examples of the alkanesulfonyloxy group and the arenesulfonyloxy group of T 1 include methanesulfonyloxy, trifluoromethanesulfonyloxy, benzenesulfonyloxy, and p-toluenesulfonyloxy group.
• Specific bases used include metal alkoxides such as sodium methoxydo, sodium ethoxydo, lithium methoxydo, lithium ethoxydo, lithium tert-butoxide, potassium tert-butoxide, pyridine, triethylamine, N, N-dimethylaniline. , Organic amines such as 4-dimethylaminopyridine, inorganic hydroxides such as sodium hydroxide, lithium hydroxide, potassium hydroxide, barium hydroxide, tetra-n-butylammonium hydroxide, sodium carbonate, sodium hydrogencarbonate.
• metal alkoxides such as sodium methoxydo, sodium ethoxydo, lithium methoxydo, lithium ethoxydo, lithium tert-butoxide, potassium tert-butoxide, pyridine, triethylamine, N, N-dimethylaniline.
• Organic amines such as 4-dimethylaminopyridine
• Inorganic carbonates such as lithium carbonate, potassium carbonate, metal hydrides such as borane, alkylboran, sodium hydride, lithium hydride, potassium hydride, calcium hydride, trityl lithium, trityl sodium, trityl potassium, methyl lithium , Phenyllithium, sec-butyllithium, tert-butyllithium, methylmagnesium chloride, ethylmagnesium chloride, ethylmagnesium bromide and other alkyl metal compounds, sodium amide, potassium amide, lithium diisopropylamide, potassium diisopropylamide, lithium dicyclohexylamide, Examples thereof include metal amides such as potassium dicyclohexylamide, lithium 2,2,6,6-tetramethylpiperidine, lithium bistrimethylsilylamide, sodium bistrimethylsilylamide, potassium bistrimethylsilylamide, lithium isopropylcyclohexylamide and bromo
• solvent water, ethers such as tetrahydrofuran, diethyl ether, di-n-butyl ether, 1,4-dioxane, hydrocarbons such as n-hexane, n-heptane, benzene, toluene, xylene, cumene, methanol, ethanol , Alcohols such as isopropyl alcohol and tert-butyl alcohol, aprotonic polar solvents such as dimethylsulfoxide (DMSO) and N, N-dimethylformamide (DMF), chlorine-based organics such as methylene chloride, chloroform and carbon tetrachloride. Solvents can be selected alone or in combination depending on the reaction conditions. The above base itself may be used as a solvent.
• ethers such as tetrahydrofuran, diethyl ether, di-n-butyl ether, 1,4-dioxane, hydrocarbons such as n-he
• the reaction temperature and time vary depending on the reagents and conditions.
• T 1 is a bromine atom and potassium carbonate is used as a base
• the reaction temperature is rapidly set to room temperature to 120 ° C, preferably 30 ° C to 90 ° C. It is preferable to complete the reaction.
• the reaction time is preferably about 1 to 60 hours in terms of yield, although it is desirable to follow the reaction by gas chromatography (GC) or silica gel thin layer chromatography (TLC) to complete the reaction.
• GC gas chromatography
• TLC silica gel thin layer chromatography
• the aryl ether compound (1Bf) can be obtained from the reaction mixture by a usual aqueous work-up, and if necessary, it can be purified by a conventional method such as distillation or chromatography.
• Step v) is a step of leading to the phenol compound of the present invention by the deprotection reaction of the aryl ether compound (1Bf).
• solvent examples include 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; acetone, 2-butanone and the like. Ketones; esters such as ethyl acetate and butyl acetate; nitriles such as acetonitrile; alcohols such as methanol and ethanol; aprotonic polarities such as N, N-dimethylformamide, N, N-dimethylacetamide and dimethylsulfoxide.
• Solvents Can be selected from water and used alone or in admixture of two or more. Further, the reaction can be carried out without a solvent.
• the deprotection reaction can be carried out in the presence of acid.
• the acid include 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, boron trifluoride and trimethylsilyltric acid.
• Aluminum chloride, magnesium chloride, iron chloride, zinc chloride, titanium chloride and other Lewis acids can be used.
• the amount of the acid used is preferably 0.001 to 5 mol, particularly 0.01 to 0.5 mol, per 1 mol of the aryl ether compound (1Bf).
• a base for example, amines such as ammonia, triethylamine, pyridine, lutidine, colidin, N, N-dimethylaniline and the like may be added in order to suppress the acidity.
• an appropriate reaction temperature can be selected depending on the reaction conditions, but the reaction may not proceed under low temperature conditions, so 40 to 120 ° C. is usually preferable.
• the reaction time is preferably determined by tracking the progress of the reaction by thin layer chromatography, gas chromatography, or the like in order to improve the yield, but it is usually about 2 hours to 1 day.
• the reaction can be carried out by diluting the aryl ether compound (1Bf) with a solvent, adding an acid, and heating and stirring.
• the phenol compound (1Ba) can also be obtained by ordinary aqueous post-treatment (aquious work-up), and if necessary, it can be purified according to a conventional method such as distillation, recrystallization, or chromatography.
• the conductive paste composition of the present invention contains (A) a conductive filler, (B) a phenol compound, (C) an elastomer resin, and (D) a solvent, and the phenol compound of the component (B) is said. It is characterized by being a phenol compound represented by the following general formula (1A) or (1B).
• R 1 represents a hydrogen atom, a halogen atom, a cyano group or a hydroxyl group.
• Az is a linear, branched or cyclic (ka + 2) -valent hydrocarbon group or fluorinated hydrocarbon having 1 to 20 carbon atoms.
• R 2 and R 3 are linear, branched, or cyclic alkyl groups or phenyl groups having 1 to 6 carbon atoms.
• Xf is a hydrogen atom, a halogen atom, and a fluorine atom having 1 to 10 carbon atoms, respectively.
• a linear, branched or cyclic monovalent hydrocarbon group which may be substituted with, an alkoxy group or an electron-withdrawing group which may be substituted with a fluorine atom having 1 to 10 carbon atoms.
• Each ring ZZ independently represents an aromatic monocyclic or polycyclic ring having 5 to 20 carbon atoms.
• the carbon atom of the ring ZZ may be substituted with a nitrogen atom, an oxygen atom or a sulfur atom.
• .Ka indicates an integer of 0 to 2.
• kb and kd indicate 1 or 2.
• kc and ke indicate an integer of 0 to 2.
• Az' represents a linear, branched or cyclic (ka + 2) -valent hydrocarbon group or fluorinated hydrocarbon group having 1 to 19 carbon atoms, and constitutes the above-mentioned (ka + 2) -valent hydrocarbon group.
• ka indicates 0 or 1.
• R 1 , R 2 , and R 3 are the same as above.
• ⁇ Ingredient (A)> As the conductive filler of the component (A) used in the conductive paste composition of the present invention, gold, silver, silver chloride, platinum, copper, tin, iron, titanium, nickel, palladium, aluminum, tungsten, molybdenum, ruthenium, It is preferably selected from chromium, indium, solder, and carbon or a composite thereof.
• metal particles or alloy particles such as gold, silver, platinum, copper, tin, iron, titanium, nickel, palladium, aluminum, tungsten, molybdenum, ruthenium, chromium, indium, solder, and these silver-plated powders, or carbon. Examples include powders of black, carbon nanotubes, silver chloride, zinc oxide, titanium oxide, tin oxide and the like.
• Gold, silver, platinum are preferable from the viewpoint of conductivity, silver, copper, tin, iron, titanium, nickel, aluminum, tungsten, molybdenum, ruthenium, chromium, and stainless steel are preferable from the viewpoint of price, and silver (silver powder) is generally used. Most preferred.
• the conductive filler of the component (A) is preferably silver powder having an average particle size of 5 nm to 10 ⁇ m.
• the method for measuring the average particle size is not particularly limited, but for example, it can be measured using a laser diffraction type particle size distribution device.
• Examples of the shape of the particles of the conductive filler include spherical, granular, angular, dendritic, flake-shaped, needle-shaped, amorphous, etc., and a plurality of types of fillers can be used in combination.
• the amount of the conductive filler added is preferably in the range of more than 70 parts by mass, more preferably 80 parts by mass or more and 90 parts by mass with respect to 100 parts by mass of the total of (A) the conductive filler and (C) the elastomer resin. It is as follows.
• the amount of the phenol compound added is preferably in the range of more than 0.5 parts by mass with respect to 100 parts by mass in total of (A) the conductive filler, (C) the elastomer resin and (B) the phenol compound, and more preferably. Is 1 part by mass or more and 10 parts by mass or less.
• the solvent of the component (D) adjusts the viscosity of the conductive paste composition of the present invention to make workability in printing or the like suitable. It may be the same as or different from the organic solvent used for the polymerization of polyurethane described later.
• Solvent 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, di Ethylene 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 -Ether-based solvents such as tert-amyl ether, di-n-hexyl ether, anisole, ethylene glycol monobuty
• Diethylene glycol monobutyl ether, diethylene glycol monoethyl ether acetate, and diethylene glycol monobutyl ether acetate are particularly preferable because the solvent does not easily volatilize during printing and gives a viscosity suitable for printing.
• the amount of the solvent added (D) is preferably in the range of 100 to 1,000 parts by mass with respect to 100 parts by mass of the (C) elastomer.
• the elastomer resin of the component (C) used in the conductive paste composition of the present invention is not particularly limited, but is limited to polyurethane, polyester, polyamide, polyvinyl chloride, polystyrene, polyolefin, acrylic rubber, butadiene rubber, styrene butadiene rubber, and isoprene rubber. , Elastomer propylene rubber, chloroprene rubber, silicone rubber, fluororubber and the like, and more preferably polyurethane.
• the expansion and contraction performance of the fired product obtained from the conductive paste composition of the present invention is sufficiently exhibited.
• the elastomer of the component (C) is more preferably polyurethane containing the structures represented by the following general formulas (1a) to (1c).
• R represents a hydrogen atom, a fluorine atom or a linear, branched or cyclic hydrocarbon group having 1 to 10 carbon atoms
• R f is a fluorine atom or 1 carbon atom.
• n is an integer of 1 or 2 and the broken line indicates a bond.
• R 4 is a hydrogen atom or a monovalent hydrocarbon group having 1 to 3 carbon atoms.
• R 5 and R 6 are independently hydrogen atoms or linear, branched or cyclic groups having 1 to 6 carbon atoms, respectively.
• R 5 and R 6 may be bonded to each other to form a non-aromatic ring having 3 to 8 carbon atoms together with the carbon atom to which they are bonded.
• the polyurethane containing the structures represented by the general formulas (1a) to (1c) is represented by a polyisocyanate and the general formulas (1a) to (1c) by a known method such as a one-shot method or a prepolymer method. It is obtained by reacting a polyol, polyamine, polycarboxylic acid or the like having such a structure, and the prepolymer method is preferably used.
• a diisocyanate and a high molecular weight polyol are reacted with an excess of isocyanate groups to obtain a reaction mixture containing an isocyanate group-terminated prepolymer, and (b) the prepolymer is associated with a low molecular weight diol, diamine or dicarboxylic.
• Polyurethane is synthesized by a step of increasing the molecular weight of the prepolymer by reacting with an acid (chain extender). Further, a polyurethane having a crosslinked structure can be obtained by adding a polyisocyanate having 3 or more reaction groups, or a polyol, polyamine, or polycarboxylic acid having 3 or more reaction groups.
• a capping agent having a reactive group (hydroxyl group, amino group, carboxyl group, etc.) capable of reacting with the isocyanate group is added to the capping agent at the urethane terminal.
• Derived functional groups can also be introduced.
• the structures represented by the general formulas (1a) to (1c) can react with isocyanate, the structures represented by the general formulas (1a) to (1c) are made into polyurethane while being protected by an appropriate protecting group. And then deprotection, polyurethane containing the structures represented by the above general formulas (1a) to (1c) can be synthesized.
• the conductive paste composition of the present invention is more preferably polyurethane in which the elastomer resin of the component (C) contains the structures represented by the following general formulas (2a) to (2c).
• R4 is a hydrogen atom or a monovalent hydrocarbon group having 1 to 3 carbon atoms
• Aa is a single bond or a linear, branched or cyclic divalent having 1 to 20 carbon atoms.
• R 8 is a hydrogen atom or a linear or branched alkyl group having 1 to 4 carbon atoms.
• N 2 , n 4 are integers from 0 to 10
• n 3 is an integer of 0 or 1, and the broken line indicates a bond.
• Polyisocyanate Polyisocyanates that are constituents of polyurethane include ethylene diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate (HDI), octamethylene diisocyanate, nonamethylene diisocyanate, and 2-methylpentane-1,5-.
• the above polyisocyanate may be used alone or in combination of two or more.
• High molecular weight polyol As the high molecular weight polyol which is a constituent component of polyurethane, a polyol having two or more hydroxyl groups capable of reacting with an isocyanate group and having a number average molecular weight of 500 to 5,000 can be used. Examples thereof include polyether polyols, polyester polyols, polycarbonate polyols, acrylic polyols, terminal hydroxylated polyolefins, silicone polyols, castor oil-based polyols and the like.
• polyether polyol examples include polyoxypropylene glycols, polyoxyethien glycols, polyoxytetramethylene glycols, and copolymers thereof.
• Polyoxypropylene glycols and polyoxyethylene glycols are addition polymers of alkylene oxides using low molecular weight polyols, polyamines and aminoalcohols as initiators, and low molecular weight polyols include ethylene glycol, 1,2-propanediol and the like.
• 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-dimethylolheptan, 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, cycl
• Examples of the low molecular weight amino alcohol include ethanolamine, dimethanolamine and triethanolamine
• examples of the low molecular weight polyamine include ethylenediamine, propylenediamine, butanediamine, pentamethylenediamine, hexamethylenediamine, isophoronediamine, piperazine and toluenediamine.
• examples thereof include metaphenylenediamine, diphenylmethanediamine, xylylenediamine, dimethylthiotoludiamine, 4,4-methylenebis- réelle-chloroaniline and the like.
• the initiator may be used alone or in combination of two or more.
• a polyether polyol containing the structures represented by the general formulas (1a) to (1c) can be obtained. can. It is also possible to carry out polymerization in a state where the structures represented by the above general formulas (1a) to (1c) are protected, and then deprotect and synthesize.
• alkylene oxide examples include ethylene oxide, propylene oxide, butylene oxide, etc., and they can be used alone or in combination of two or more.
• polyalkylene polyol in which two or more types are used in combination either a block type or a random type structure may be used.
• Polyoxytetramethylene glycol is a ring-opening polymer obtained by cationic polymerization of tetrahydrofuran (THF), such as crystalline polytetramethylene glycol, alkyl-substituted tetrahydrofuran such as 3-methyltetrahydrofuran in THF, and the above-mentioned dihydric alcohol.
• THF tetrahydrofuran
• Examples thereof include amorphous polytetramethylene glycol obtained by copolymerizing the above.
• polyester polyol examples include a polymerization condensate of the above-mentioned low molecular weight polyol and a polyvalent carboxylic acid or an oligomer acid, or a lactone or lactide ring-opening polymer using a low molecular weight polyol as an initiator.
• polyvalent carboxylic acids include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic 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, ⁇ -hydromuconic acid, ⁇ -hydromuconic acid, phthalic acid, Examples thereof include orthophthalic acid, terephthalic acid, isophthalic acid, toluenedicarboxylic acid, naphthalenedicarboxylic acid, hetic acid, dimer acid and hydrogenated dimer acid, and derivatives thereof, acid anhydrides, acid halides and the like can also be used.
• lactone examples include ⁇ -propiolactone, ⁇ -butyrolactone, ⁇ -butyrolactone, ⁇ -valerolactone, ⁇ -valerolactone, ⁇ -caprolactone and the like
• lactide examples include L-lactide and D-lactide
• the low molecular weight polyol, polyvalent carboxylic acid, oligomer acid, lactone, or lactide, which are constituents of the polyester polyol, may be used alone or in combination of two or more.
• polyester-amide polyol obtained by substituting the above-mentioned low molecular weight polyamine or amino alcohol for a part of the low molecular weight polyol of the polyester polyol.
• polycarbonate polyol examples include a polycondensate of the above-mentioned polyol and a carbonate compound.
• Examples of the carbonate compound include dimethyl carbonate, diethyl carbonate, ethylene carbonate, propylene carbonate, diphenyl carbonate, dinaphthyl carbonate, dianthryl carbonate, diphenanthryl carbonate, diindanyl carbonate, tetrahydronaphthyl carbonate and the like.
• the low molecular weight polyol or carbonate compound which is a constituent component of the polycarbonate polyol may be used alone or in combination of two or more.
• acrylic polyol examples include a copolymer obtained by copolymerizing a hydroxy group-containing (meth) acrylate and a vinyl monomer.
• Examples of the hydroxyl group-containing (meth) acrylate include 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, 3-hydroxy-2,2-dimethylpropyl acrylate, and 2,2-dihydroxy. Examples thereof include methylbutyl (meth) acrylate, pentaerythritol tri (meth) acrylate, polyhydroxyalkylmalate, and polyhydroxyalkylfumarate.
• the above-mentioned (meth) acrylate may be used alone or in combination of two or more.
• Vinyl monomers include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, s-butyl (meth) acrylate, and t-.
• a carboxyl group-containing vinyl monomer such as vinyl oxide, fumaric acid, maleic acid, and itaconic acid, or an alkyl ester thereof, a monomer containing an isocyanate group such as 3- (2-isocyanide-2-propyl) - ⁇ -methylstyrene, and tetra.
• Fluorine-containing vinyl monomers such as fluoroethylene, chlorotrifluoroethylene, trichlorofluoroethylene, hexafluoropropylene, vinylidene fluoride, vinyl fluoride, trifluoromethyltrifluoroethylene, ⁇ - (meth) acryloxypropyltrimethoxysilane, etc. Silicone monomer and the like can be mentioned.
• the above-mentioned monomers may be used alone or in combination of two or more.
• terminal hydroxylated polyolefin examples include compounds in which one or more types of olefin polymers are hydroxylated at the ends.
• examples of the olefin include ethylene, propylene, butadiene, isoprene, styrene, acrylonitrile, vinyl ether, and vinyl acetate, and a part of the above structure may be substituted with a halogen such as fluorine, chlorine, or bromine.
• silicone polyol examples include a vinyl group-containing silicone compound obtained by polymerizing ⁇ -methacryloxypropyltrimethoxysilane and the like, and ⁇ , ⁇ -dihydroxypolydimethylsiloxane and ⁇ , ⁇ -dihydroxy having at least one terminal hydroxyl group in the molecule.
• silicone polyol examples include polysiloxane such as polydiphenylsiloxane.
• Examples of the vegetable oil-based polyol include castor oil, hydroxyl group-containing vegetable oil such as palm oil, ester-modified castor oil polyol obtained by reaction of castor oil fatty acid and polyol, dehydrated castor oil, partially dehydrated castor oil, hydrogenated castor oil and the like. Can be mentioned.
• the number average molecular weight of the high molecular weight polyol is preferably in the range of 500 or more and 5,000 or less, more preferably 1,000 or more and 3,000 or less, and further preferably 1,000 or more and 2,000 or less.
• the number average molecular weight of the high molecular weight polyol is not less than the lower limit, it is possible to suppress an excessive increase in the urethane group concentration in polyurethane and the accompanying decrease in performance such as an increase in hardness and a decrease in elasticity. Further, when the number average molecular weight is not more than the upper limit, it is possible to suppress an excessive decrease in the urethane group concentration, prevent a decrease in the strength derived from the urethane bond, and achieve both appropriate strength and elasticity.
• the high molecular weight polyol is preferably a bifunctional polyol or a trifunctional polyol, more preferably a bifunctional polyol.
• Chain extender examples include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, and 1,5-pentanediol.
• polyols described in the following general formulas (3a) to (3c) can be used as the chain length extender and introduced into the side chain of polyurethane.
• chain length extender the polyols represented by the general formulas (3a) to (3c) may be used alone or in combination with the above-mentioned chain extender. (In the formula, R 4 , A a , n 1 , n 2 , and n 4 are the same as described above.)
• linear, branched or cyclic hydrocarbon group having 1 to 20 carbon atoms of Aa include the following examples.
• Examples thereof include those substituted with ⁇ ( R8 is a hydrogen atom or a linear or branched alkyl group having 1 to 4 carbon atoms).
• Examples of the chain length extender represented by the general formulas (3a) to (3c) include, but are not limited to, the following. (In the formula, R 4 , R 5 , R 6 , and R 8 are the same as described above.)
• the chain extender having the structure represented by the general formulas (3a) to (3c) is preferably used in an amount of 5 to 50% by mass, more preferably 20 to 40% by mass, based on the total amount of the constituent components of urethane.
• Cross-linking agent As the cross-linking agent, trihydric alcohols such as glycerin, trimethylolpropane and triisopropanolamine, and polyhydric alcohols such as pentaerythritol, ⁇ -methylglucoside and diglycerin are used.
• the amount of the cross-linking agent added is preferably in the range of 0 to 5% by mass, more preferably 0 to 3% by mass, based on the total amount of the urethane constituents.
• the amount of the cross-linking agent added is not more than the upper limit, the strength does not increase excessively and the flexibility and elasticity are not impaired, so that it is suitable for use in the conductive paste composition of the present invention.
• Organic solvent Polyurethane is synthesized by bulk polymerization or solution polymerization.
• examples of the organic solvent used for solution polymerization include toluene, xylene, cumene, 1,2,3-trimethylbenzene, 1,2,4-trimethylbenzene, 1,3,5-trimethylbenzene, styrene, and ⁇ -methylstyrene.
• Hydrohydrogen-based solvent n-heptane, isoheptane, n-hexane, octane, 3-methylhexane, 2,3-dimethylpentane, 3-ethylpentane, 1,6-heptadiene, 5-methyl-1-hexene, norbornane , Norbornene, dicyclopentadiene, 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-hep
• 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, acetic acid-tert-butyl, ethyl pyruvate, 3-methoxy Ester solvents such as methyl propionate, ethyl 3-ethoxypropionate, tert-but
• the amount of the organic solvent added is preferably in the range of 20 parts by mass or more and 500 parts by mass or less with respect to 100 parts by mass of the total amount of the polyurethane constituent components (polyisocyanate, high molecular weight polyol, chain extender, cross-linking agent). More preferably, it is 25 parts by mass or more and 100 parts by mass or less.
• the organic solvent may be removed by distillation under reduced pressure or crystallization after the polymerization reaction, or may be applied to the conductive paste composition as a polyurethane solution without being removed.
• a known catalyst can be appropriately selected and used, and examples thereof include an amine-based catalyst, an ammonium salt-based catalyst, a potassium salt-based catalyst, and an organic metal catalyst.
• Examples of the amine-based catalyst include triethylamine, N, N-dimethylcyclohexylamine, triethylenediamine, 2-methyltriethylenediamine, N, N, N', N'-tetramethylethylenediamine, N, N, N', N'.
• ammonium salt-based catalyst examples include a quaternary ammonium salt such as tetraethyl hydroxylammonium, 1,8-diazabicyclo (5,4,0) -undecene-7 or 1,5-diazahicyclo (4,3,0)-.
• quaternary ammonium salt such as tetraethyl hydroxylammonium, 1,8-diazabicyclo (5,4,0) -undecene-7 or 1,5-diazahicyclo (4,3,0)-.
• potassium salt-based catalyst examples include potassium carbonate, potassium acetate, potassium octylate and the like.
• organic metal catalyst examples include tin acetate, tin octylate (tin 2-ethylhexanoate), tin oleate, tin laurate, dibutyltin diacetate, dimethyltin dilaurate, dibutyltin dilaurate, dibutyltin dimercaptide, and dibutyltin.
• Organic tin compounds such as maleate, dibutyltin dilaurate, dibutyltin dineodecanoate, dioctyltin dimercaptide, dioctyltin dilaurylate, dibutyltin dichloride, organic lead compounds such as lead octanoate and lead naphthenate, and organics such as nickel naphthenate.
• nickel compounds include organic cobalt compounds such as cobalt naphthenate, organic copper compounds such as copper octene, and organic bismuth compounds such as bismuth octylate and bismuth neodecanoate.
• the polyurethane used as the elastomer of the component (C) of the present invention contains the structures represented by the general formulas (1a) to (1c), it may inhibit the activity of the basic catalyst. It is preferable to use, and more preferably, an organic bismuth compound is mentioned.
• urethanization catalysts can be used alone or in combination of two or more.
• the amount of the urethanization catalyst used is preferably in the range of 0 parts by mass or more and 5 parts by mass or less, and in the range of 0.1 parts by mass or more and 2 parts by mass or less with respect to 100 parts by mass of the total amount of polyurethane components. It is more preferable to be used in.
• a functional group derived from the cap agent can be introduced into the polyurethane terminal by adding a terminal cap agent after polymerizing with an excess of isocyanate groups.
• urethane acrylate can be synthesized by using the following hydroxy (meth) acrylate as a cap agent at the end of polyurethane.
• R 7 is a hydrogen atom or a methyl group
• Et is an ethyl group
• Ph is a phenyl group.
• R 4 is the same as above.
• Urethane acrylate is polymerized by irradiating it with heat or ultraviolet rays, visible light, laser light, electron beam, X-ray, ⁇ -ray, plasma, microwave or other active energy rays together with a reactive monomer and a polymerization initiator as necessary.
• Examples of the reactive monomer include methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, t-butyl (meth) acrylate, isobutyl (meth) acrylate, and isoamyl.
• polymerization initiator examples include acetophenone, 2,2-diethoxyacetophenone, p-dimethylaminoacetophenone, benzophenone, 2-chlorobenzophenone, 4,4'-bisdiethylaminobenzophenone, benzoinethyl ether, and benzoin-n-propyl ether.
• Benzoin isopropyl ether benzoin isobutyl ether, benzoin-n-butyl ether, benzoin dimethyl ketal, thioxanthone, p-isopropyl- ⁇ -hydroxyisobutylphenone, 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexylphenylketone , 2-Methyl-1- [4- (Methylthio) Phenyl] -2-morpholinopropane-1-one, 2-hydroxy-2-methyl-1-phenylpropane-1-one, 2,4,6-trimethyl Benzophenone, 4-methylbenzophenone, (2,4,6-trimethylbenzoyl) -diphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphinoxide, 2,2-dimethoxy-1,2- Examples thereof include diphenyletanone, but 1-hydroxycyclohexylphenyl
• the structures represented by the general formulas (1a) to (1c) can be introduced into the polyurethane terminal.
• the following compounds containing a hydroxyl group or an amino group that reacts with the structure represented by the general formulas (1a) to (1c) and isocyanate can be mentioned.
• Ra indicates the structure represented by the above-mentioned general formulas (3a) to (3c).
• M1 and m2 are integers of 0 to 20.
• R4 is the same as described above.
• the reaction temperature at the time of polyurethane synthesis is appropriately changed depending on the type of reaction substrate, but is usually preferably 30 to 200 ° C, more preferably 40 to 120 ° C.
• the weight average molecular weight of polyurethane is preferably 10,000 to 500,000, more preferably 15,000 to 200,000. More preferably, it is 20,000 to 150,000.
• the polyurethane according to this embodiment may further contain an antioxidant, an antifoaming agent, an ultraviolet absorber and the like as additives, if necessary.
• the present invention provides a conductive wiring formed on a substrate by using the above conductive paste composition. Further, the present invention provides a stretchable conductive wiring formed on a stretchable base material using the above conductive paste composition.
• the stretchable conductive wiring of the present invention will be described, but the present invention is not limited thereto.
• the base material forming the elastic conductive wiring examples include polyurethane, polyester, silicone, nitrile rubber, butadiene rubber, polyethylene, polypropylene, polyolefin, PTFE, PFA and the like.
• the base material is preferably stretchable, more preferably a stretchable sheet or film, still more preferably a stretchable polyurethane base material, and particularly preferably a thermoplastic polyurethane base material.
• the surface of the sheet may be flat, but may be uneven. When the unevenness is formed, it is possible to form an elastic wiring having a bellows structure in the direction perpendicular to the base material, and it is possible to suppress a change in conductivity during expansion and contraction. It is also possible to use a non-woven fabric or a cloth made of elastic fibers.
• the stretchable base material preferably has a maximum stretchability of 1000%. It is said that the degree of elongation of the skin with respect to human movement is 10% on the bones such as the chest, 20% on the abdomen, and 50% on the joints, and it is required for conductive wiring depending on the part to be attached to the skin. Elasticity is different.
• a conductive wiring made of the conductive paste composition of the present invention is formed on a stretchable base material.
• the method of applying the conductive wiring on the elastic base material is not particularly limited, but for example, dip coating, spray coating, spin coating, roll coating, flow coating, doctor coating, screen printing, flexographic printing, gravure printing, inkjet printing, etc. Method is suitable. In particular, productivity can be improved by forming a wiring pattern by printing, and free design including wiring width becomes possible.
• the film thickness of the conductive wiring is preferably in the range of 10 nm to 1000 ⁇ m. More preferably, it is 5 to 50 ⁇ m.
• the conductive paste composition is applied by printing on the elastic base material, and then fired.
• the firing temperature is preferably 60 to 160 ° C., more preferably 120 ° C. to 150 ° C., and the time is preferably 1 second to 10 hours, more preferably 10 minutes to 5 hours.
• the firing can be performed in a hot plate or an oven, but it can also be performed at a temperature higher than the above temperature in a short time by flash annealing, and it is also possible to perform firing by irradiation with infrared light.
• Conductivity can be evaluated by forming elastic conductive wiring on the base material and measuring the electrical resistance between both ends of the elastic conductive wiring. It can be said that the smaller the change in electrical resistance before and during stretching the base material, the smaller the deterioration of conductivity when the stretched base material is contracted and returned to its original state, the better the stretchable conductive wiring. .. Further, it is preferable that the change in electrical resistance is small without breaking the wiring when the wiring is repeatedly expanded and contracted.
• the electric resistance at 20% extension is preferably 500% or less of the electric resistance before extension, and the lower limit is not particularly limited, and a lower value is preferable, for example, 150% or more.
• the maximum electrical resistance when repeatedly expanded and contracted 1000 times at an elongation rate of 20% is preferably 5000% or less of the electrical resistance before expansion and contraction, and the lower limit is not particularly limited, and a low value is preferable, for example, 300% or more.
• the electric resistance can be obtained by the measurement method described later.
• a cover film for covering the conductive wiring can be provided.
• the material of the cover film can be selected from polyurethane, urethane acrylate, polyester, silicone, nitrile rubber, butadiene rubber, polyethylene, polypropylene, polyolefin, PTFE, PFA and the like as well as the base material.
• the film thickness of the cover film is preferably in the range of 10 nm to 1 mm.
• the conductive paste composition of the present invention for example, when the conductive filler of the component (A) is silver powder, the functional groups represented by the general formulas (1a) to (1c) and silver in the elastomer resin of the component (C). It is presumed that a silver salt is formed by the oxide film of the powder, and the silver salt is reduced by heat or the like to generate silver nanoparticles. Further, it is presumed that the phenol compound of the above component (B) also has weak acidity, forms an oxide film of silver powder and a silver salt, and produces silver nanoparticles by reduction in the same manner as described above. ..
• the phenol compound of the component (B) is the phenol compound of the general formulas (1A) and (1B), it has a fluorine atom on the aromatic ring, and the fluorine atom and the silver salt are used to obtain the fluorine atom.
• the nuclear substitution reaction proceeds, and silver fluoride is produced as a by-product in the process. It is presumed that this is reduced by heat or the like to produce silver nanoparticles.
• the conductive wiring formed by using the conductive paste composition of the present invention it is presumed that silver nanoparticles are generated by three routes as described above in the firing process of the wiring, and the generated silver nanoparticles are silver powder. It exhibits high conductivity by being dispersed in the insulating polymer between the bodies. In addition, even when the wiring is extended and the distance between the silver powders is widened, the silver nanoparticles dispersed between the silver powders make it difficult for the conductive path to be cut, so that disconnection is unlikely to occur and the change in conductivity is small. ..
• Me represents a methyl group
• Mw weight average molecular weight
• Mn number average molecular weight
• the measurement conditions of GPC are as follows. Column: TSKgel G4000H XL , TSKgel G3000H XL , TSKgel G2000H XL 2 mobile phase: tetrahydrofuran Column oven temperature: 40 ° C. Sample concentration: 0.20% by mass Sample injection volume: 100 ⁇ L Flow rate: 1 mL / min
• Example 1 The phenolic compound of the present invention was synthesized by the method shown below. [Example 1-1] Synthesis of phenol 1
• Example 1-1-1 Synthesis of bromobenzene 1 Methanesulfonic acid (4.8 g) is added to a toluene (10 g) solution of bromophenol 1 (76.4 g) and isoamylene (112.2 g) under a nitrogen atmosphere. It was added at ⁇ 20 to ⁇ 10 ° C. After stirring at the same temperature for 3 hours, triethylamine (10.1 g) and then 25 mass% caustic soda water (32.0 g) were added dropwise to stop the reaction. Normal aqueous post-treatment (aqueous work-up) was performed. Bromobenzene 1 (84.6 g, yield 81%) was obtained by distillation under reduced pressure. Boiling point: 67 ° C / 10 Pa.
• Example 1-1-3 Synthesis of protected phenol 1 A slurry of intermediate phenol 1 (13.9 g), potassium carbonate (10.6 g), sodium iodide (100 mg), and dimethyl formaldehyde (50 g) under a nitrogen atmosphere. Aetherizing agent 1 (20.9 g) was added to the solution at 60-80 ° C. After stirring at the same temperature for 6 hours, water (100 g) was added dropwise to stop the reaction. A usual aqueous post-treatment (aqueous work-up) was carried out to obtain protected phenol 1 (24.5 g, yield 95%).
• IR (D-ATR): ⁇ 3402, 2953, 2942, 2920, 2870, 2854, 1607, 1516, 1479, 1471, 1460, 1398, 1313, 1275, 1255, 1205, 1158, 111, 1028, 840, 788 cm. -1 .
• 1 1 H-NMR (600 MHz in DMSO-d6): ⁇ 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.
• 19 F-NMR (565 MHz in DMSO-d6): ⁇ -133.7 (1F, t) ppm.
• Example 1-2-1 Synthesis of bromobenzene 2 Fluorobenzene 1 (100 g) is added to a solution of t-butoxypotassium (63.9 g) in THF (360 g) at 0 to 10 ° C. under a nitrogen atmosphere. Dropped. After stirring at the same temperature for 10 hours, water (150 g) was added dropwise to stop the reaction. Normal aqueous post-treatment (aqueous work-up) was performed. Bromobenzene 2 (98.6 g, yield 77%) was obtained by distillation under reduced pressure. Boiling point: 97-100 ° C / 700 Pa.
• Example 1-2-2 Synthesis of intermediate phenol 2 Intermediate phenol 2 was obtained in the same manner as in [Example 1-1-2] except that bromobenzene 1 was changed to bromobenzene 2. Yield 77%).
• Example 1-3-1 Synthesis of bromobenzene 3
• Bromobenzene 3 was obtained in the same manner as in [Example 1-1-3] except that the intermediate phenol 1 was changed to bromophenol 1. Rate 94%).
• Example 1-7-1 Synthesis of phenol 7 To a slurry solution of dihydroxybenzene 1 (55.9 g), potassium carbonate (41.5 g), sodium iodide (100 mg), and dimethylformaldehyde (300 g) under a nitrogen atmosphere. , Etherealizing agent 2 (19.3 g) was added at 60-80 ° C. After stirring at the same temperature for 3 hours, water (400 g) was added dropwise to stop the reaction. Normal aqueous post-treatment (aqueous work-up) was performed. Recrystallization was performed from a mixed solvent of ethyl acetate / n-hexane to obtain phenol 7 (15.4 g, yield 52%).
• Example 1-16-1 Synthesis of protected phenol 11 [Example 1-1-3] except that the intermediate phenol 1 was changed to the intermediate phenol 2 and the etherifying agent 1 was changed to the etherifying agent 5. Protected phenol 11 was obtained in the same manner (yield 89%).
• Example 1-20-1 Synthesis of protected phenol 15 Under a nitrogen atmosphere, a solution of intermediate phenol 1 (10.0 g), triethylamine (6.5 g) and acetonitrile (30 g) at an internal temperature of 20 to 40 ° C. Then, a solution of acid chloride 1 (5.8 g) and acetonitrile (10 g) was added dropwise. Stirring was continued for 3 hours at the same reaction temperature. Then, water (40 g) was added at an internal temperature of 30 ° C. or lower to stop the reaction. The usual post-treatment method was carried out to obtain protected phenol 15 (14.2 g, yield 96%).
• the polyurethane used in the conductive paste composition of the present invention was synthesized by the method shown below.
• PU2-14 were synthesized (synthesis) by the same procedure as in [Synthesis Example 1] above, except that the types of polyisocyanate, high molecular weight polyol, chain extender, compounding ratio and amount of catalyst used were changed as shown in Table 1. Examples 2-14).
• phenols 1 to 26 described in Example 1 above were used, and as the additive for the comparative example, the following comparative additives 1 to 4 were used.
• -Silver powder A Average particle size ( DL50 ) is 2.1 ⁇ m -Silver powder B: Average particle size ( DL50 ) is 5.3 ⁇ m -Silver powder C: Average particle size ( DL50 ) is 1.2 ⁇ m -Silver powder D: Average particle size ( DL50 ) is 0.67 ⁇ m -Silver powder E: Average particle size ( DL50 ) is 1.72 ⁇ m -Copper powder A: Average particle size ( DL50 ) is 5.5 ⁇ m -Copper powder B: Average particle size ( DL50 ) is 1.3 ⁇ m The average particle size was measured by measuring the particle size distribution using a laser diffraction particle size distribution device, and the integrated value of 50% was determined as the average particle size.
• Examples 3-1 to 50, Comparative Examples 2-1 to 13 Evaluation of elastic conductive wiring ⁇ Preparation of evaluation sample>
• a screen printing machine MT-320TVC manufactured by Microtech Co., Ltd. is used to apply a conductive paste composition on a polyurethane film and then heat-treated with a hot air dryer to obtain a line width of 3 mm, a length of 100 mm, and a film thickness of 15 ⁇ m. Conductive wiring was formed.
• an electrode is installed inside the sample fixing jig of the tensile tester (precision universal tester AG-Xplus HS), and a PXIe-4136SMU resistance measuring device manufactured by National Instruments Co., Ltd. is used to measure 4 terminals. It was performed by the resistance measurement method.
• -Change in maximum electrical resistance value when repeatedly expanding and contracting 1000 times at an elongation rate of 0 to 20% [Maximum electrical resistance ( ⁇ ) in repeated expansion and contraction test] ⁇ [Initial electrical resistance ( ⁇ )] x 100
• Tables 4 and 5 show the maximum changes in electrical resistance when the product is repeatedly expanded and contracted 1000 times at an elongation rate of 20%.
• the present invention is not limited to the above embodiment.
• the above-described embodiment is an example, and any one having substantially the same structure as the technical idea described in the claims of the present invention and having the same effect and effect is the present invention. Is included in the technical scope of.

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