Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
  • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
  • C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
  • C08G69/28—Preparatory processes
• • 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
  • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
  • C08K3/013—Fillers, pigments or reinforcing additives
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
  • C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
  • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
  • H01G11/22—Electrodes
  • H01G11/30—Electrodes characterised by their material
  • H01G11/32—Carbon-based
  • H01G11/38—Carbon pastes or blends; Binders or additives therein
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
  • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
  • H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
  • H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M4/00—Electrodes
  • H01M4/02—Electrodes composed of, or comprising, active material
  • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M4/00—Electrodes
  • H01M4/02—Electrodes composed of, or comprising, active material
  • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
  • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
  • Y02E60/10—Energy storage using batteries
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
  • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
  • Y02E60/13—Energy storage using capacitors

Definitions

• the present invention relates to a resin composition, a laminate and a method for producing the same, an electrode, a secondary battery, and an electric double layer capacitor.
• Lithium-ion batteries as rechargeable high-capacity batteries, have made it possible to improve the functionality of electronic devices and operate them for a long time. Furthermore, lithium-ion batteries are installed in automobiles and the like, and are regarded as promising batteries for hybrid vehicles and electric vehicles.
• the negative electrode has a negative electrode formed by applying a slurry containing a carbon-based active material and a binder such as PVDF or styrene-butadiene rubber (SBR) onto a copper foil.
• an active material such as lithium cobalt oxide and a binder such as polyvinylidene fluoride (PVDF)
• PVDF polyvinylidene fluoride
• the negative electrode has a negative electrode formed by applying a slurry containing a carbon-based active material and a binder such as PVDF or styrene-butadiene rubber (SBR) onto a copper foil.
• PVDF polyvinylidene fluoride
• the negative electrode active material In order to further increase the capacity of the lithium ion battery, it is being considered to use silicon, germanium or tin as the negative electrode active material. Since the negative electrode active material using silicon, germanium, tin, etc. can receive a large amount of lithium ions, there is a large change in volume between when it is sufficiently charged and when it is sufficiently discharged. On the other hand, the above-mentioned binders such as PVDF and SBR cannot follow the volume change of the active material.
• the polyimide resin generally dissolves only in an organic solvent such as N-methylpyrrolidone or N, N'-dimethylacetamide, and has a problem of high environmental load. Therefore, studies are underway to mix the resin with an aqueous solvent and use it as an aqueous binder.
• an aqueous solution obtained by adding a water-soluble organic amine or an imidazole-based compound to the polyimide precursor see, for example, Patent Document 1
• a hydroxyl group, a carboxyl group or a sulfonic acid group is introduced into the side chain.
• An aqueous solution in which the above-mentioned polyimide, polyamideimide, or polybenzoxazole is mixed with an alkali metal hydroxide or the like is known (see, for example, Patent Documents 2 to 3 and Non-Patent Document 1).
• the polyamide-based resin As for the polyamide-based resin, an aqueous solution obtained by mixing a polyamide-based resin in which a hydroxyl group, a carboxyl group or a sulfonic acid group is introduced into a side chain and a basic compound is known (see, for example, Patent Document 4).
• Japanese Unexamined Patent Publication No. 2014-078416 Japanese Unexamined Patent Publication No. 2011-137063 International Publication No. 2019/009135 International Publication No. 2017/11710
• the aqueous solution of the polyimide precursor as described in Patent Document 1 has a problem in storage stability because the polymer main chain is hydrolyzed and the aqueous solution deteriorates. Further, the aqueous solutions of polyimide, polyamide-imide, polyamide resin and the like as described in Patent Documents 2 and 4 and Non-Patent Document 1 have a problem that cracks occur at the time of forming a thick film. Although the polyimide described in Patent Document 3 has a purpose of suppressing such shrinkage, it cannot be said that it is sufficient for further thickening of the electrode as the capacity of the battery increases, and there is a problem in crack resistance.
• the initial efficiency is the efficiency of the first cycle (the efficiency of the discharge capacity with respect to the charge capacity) when charging and discharging are repeated.
• a binder such as PVDF or SBR is used, and there is a problem of characteristic deterioration in a long-term charge / discharge cycle.
• the present invention provides a resin composition having good storage stability, improved crack resistance during thick film formation, and improved initial efficiency and long-term cycle characteristics when used as a negative electrode binder.
• the purpose is.
• the present invention is a resin composition containing (a) a polyamide resin, wherein the (a) polyamide resin has a structure in which a hydrogen atom bonded to a nitrogen atom of an amide group is substituted with another group in the main chain. Moreover, it is a resin composition which is a resin which contains at least one anion selected from the group consisting of a phenoxide anion, a carboxylate anion and a sulfonic acid anion, and a counter cation with respect to the anion in a side chain.
• the resin composition according to the embodiment of the present invention is a resin composition containing (a) a polyamide resin, and the above (a) polyamide resin has a hydrogen atom bonded to a nitrogen atom of an amide group as another group.
• the (a) polyamide resin used in the present invention has a structure in which the hydrogen atom bonded to the nitrogen atom of the amide group is replaced with another group in the main chain, and has a phenoxide anion, a carboxylate anion and a sulfonate anion.
• the side chain contains at least one anion selected from the group consisting of the above anions and a counter cation to the anion.
• the polyamide resin has at least one anion selected from the group consisting of a phenoxide anion, a carboxylate anion, and a sulfonic acid anion, and a counter cation to the anion in the side chain, so that the polyamide resin becomes soluble in water. Excellent.
• Having the anion and its counter-cation in the side chain means, in other words, having the structure of at least one salt selected from the group consisting of phenol salt, carboxylate and sulfonate in the side chain. Can be done.
• the main chain is a linear molecular chain that serves as a trunk in a polymer constituting a resin, and mainly refers to a chain in which carbon atoms are connected.
• the side chain refers to a part other than the main chain.
• the hydrogen atom bonded to the nitrogen atom of the amide group has a structure in which the hydrogen atom is substituted with another group in the main chain can be paraphrased as follows.
• the amide group as a repeating structure in the polyamide resin is represented by -CO-NH-, but in the (a) polyamide resin used in the present invention, the hydrogen atom (H) in the above structure is any other option. Including those substituted with the group of.
• the polyamide resin has a structure in which the hydrogen atom bonded to the nitrogen atom of the amide group is replaced with another group in the main chain, so that the number of hydrogen bonding sites is reduced as compared with the normal polyamide resin. Therefore, it is considered that the intermolecular interaction between the polyamide resins becomes small and the solubility in a solvent, particularly water, is improved. Further, since the intermolecular interaction is small, when the resin composition according to the present invention is applied to form a thick film, the resin component does not shrink rapidly even if the solvent is volatilized by prebaking, and cracks occur. Is unlikely to occur.
• polyamide resin has little electrochemical deterioration, so when it is used as a binder for electrodes of lithium-ion batteries, the initial efficiency and long-term cycle characteristics of the batteries are improved. do.
• the (a) polyamide resin used in the present invention is preferably a resin containing a structure represented by the following general formula (1) as a repeating unit.
• R 1 represents an organic group having 2 to 30 carbon atoms.
• R 2 represents an organic group having 3 to 50 carbon atoms.
• R 3 and R 4 each independently represent a halogen atom or an organic group having 1 to 10 carbon atoms. At least one of R 3 and R 4 may be connected to a part of R 1 to form an annular structure. Further, R 3 and R 4 may be directly bonded to form an annular structure.
• R 5- and R 6- each independently represent at least one anion selected from the group consisting of phenoxide anions, carboxylate anions and sulfonic acid anions.
• M + represents the counter cation for the anion.
• a 1 and a 2 are integers from 0 to 4, and a 1 + a 2 > 0.
• R 1 is preferably a hydrocarbon group, more preferably a hydrocarbon group having 2 to 20 carbon atoms, and further preferably a hydrocarbon group having 2 to 15 carbon atoms. It is preferably a hydrocarbon group having 2 to 10 carbon atoms. Further, from the viewpoint of the initial efficiency of the battery when used as a negative electrode binder, R 1 is preferably an aliphatic group.
• R 5- is preferably a carboxylate anion from the viewpoint of adhesiveness to the substrate.
• a 1 is preferably 0 to 2.
• R 1 moiety of the diamine to give benzidine, diaminodiphenyl ether, diaminodiphenylmethane, diaminodiphenyl sulfone, diaminodiphenyl sulfide, bis (4-aminophenoxy) Benzene, bis (3-aminophenoxy) benzene, phenylenediamine, naphthalenediamine, bis [4- (4-aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] sulfone, 4,4'- Bis (4-aminophenoxy) biphenyl, bis [4- (4-aminophenoxy) phenyl] ether, 2,2'-dimethyl-4,4'-diaminobiphenyl, 2,2'-diethyl-4,4'- Diaminobiphenyl, 3,
• 1 to 10 mol% of ⁇ R 1 ( ⁇ R 5-5 M + ) a 1 ⁇ may be a residue of a diamine containing a siloxane bond.
• Specific diamines that give residues of diamines containing a siloxane bond include 1,3-bis (3-aminopropyl) tetramethyldisiloxane.
• R 3 and R 4 include fluoro group, chloro group, bromo group, iodo group, methyl group, ethyl group, propyl group, butyl group, isopropyl group, isobutyl group, t-butyl group, isopentyl group and hexyl.
• examples thereof include a group, a trifluoromethyl group, a pentafluoroethyl group, a cyclobutyl group, a cyclohexyl group, a cyclopentyl group, a phenyl group and a naphthyl group.
• R 3 and R 4 may be connected to a part of R 1 to form an annular structure.
• a residue of bipiperidine and the like can be mentioned. Be done.
• a 1 is an integer of 1 to 4 residues of 3,3'-bipiperidin-4,4'-disodium dicarboxylic acid and the like can be mentioned.
• R 3 and R 4 may be directly bonded to form an annular structure.
• -N (R 3 ) -R 1 (-R 5- M + ) a 1 -N (R 4 )-in that case, when a 1 is 0, piperazine, homopiperazin, and methyl Examples thereof include residues of piperazine and dimethylpiperazine.
• a 1 is an integer of 1 to 4 residues of sodium piperazine-2-carboxylate, sodium homopiperazin-2-carboxylate, and the like can be mentioned.
• R 7 to R 10 are independently methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group or t-butyl group, respectively.
• R 11- , R 13- , R 15- , R 17- , R 19- and R 21- each independently represent at least one anion selected from the group consisting of carboxylate anions and sulfonic acid anions.
• M + represents the counter cation for the anion.
• R 12 , R 14 , R 16 , R 18 , R 20 and R 22 each independently represent a hydrocarbon group having 1 to 4 carbon atoms.
• a 3 represents an integer of 1 to 6.
• a 5 , a 7 , a 9 , a 11 , a 13 and a 15 each independently represent an integer of 0 to 4.
• a 4 + a 5 , a 6 + a 7 , a 12 + a 13 and a 14 + a 15 each independently represent an integer of 0 to 4.
• a 8 + a 9 represents an integer from 0 to 5.
• a 10 + a 11 represents an integer from 0 to 6.
• R 2 is a residue of a dicarboxylic acid, a tricarboxylic acid, a tetracarboxylic acid, or the like.
• R 2 is preferably an organic group having 3 to 30 carbon atoms.
• R 2 is preferably a hydrocarbon group, more preferably a hydrocarbon group having 3 to 30 carbon atoms, and further preferably a hydrocarbon group having 3 to 15 carbon atoms. It is preferably a hydrocarbon group having 3 to 10 carbon atoms.
• R 2 is preferably an aliphatic group.
• R 6- is preferably a carboxylate anion from the viewpoint of adhesiveness to the substrate.
• a 2 is preferably an integer of 0 to 2 from the viewpoint of crack resistance.
• R 2 when a 2 is 0 examples include a residue of a dicarboxylic acid.
• terephthalic acid, isophthalic acid, diphenyl ether dicarboxylic acid, diphenylsulfone dicarboxylic acid, diphenylmethanedicarboxylic acid, biphenyldicarboxylic acid, 2,2'-bis (carboxyphenyl) propane, 2,2'-bis (carboxyphenyl) hexafluoro Residues of propane, adipic acid, fumaric acid, succinic acid, oxalic acid, cyclohexane-decarboxylic acid, cyclopentanedicarboxylic acid and the like can be mentioned.
• -R 2 (-R 6- M + )-when a 2 is 1 include a residue of dicarboxylic acid, and when R 6- is a carboxylate anion, trimellitic acid and trimesic acid. , Residues of tricarboxylic acids such as diphenyl ether tricarboxylic acid and biphenyl tricarboxylic acid.
• pyromellitic acid biphenyltetracarboxylic acid, benzophenone tetracarboxylic acid, 2,2-bis (dicarboxyphenyl) hexafluoropropane, 1,1-bis (dicarboxyphenyl) ethane, bis (dicarboxyphenyl) Methan, bis (dicarboxyphenyl) sulfone, bis (dicarboxyphenyl) ether, naphthalenetetracarboxylic acid, 4,4'-(4,4'-isopropyridene diphenoxy) diphthalic acid, pyridinetetracarboxylic acid, perylenetetracarboxylic acid Residues of aromatic tetracarboxylic acids such as acids and semi-aromatics such as 4- (2,5-dioxo tetrahydrofuran-3-yl) -1,2,3,4-tetrahydronaphthalene-1,2-dica
• R 2 (R 6- M + ) a 2 - following structures may be mentioned as preferred examples of R 2 moieties.
• R 23 to R 32 are independently methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group or t-butyl group, respectively. From the viewpoint of crack resistance, it is preferably a methyl group or an ethyl group.
• a 16 , a 17 and a 20 to a 26 represent integers from 0 to 4. From the viewpoint of crack resistance, it is preferably 0. a 18 represents an integer from 1 to 10. From the viewpoint of crack resistance, it is preferably 1 to 4. a 19 represents an integer of 0 to 3. From the viewpoint of crack resistance, it is preferably 0.
• X 1 to X 4 are independently single-bonded, -O-, -S-, -CH 2- , -C (CH 3 ) 2- , -C (CF 3 ) 2- , -CO- or-. It is a group represented by SO 2-.
• R 33 to R 42 are independently methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group or t-butyl group, respectively. From the viewpoint of crack resistance, it is preferably a methyl group or an ethyl group.
• a 27 , a 28 , a 31 , a 33 and a 35 each independently represent an integer of 0 to 3. From the viewpoint of crack resistance, it is preferably 0.
• a 32 , a 34 , a 36 and a 37 each independently represent an integer of 0-4. From the viewpoint of crack resistance, it is preferably 0.
• a 29 represents an integer from 1 to 10. From the viewpoint of crack resistance, it is preferably 1 to 4.
• a 30 represents an integer of 0 to 3. From the viewpoint of crack resistance, it is preferably 0.
• X 5 to X 8 are independently single-bonded, -O-, -S-, -CH 2- , -C (CH 3 ) 2- , -C (CF 3 ) 2- , -CO- or-. It is a group represented by SO 2-.
• R 43 to R 52 are independently methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group or t-butyl group, respectively. From the viewpoint of crack resistance, it is preferably a methyl group or an ethyl group.
• a 38 and a 39 each independently represent an integer of 0 to 2. From the viewpoint of crack resistance, it is preferably 0.
• a 40 to a 44 and a 46 each independently represent an integer of 0 to 3. From the viewpoint of crack resistance, it is preferably 0.
• a 45 and a 47 each independently represent an integer from 0 to 4. From the viewpoint of crack resistance, it is preferably 0.
• X 9 to X 12 are independently single-bonded, -O-, -S-, -CH 2- , -C (CH 3 ) 2- , -C (CF 3 ) 2- , -CO- or-. It is a group represented by SO 2-.
• R 53 to R 62 independently represent a hydrogen atom, a halogen atom, or an organic group having 1 to 6 carbon atoms.
• Preferred specific examples of R 53 to R 62 include a hydrogen atom, a chlorine atom, a fluorine atom, a saturated hydrocarbon group having 1 to 4 carbon atoms, a cyclic saturated hydrocarbon group having 4 to 6 carbon atoms, and a trifluoromethyl group.
• R 53 to R 62 are more preferably methyl groups or ethyl groups.
• a 48 and a 49 are independently integers from 0 to 4, and a 48 + a 49 ⁇ 5.
• a 51 is an integer from 0 to 6.
• a 50 and a 52 are each independently an integer of 0 to 2.
• a 48 + a 49 ⁇ 2 is preferable, a 51 is preferably 0 to 2, more preferably 0, and a 50 and a 52 are 0-1. It is preferable, and it is more preferable that it is 0.
• R 2 is at least one selected from the following structures in the general formula (1).
• a 53 represents an integer from 1 to 10. From the viewpoint of crack resistance, it is preferably 1 to 4.
• R 1 the carbon atom to carbon atom and an amide group in which the -R 5-M + is bound is bonded are adjacent (This is referred to as "bonding condition A") is preferable.
• R 2 it is preferable that the carbon atom to which the -R 6- M + is bonded and the carbon atom to which the amide group is bonded are adjacent to each other (this is referred to as “bonding condition B"). Then, it is particularly preferable that both the binding condition A and the binding condition B are satisfied. By satisfying at least one of the binding condition A and the binding condition B, the interaction between the molecules is weakened, and the rapid shrinkage during solvent evaporation is suppressed.
• the unit structure represented by the general formula (1) is, for example, [1] a structure obtained by reacting a diamine composed of a secondary amine having a bifunctional group with a dicarboxylic acid having an acidic functional group or a derivative thereof, [1]. 2] A structure obtained by reacting a diamine composed of a secondary amine with a difunctional group and a tetracarboxylic acid or a derivative thereof, and [3] reacting a diamine composed of a secondary amine with a difunctional group with a tricarboxylic acid or a derivative thereof.
• a diamine having an acidic functional group and having a secondary amine in both of the bifunctional groups is reacted with a tricarboxylic acid or a derivative thereof. It is preferable that the structure is obtained by subjecting the mixture, but the structure is not limited thereto.
• the unit structure represented by the general formula (1) is preferably contained in an amount of 50 mol% or more, preferably 70 mol% or more, in the total repeating unit structure contained in the (a) polyamide resin. It is more preferably contained, and more preferably 90 mol% or more.
• the content of the unit structure represented by the general formula (1) in the resin can be estimated by the following method.
• One is infrared spectroscopy (FT-IR), nuclear magnetic resonance (NMR), thermogravimetric analysis-mass spectrometry (TG-MS), time-of-flight secondary ion mass spectrometry (TOF-SIMS), etc. It is a method to analyze with.
• Another method is to decompose the resin into each component and then analyze it by gas chromatography (GC), high performance liquid chromatography (HPLC), mass spectrometry (MS), FT-IR, NMR or the like.
• Yet another method is to incinerate the resin at a high temperature and then analyze it by elemental analysis or the like.
• the resin is decomposed into each component and then analyzed by combining high performance liquid chromatography (HPLC) and mass spectrometry (MS).
• HPLC high performance liquid chromatography
• MS mass spectrometry
• R 63 , R 67 and R 70 each independently represent an organic group having 2 to 30 carbon atoms. From the viewpoint of solubility in water, it is preferably a hydrocarbon group, more preferably a hydrocarbon group having 2 to 20 carbon atoms, further preferably a hydrocarbon group having 2 to 15 carbon atoms, and carbon. Most preferably, it is a hydrocarbon group having a number of 2 to 10. Further, from the viewpoint of the initial efficiency of the battery when used as the negative electrode binder, R 63 , R 67 and R 70 are preferably aliphatic groups.
• R 65- , R 69- and R 72- each independently represent at least one anion selected from the group consisting of phenoxide anions, carboxylate anions and sulfonic acid anions.
• M + represents the counter cation for the anion.
• a 54 , a 56, and a 57 are each independently an integer of 0 to 4. Since a 54 + a 55 is> 0, when a 55 is 0, a 54 is an integer of 1 to 4. From the viewpoint of solubility in water , it is preferable that a 54 , a 56 and a 57 are independently integers of 0 to 4.
• R 63 , R 67 and R 70 include the same as those listed in R 1.
• -R 63 (-R 65- M + ) a 54 -, - R 67 (-R 69- M +) a 56 - and -R 70 (-R 72- 1 to 10 mol% of M + ) a 57 ⁇ may be independently diamine residues containing a siloxane bond.
• R 64 , R 68 and R 71 each independently represent an organic group having 3 to 50 carbon atoms, and an organic group having 3 to 30 carbon atoms is preferable.
• R 64 , R 68 and R 71 are preferably hydrocarbon groups, more preferably hydrocarbon groups having 3 to 30 carbon atoms, and hydrocarbons having 3 to 15 carbon atoms. It is more preferably a group, and most preferably a hydrocarbon group having 3 to 10 carbon atoms.
• R 64 , R 68 and R 71 each independently have an aliphatic skeleton.
• R 66- represents at least one anion selected from the group consisting of phenoxide anions, carboxylate anions and sulfonic acid anions.
• M + represents the counter cation for the anion.
• a 55 is an integer from 0 to 4. Since a 54 + a 55 is> 0, when a 54 is 0, a 55 is an integer of 1 to 4. From the viewpoint of crack resistance, it is preferred that a 55 is an integer of 0 to 2.
• R 64 include the same as those listed in R 2 when a 2 is 0 to 1.
• R 68 include the same as those listed in R 2 when a 2 is 2.
• R 71 include residues of trimellitic acid, trimesic acid, diphenyl ether tricarboxylic acid, and biphenyl tricarboxylic acid.
• the resin composition according to the embodiment of the present invention may be used by being mixed with a resin other than (a) polyamide resin (hereinafter, referred to as "other resin”).
• other resins include polyimide, (a) polyamides that do not correspond to polyamide resins, polyamideimides, polybenzoxazoles, acrylic resins, methacrylic resins, vinyl resins, phenol resins, cellulose resins and the like.
• Particularly preferred examples include polyvinyl alcohol, polyvinylpyrrolidone and carboxymethyl cellulose.
• the (a) polyamide resin is preferably contained in an amount of 80 mol% or more, more preferably 85 mol% or more, and further preferably 90 mol% or more. % Or more, most preferably 95 mol% or more.
• the terminal skeleton of the resin containing the structure represented by the general formula (1) as a repeating unit is represented by the following general formulas (5), (6) and (7). It is preferable to include at least one selected from the structures to be used. These structures are introduced into the (a) polyamide resin by using (a) end-capping agents such as acid anhydrides, monocarboxylic acids, and monoamine compounds when polymerizing the polyamide resin.
• R 73 , R 76 and R 78 each independently represent an organic group having 3 to 30 carbon atoms. From the viewpoint of solubility in water, it is preferably a hydrocarbon group, more preferably a hydrocarbon group having 2 to 15 carbon atoms, and even more preferably a hydrocarbon group having 2 to 10 carbon atoms. Further, from the viewpoint of initial efficiency when used as a negative electrode binder, it is preferably an aliphatic group.
• R 75- , R 77- and R 79- each independently represent at least one anion selected from the group consisting of phenoxide anions, carboxylate anions and sulfonic acid anions.
• M + represents the counter cation for the anion.
• a 58 to a 60 are independently integers of 0 to 3. From the viewpoint of solubility in water, a 58 to a 60 are preferably integers of 1 to 3 independently of each other.
• R 74 represents a halogen atom or an organic group having 1 to 10 carbon atoms.
• Preferred specific examples of R 74 include a fluoro group, a chloro group, a bromo group, an iodo group, a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, an isobutyl group, a t-butyl group, an isopentyl group and a hexyl group.
• R 74 may be connected to a part of R 73 to form an annular structure.
• amine giving the terminal structure represented by the general formula (5) include disodium 3,3'-iminodipropionate, sodium 3-piperidinecarboxylate, sodium azetidine-3-carboxylate, and 4-piperidinecarboxylic acid. Examples thereof include sodium acid and sodium 2-piperidine carboxylate.
• Specific examples of the acid giving the terminal structure represented by the general formula (6) include sodium succinate, sodium maleate, sodium fumarate, sodium adipate, -4-sodium benzoate hydroxide, sodium nadicate, and cyclohexanedicarboxylic acid. Examples thereof include sodium acid and sodium phthalate-3-carboxylic acid.
• Specific examples of the acid giving the terminal structure represented by the general formula (7) include sodium phthalic acid-3-carboxylate, phthalic acid-3-sodium hydroxide and the like.
• the end sealant can be used alone or in combination of two or more. Moreover, you may use the terminal encapsulant other than these in combination.
• the content of the terminal encapsulant in the polyamide resin is preferably in the range of 0.1 to 60 mol% of the number of moles of the component monomers constituting the carboxylic acid residue and the amine residue, and is 5 to 5 to. 50 mol% is more preferable. Within such a range, it is possible to obtain a resin composition having an appropriate viscosity of the solution at the time of application and having excellent film physical characteristics.
• a preferred method for forming a structure containing anions and cations is a method in which a basic compound is allowed to act on a phenolic hydroxyl group, a carboxylic acid and / or a sulfonic acid contained in polyamide.
• Examples of basic compounds include hydroxides, carbonates, and organic amines of alkali metals and alkaline earth metals.
• the counter cations in the present invention are alkali metal cations, alkaline earth metal cations, and ammonium cations, respectively.
• a compound containing an alkali metal element is preferable from the viewpoint of further improving the strength and chemical resistance of the coating film prepared from the resin composition and from the viewpoint of long-term cycle characteristics.
• M + in the general formula (1) is an alkali metal cation.
• alkali metal hydroxides examples include lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide and cesium hydroxide. Two or more kinds of these may be contained. Lithium hydroxide, sodium hydroxide and potassium hydroxide are preferred from the viewpoint of improving the solubility and dispersion stability of the resin composition in water.
• alkali metal carbonates include lithium carbonate, lithium hydrogen carbonate, sodium carbonate, sodium hydrogen carbonate, potassium carbonate, potassium hydrogen carbonate, rubidium hydrogen carbonate, cesium carbonate, cesium hydrogen carbonate and potassium sodium carbonate. can. Two or more kinds of these may be contained. From the viewpoint of solubility and dispersion stability of the resin composition in water, sodium carbonate, sodium hydrogen carbonate, potassium carbonate, potassium hydrogen carbonate and potassium sodium carbonate are preferable, sodium carbonate and sodium hydrogen carbonate are more preferable, and sodium carbonate is preferable. More preferred.
• organic amines include aliphatic tertiary amines such as trimethylamine, triethylamine, triisopropylamine, tributylamine, triethanolamine and N-methylethanolamine, and aromatics such as pyridine, N, N-dimethylaminopyridine and rutidin.
• aromatics such as pyridine, N, N-dimethylaminopyridine and rutidin.
• quaternary ammonium salts such as amines, tetramethylammonium hydroxides and tetraethylammonium hydroxides. Two or more of these may be used.
• sodium carbonate is most preferable as the basic compound. That is, it is preferable that M + is Na +.
• the amount of the basic compound to be blended is such that the amount of alkali metal cations and ammonium cations contained therein is 100 mol% based on the total amount of phenoxide anion, carboxylate anion and sulfonic acid anion in (a) polyamide resin. From the viewpoint of sufficient solubility and long-term cycle characteristics, it is preferably blended in an amount of 20 mol% or more, more preferably 50 mol% or more, and 80 mol% or more. It is more preferable that the mixture is formulated so as to become.
• the mixture is blended so as to be 450 mol% or less, and 300 mol% or less. It is more preferable that the mixture is blended in such a manner, more preferably 250 mol% or less, and most preferably 150 mol% or less.
• the solvent used in the polycondensation reaction is not particularly limited as long as the produced resin dissolves, but N-methyl-2-pyrrolidone, N-methylcaprolactam, N, N-dimethylacetamide, and the like.
• Aprotic polar solvents such as N, N-dimethylformamide, dimethyl sulfoxide, ⁇ -butyrolactone and dimethylimidazoline, phenolic solvents such as phenol, m-cresol, chlorophenol and nitrophenol, polyphosphoric acid and phosphorus pentaoxide in phosphoric acid.
• a phosphorus-based solvent or the like to which the above is added can be preferably used.
• a polyimide polymer is obtained by reacting an acid anhydride or a dicarboxylic acid diester with a diamine or a diisocyanate at a temperature of 150 ° C. or higher in these solvents. Further, in order to promote the reaction, bases such as triethylamine and pyridine can be added as a catalyst. Then, it is put into water or the like to precipitate a resin and dried to obtain a polymer as a solid, and then mixed with a basic compound to form a salt in a side chain.
• bases such as triethylamine and pyridine
• a basic compound More preferably, a dicarboxylic acid or a derivative thereof, a tricarboxylic acid or a derivative thereof, a tetracarboxylic acid or a derivative thereof is added to water containing a basic compound or a diamine for polymerization.
• the resin composition according to the embodiment of the present invention preferably contains (b) water as a solvent.
• the water (b) in the solvent preferably accounts for 80% by mass or more of the solvent contained in the resin composition. It is more preferably 90% by mass or more, and most preferably 99% by mass or more.
• the resin composition according to the embodiment of the present invention preferably contains (a) 50 to 1,000,000 parts by mass of water with respect to 100 parts by mass of the polyamide resin.
• a 50 to 1,000,000 parts by mass of water with respect to 100 parts by mass of the polyamide resin.
• water is preferably 50 parts by mass or more, preferably 100 parts by mass or more. Is more preferable.
• the amount of water (b) is preferably 100,000 parts by mass or less, and more preferably 3,000 parts by mass or less, based on 100 parts by mass of the resin of (a). ..
• the viscosity of the resin composition according to the embodiment of the present invention is preferably in the range of 1 mPa ⁇ s to 100 Pa ⁇ s at 25 ° C. from the viewpoint of workability.
• the resin composition according to the embodiment of the present invention may contain a surfactant or the like from the viewpoint of further improving the coatability. It may also contain an organic solvent such as a lower alcohol such as ethanol or isopropyl alcohol or a polyhydric alcohol such as ethylene glycol or propylene glycol.
• the content of the organic solvent in the resin composition is preferably 50% by mass or less, more preferably 10% by mass or less of the entire resin composition.
• the method for preparing the resin composition according to the embodiment of the present invention is not particularly limited, but it is safe to dissolve the resin powder little by little after dissolving a predetermined amount of the basic compound in water. It is preferable from the viewpoint of.
• the neutralization reaction may be heated in a water bath or an oil bath at about 30 to 110 ° C., or may be subjected to ultrasonic treatment. After dissolution, water may be further added or concentrated to adjust the viscosity to a predetermined value.
• a dicarboxylic acid or a derivative thereof, a tricarboxylic acid or a derivative thereof, a tetracarboxylic acid or a derivative thereof is added to water containing a basic compound or a diamine for polymerization.
• the resin composition according to the embodiment of the present invention may contain (c) a filler.
• the resin composition contains the filler (c)
• the mechanical strength and heat resistance of the film produced from the resin composition are improved.
• the resin composition can be used as an electronic material or an optical material.
• the resin composition containing the filler may be in the form of a slurry.
• Preferred examples of the filler (c) include compounds containing at least one atom selected from the group consisting of carbon, manganese, aluminum, barium, cobalt, nickel, iron, silicon, titanium, tin, and germanium. These compounds serve as electrode active materials, strength reinforcing materials, heat conductive materials or highly dielectric materials. Therefore, when the resin composition according to the embodiment of the present invention contains a filler and is formed into a slurry, it can be used as a slurry for functional members such as electronic parts, secondary batteries, and electric double layer capacitors.
• fillers for positive electrodes in secondary batteries and electric double layer capacitors include lithium iron phosphate, lithium cobalt oxide, lithium nickel oxide, lithium manganate, activated carbon and carbon nanotubes.
• fillers for negative electrodes in secondary batteries and electric double layer capacitors include silicon alone, silicon oxide, silicon carbide, tin, tin oxide, germanium, lithium titanate, hard carbon, soft carbon, activated carbon and carbon nanotubes. Can be mentioned.
• storage batteries using silicon, tin, or germanium as the active material have a large volume expansion of the active material during charging. Therefore, it is recommended to use a resin having high mechanical strength such as (a) polyamide resin as the active material. It is preferable to prevent the pulverization of the resin.
• the filler is lithium titanate, a secondary battery or an electric double layer capacitor having excellent rate characteristics can be obtained.
• fillers for negative electrodes are elemental silicon, silicon oxide, lithium titanate, silicon carbide, mixtures of two or more of them, mixtures of one or more of them and carbon. At least one selected from the group consisting of a mixture of the above, and one or two or more of them whose surface is carbon-coated.
• a simple substance of silicon is a substance composed of only silicon (silicon), and can be a component of a resin composition. These active materials have a particularly strong binding property due to the (a) polyamide resin, and a secondary battery or an electric double layer capacitor having a high capacity retention rate can be obtained.
• the content of (d) filler in the resin composition according to the embodiment of the present invention is (a) that the mechanical strength and heat resistance of the film obtained from the resin composition can be improved with respect to 100 parts by mass of the polyamide resin. , 0.01 part by mass or more is preferable, and 0.1 part by mass or more is more preferable. Further, in terms of maintaining the coating film strength of the resin composition, it is preferably 100,000 parts by mass or less, and more preferably 10,000 parts by mass or less.
• the slurry can be obtained, for example, by adding a filler and, if necessary, other components to a resin dissolved or dispersed in water or a solvent, and uniformly mixing them.
• examples of the mixing include a method using a planetary mixer, a rotation / revolution type mixer, a three-roll, a ball mill, a mechanical stirrer, a thin film swirl type mixer, and the like.
• the laminate according to the embodiment of the present invention has a layer formed from the above-mentioned resin composition on at least one side of the base material.
• This laminate can be obtained, for example, by applying the resin composition to one side or both sides of the base material and drying it.
• metal foils such as copper foil, aluminum foil, and stainless steel foil, silicon substrates, glass substrates, plastic films, and the like are preferably used.
• the coating method include a method using a roll coater, a slit die coater, a bar coater, a comma coater, a spin coater, and the like.
• the drying temperature is preferably 30 ° C. or higher, more preferably 50 ° C. or higher in order to completely remove water. Further, from the viewpoint of preventing cracks in the electrodes, the temperature is preferably 500 ° C. or lower, more preferably 200 ° C. or lower.
• the resin composition according to the embodiment of the present invention when used as a slurry for electrodes, it may contain a conductive auxiliary agent such as acetylene black, ketjen black, and carbon nanotubes.
• a conductive auxiliary agent such as acetylene black, ketjen black, and carbon nanotubes.
• the content of the conductive auxiliary agent is preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of the active material in order to achieve both conductivity and capacity.
• the resin composition according to the embodiment of the present invention may contain a sodium salt of carboxymethyl cellulose for adjusting the viscosity.
• the content is preferably 50 parts by mass or less with respect to 100 parts by mass of the active material from the viewpoint of having a high capacity retention rate in the secondary battery and the electric double layer capacitor.
• the manufacturing method of the laminated body is as follows, for example. A resin composition or a resin composition containing a filler is applied to one or both sides of a base material to form a coating film. Then, the coating film is dried to form a laminated body.
• the base material examples include an insulating base material and a conductive base material, but when used as an electronic device, a conductive base material or an insulating base material having conductive wiring is preferable.
• a resin composition containing an electrode active material as a filler is applied to one or both sides of a current collector such as copper foil, aluminum foil, or stainless steel foil. It can be obtained by applying and drying.
• a plurality of positive and negative electrodes obtained in this manner are laminated via a separator, placed in an exterior material such as a metal case together with an electrolytic solution, and sealed to store electricity such as a secondary battery or an electric double layer capacitor. You can get the device.
• separators include microporous films and non-woven fabrics made of polyolefins such as polyethylene and polypropylene, cellulose, polyphenylene sulfide, aramid, and polyimide.
• carbonate compounds such as propylene carbonate, ethylene carbonate, dimethyl carbonate, ethylmethyl carbonate and vinylene carbonate, acetonitrile, sulfolane, ⁇ -butyrolactone and the like can be used. Two or more of these may be used.
• electrolytes examples include lithium salts such as lithium hexafluorophosphate, lithium borofluoride, and lithium perchlorate, and ammonium salts such as tetraethylammonium tetrafluoroborate and triethylmethylammonium tetrafluoroborate.
• lithium salts such as lithium hexafluorophosphate, lithium borofluoride, and lithium perchlorate
• ammonium salts such as tetraethylammonium tetrafluoroborate and triethylmethylammonium tetrafluoroborate.
• ⁇ Evaluation of stability of aqueous solution> The aqueous solutions A to U were left in a refrigerator (3 ° C.) for 1 month and 6 months, respectively, and then visually observed to confirm the stability of the aqueous solution. Those in which no precipitation, gelation, or cloudiness was observed were good, and those with any change were described as the changes that occurred. Good ones were accepted after being left in the refrigerator for 6 months, and those with any change after being left in the refrigerator for 6 months were rejected.
• This slurry was applied onto an aluminum foil with a bar coater in a width of 10 cm after adjusting the thickness so that the average value of the film thickness after heat treatment was 50 ⁇ m. After coating, it was dried at 50 ° C. for 30 minutes, then heated to 150 ° C. over 30 minutes, heat-treated at 150 ° C. for 1 hour, and then cooled to 50 ° C. or lower. After cooling, the membrane was cut into five circles having a diameter of 16 mm, immersed in a solution containing 50% by weight of diethyl carbonate and ethylene carbonate, and left at 40 ° C. and 60 ° C. for 1 week, respectively. After standing, the membrane was taken out from the solution, washed with water, dried at 50 ° C.
• ⁇ Battery characteristic evaluation> (1) Preparation of Negative Electrode Using the slurry with a solid content of 50% by mass prepared in ⁇ Evaluation of film thickness characteristics (evaluation of dispersibility and binding property)>, using a bar coater on an electrolytic copper foil, at 150 ° C. The film thickness was adjusted so that the film thickness after the heat treatment was 25 ⁇ m, and the film was applied, and then dried at 110 ° C. for 30 minutes. After drying, the coated portion was punched into a circle having a diameter of 16 mm, and vacuum dried at 150 ° C. for 24 hours to obtain a negative electrode.
• the negative electrode, the separator, and the positive electrode were stacked in this order, and 1 mL of MIRET1 (manufactured by Mitsui Chemicals, Inc.) was injected as an electrolytic solution and then sealed to obtain a lithium ion battery.
• MIRET1 manufactured by Mitsui Chemicals, Inc.
• the lithium ion battery produced as described above was charged and discharged.
• the battery is charged with a constant current of 6 mA until the battery voltage reaches 4.2 V, then charged with a constant voltage of 4.2 V until a total of 2 hours and 30 minutes is reached from the start of charging, and then paused for 30 minutes.
• One cycle was to discharge the battery with a constant current of 6 mA until the battery voltage reached 2.7 V.
• Synthesis Example 1 Synthesis of Resin A In a well-dried four-necked flask, 119.48 g of water and 8.815 g (100 mmol) of N, N'-dimethylethylenediamine (manufactured by Tokyo Chemical Industry Co., Ltd., hereinafter DMEDA) ), Sodium carbonate 10.60 g (100 mmol) was dissolved at room temperature with stirring under a nitrogen atmosphere. Then, 44.42 g (100 mmol) of 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride (manufactured by Tokyo Chemical Industry Co., Ltd., hereinafter, 6FDA) and 15.00 g of water were added.
• DMEDA N, N'-dimethylethylenediamine
• the polymerization reaction was carried out at 80 ° C. for 6 hours, paying attention to the generation of carbon dioxide. After completion of the reaction, the temperature was lowered to room temperature to obtain an aqueous solution A of a polyamide resin A having a sodium carboxylate in the side chain having a concentration of 30% by mass.
• Synthesis Example 2 Synthesis of Resin B Synthetic except that 119.01 g of water and 8.614 g (100 mmol) of Piperazine (manufactured by Tokyo Chemical Industry Co., Ltd.) were used instead of 119.48 g of water and 8.815 g (100 mmol) of DMEDA.
• An aqueous solution B of a polyamide resin B having a sodium carboxylate in a side chain having a concentration of 30% by mass was obtained in the same manner as in Example 1.
• Synthesis Example 3 Synthesis of resin C 87.75 g of water, bis (3,4-dicarboxyphenyl) ether dianhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) instead of 119.01 g of water and 44.42 g (100 mmol) of 6FDA.
• an aqueous solution C of a polyamide resin C having a sodium carboxylate in the side chain having a concentration of 30% by mass was obtained in the same manner as in Synthesis Example 2 except that 31.02 g (100 mmol) of ODPA) was used.
• Synthesis Example 4 Synthesis of Resin D Instead of water 119.01 g and 6FDA 44.42 g (100 mmol), water 66.26 g and pyromellitic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd., hereinafter PMDA) 21.81 g (100 mmol) ) was used, and an aqueous solution D of a polyamide resin D having a sodium carboxylate in the side chain having a concentration of 30% by mass was obtained in the same manner as in Synthesis Example 2.
• Synthesis Example 5 Synthesis of Resin E Instead of water 119.01 g, 6FDA 44.42 g (100 mmol), water 84.01 g, 3,3', 4,4'-biphenyltetracarboxylic dianhydride (Tokyo Chemical Industry (Tokyo Chemical Industry)
• An aqueous solution E of a polyamide resin E having a sodium carboxylate in a side chain having a concentration of 30% by mass was obtained in the same manner as in Synthesis Example 2 except that 29.42 g (100 mmol) of BPDA) manufactured by Tokyo Chemical Industry Co., Ltd. was used.
• Synthesis Example 6 Synthesis of Resin F Instead of water 119.01 g, 6FDA 44.42 g (100 mmol), water 101.75 g, 3,3', 4,4'-terphenyltetracarboxylic acid dianhydride (Tokyo Chemical Industry) An aqueous solution F of a polyamide resin F having a sodium carboxylate in a side chain having a concentration of 30% by mass was obtained in the same manner as in Synthesis Example 2 except that 37.02 g (100 mmol) of TPDA (manufactured by Tokyo Chemical Industry Co., Inc.) was used.
• Synthesis Example 7 Synthesis of resin G Instead of 119.48 g of water, 8.815 g (100 mmol) of DMEDA, and 44.42 g (100 mmol) of 6FDA, 103.18 g of water, 4,4'-bipiperidine (manufactured by Tokyo Chemical Industry Co., Ltd.) An aqueous solution G of a polyamide resin G having a sodium carboxylate in a side chain having a concentration of 30% by mass was obtained in the same manner as in Synthesis Example 1 except that 16.83 g (100 mmol) and BPDA 29.42 g (100 mmol) were used.
• Synthesis Example 8 Synthesis of Resin H 64.39 g of water, 1,2,3,4-cyclopentanetetracarboxylic acid dianhydride instead of 119.01 g of water and 44.42 g (100 mmol) of 6FDA (Tokyo Chemical Industry Co., Ltd.) ),
• an aqueous solution H of a polyamide resin H having a sodium carboxylate in a side chain having a concentration of 30% by mass was obtained in the same manner as in Synthesis Example 2 except that 21.01 g (100 mmol) of CPDA) was used.
• Synthesis Example 9 Synthesis of Resin I Instead of water 119.01 g, 6FDA 44.42 g (100 mmol), water 61.59 g, 1,2,3,4-butanetetracarboxylic acid dianhydride (manufactured by Wako Chemical Co., Ltd.)
• an aqueous solution I of a polyamide resin I having a sodium carboxylate in the side chain having a concentration of 30% by mass was obtained in the same manner as in Synthesis Example 2 except that 19.81 g (100 mmol) of BTA) was used.
• Synthesis Example 10 Synthesis of Resin J In a well-dried four-necked flask, 20.31 g (100 mmol) of 2-piperazin carboxylic acid dihydrochloride (manufactured by Tokyo Chemical Industry Co., Ltd., hereinafter, 2PC) in 100 g of water. , Sodium carbonate 26.50 g (250 mmol) was dissolved at room temperature with stirring under a nitrogen atmosphere. 15.50 g (100 mmol) of succinic acid dichloride (manufactured by Tokyo Chemical Industry Co., Ltd.) dissolved in 30 g of methylene chloride was added dropwise thereto so that the temperature of the reaction vessel did not exceed 10 ° C.
• 2PC 2-piperazin carboxylic acid dihydrochloride
• Synthesis Example 11 Synthesis of Resin K
• 20.31 g (100 mmol) of 2-piperazin carboxylic acid dihydrochloride manufactured by Tokyo Chemical Industry Co., Ltd., hereinafter, 2PC
• 2PC 2-piperazin carboxylic acid dihydrochloride
• Sodium carbonate 26.50 g (250 mmol) was dissolved at room temperature with stirring under a nitrogen atmosphere.
• 18.30 g (100 mmol) of adipoyl dichloride (manufactured by Tokyo Chemical Industry Co., Ltd.) dissolved in 30 g of methylene chloride was added dropwise thereto so that the temperature of the reaction vessel did not exceed 10 ° C.
• Synthesis Example 12 Synthesis of resin L In a well-dried four-necked flask, 3,3'-dicarboxy-4,4'-diaminodiphenylmethane (manufactured by Wakayama Seika Kogyo Co., Ltd., product) was added to 131.79 g of NMP. Name "MBAA”) 27.20 g (95 mmol) and para-phenylenediamine (manufactured by Tokyo Chemical Industry Co., Ltd., hereinafter, PDA) 0.54 g (5 mmol) were dissolved at room temperature with stirring under a nitrogen atmosphere.
• MBAA 3,3'-dicarboxy-4,4'-diaminodiphenylmethane
• Synthesis Example 13 Synthesis of Resin M
• 28.63 g (100 mmol) of MBAA was dissolved in 131.79 g of NMP with stirring under a nitrogen atmosphere. Then, the flask was ice-cooled, and 20.30 g (100 mmol) of isophthaloyl chloride (manufactured by Tokyo Chemical Industry Co., Ltd., hereinafter, IPC) dissolved in 15.00 g of NMP was added dropwise while keeping the temperature of the solution at 30 ° C. or lower. did. After charging the whole amount, it was reacted at 30 ° C. for 4 hours. This solution was poured into 3 L of water, the obtained precipitate was filtered off, and washed 3 times with 1.5 L of water. The washed solid was dried in a ventilation oven at 50 ° C. for 3 days to obtain a resin M solid.
• IPC isophthaloyl chloride
• Synthesis Example 14 Synthesis of Resin N In a well-dried four-necked flask, 280.0 g of NMP and 14.44 g (95 mmol) of 3,5-diaminobenzoic acid (manufactured by Tokyo Kasei Co., Ltd., hereinafter DAB), 1.240 g (5 mmol) of 1,3-bis-3-aminopropyltetramethyldisiloxane (manufactured by Toray Dow Corning Silicone Co., Ltd., hereinafter APDS) was dissolved in a nitrogen atmosphere with stirring. Then, 31.02 g (100 mmol) of ODPA and 15.00 g of NMP were added and reacted at 50 to 60 ° C.
• DAB 3,5-diaminobenzoic acid
• APDS 1,3-bis-3-aminopropyltetramethyldisiloxane
• Synthesis Example 15 Synthesis of Negative Electrode Active Material for Lithium Ion Battery 50 g of natural graphite (manufactured by Fuji Graphite Co., Ltd., CBF1) with a particle size of about 10 ⁇ m, 60 g of nanosilicon powder (manufactured by Aldrich), and 10 g of carbon black (Mitsubishi Chemical). It was mixed with 3050) manufactured by Co., Ltd., dispersed well in a ball mill at 600 rpm for 12 hours, and then vacuum dried at 80 ° C. for 12 hours to obtain a mixed negative electrode active material of silicon-carbon.
• natural graphite manufactured by Fuji Graphite Co., Ltd., CBF1
• nanosilicon powder manufactured by Aldrich
• carbon black Mitsubishi Chemical
• Synthesis Example 16 Synthesis of Resin O Instead of water 119.48 g, 6FDA 44.42 g (100 mmol), water 136.82 g, 4,4'-(4,4'-isopropyridene diphenoxy) diphthalic anhydride (Tokyo)
• An aqueous solution O of a polyamide resin O having a sodium carboxylate in a side chain having a concentration of 30% by mass was obtained in the same manner as in Synthesis Example 2 except that 52.05 g (100 mmol) of BISDA) manufactured by Kasei Kogyo Co., Ltd. was used. rice field.
• Synthesis Example 17 Synthesis of Resin P In the same manner as in Synthesis Example 1 except that 116.40 g of water and 7.42 g (70 mmol) of sodium carbonate were used instead of 119.01 g of water and 10.60 g (100 mmol) of sodium carbonate. An aqueous solution P of a polyamide resin P having a sodium carbonate in the side chain having a concentration of 30% by mass was obtained.
• Synthesis Example 18 Synthesis of Resin Q Same as Synthesis Example 1 except that 118.46 g of water and 9.54 g (90 mmol) of sodium carbonate were used instead of 119.01 g of water and 10.60 g (100 mmol) of sodium carbonate. An aqueous solution Q of a polyamide resin Q having a sodium carbonate in the side chain having a concentration of 30% by mass was obtained.
• Synthesis Example 19 Synthesis of Resin R In the same manner as in Synthesis Example 1 except that 151.64 g of water and 24.38 g (230 mmol) of sodium carbonate were used instead of 119.01 g of water and 10.60 g (100 mmol) of sodium carbonate. An aqueous solution R of a polyamide resin R having a sodium carbonate in the side chain having a concentration of 30% by mass was obtained.
• Synthesis Example 20 Synthesis of Resin S In the same manner as in Synthesis Example 1 except that 136.80 g of water and 18.02 g (170 mmol) of sodium carbonate were used instead of 119.01 g of water and 10.60 g (100 mmol) of sodium carbonate. An aqueous solution S of a polyamide resin S having a sodium carbonate in the side chain having a concentration of 30% by mass was obtained.
• Synthesis Example 21 Synthesis of Resin T Same as Synthesis Example 1 except that 126.95 g of water and 11.22 g (200 mmol) of potassium hydroxide were used instead of 119.01 g of water and 10.60 g (100 mmol) of sodium carbonate. An aqueous solution T of a polyamide resin T having a potassium carboxylate in the side chain having a concentration of 30% by mass was obtained.
• Synthesis Example 22 Synthesis of Resin U In the same manner as in Synthesis Example 1 except that 217.83 g of water and 46.55 g (460 mmol) of triethylluamine were used instead of 119.01 g of water and 10.60 g (100 mmol) of sodium carbonate. An aqueous solution U of a polyamide resin U having a carboxylic acid triethylamine salt in a side chain having a concentration of 30% by mass was obtained.

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