WO2017099172A1 - 樹脂、スラリーおよびそれらを用いた積層体とその製造方法 - Google Patents

樹脂、スラリーおよびそれらを用いた積層体とその製造方法 Download PDF

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Publication number
WO2017099172A1
WO2017099172A1 PCT/JP2016/086530 JP2016086530W WO2017099172A1 WO 2017099172 A1 WO2017099172 A1 WO 2017099172A1 JP 2016086530 W JP2016086530 W JP 2016086530W WO 2017099172 A1 WO2017099172 A1 WO 2017099172A1
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Prior art keywords
resin
general formula
carbon atoms
group
organic group
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PCT/JP2016/086530
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English (en)
French (fr)
Japanese (ja)
Inventor
祐真 杉崎
弓場　智之
奈津子 茶山
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東レ株式会社
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Priority to KR1020187013135A priority Critical patent/KR102358212B1/ko
Priority to JP2016572603A priority patent/JP7135272B2/ja
Priority to CN201680072054.6A priority patent/CN108368263B/zh
Publication of WO2017099172A1 publication Critical patent/WO2017099172A1/ja

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    • 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
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/14—Polyamide-imides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
    • 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
    • C08G69/48—Polymers modified by chemical after-treatment
    • 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
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • 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
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1003—Preparatory processes
    • C08G73/1035—Preparatory processes from tetracarboxylic acids or derivatives and diisocyanates
    • 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
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/22—Compounds containing nitrogen bound to another nitrogen atom
    • C08K5/24—Derivatives of hydrazine
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/54—Silicon-containing compounds
    • C08K5/544—Silicon-containing compounds containing nitrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • 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
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • 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

  • Lithium ion batteries which are said to have the highest theoretical energy among batteries, are attracting attention, and are currently being developed rapidly.
  • Lithium ion batteries which are widely used at present, are formed by applying a paste containing a positive electrode active material such as lithium cobalt oxide and a composite oxide containing lithium and a binder such as polyvinylidene fluoride (PVDF) on an aluminum foil.
  • PVDF polyvinylidene fluoride
  • a negative electrode formed by coating a copper foil with a paste containing a negative electrode active material capable of occluding and releasing lithium ions, such as a carbon-based active material, and a binder such as PVDF or styrene / butadiene / rubber (SBR).
  • a separator and an electrolyte layer are connected and sealed.
  • the speeding up and downsizing of notebook personal computers and small portable terminals has led to the downsizing and thinning of parts such as semiconductors, displays, and multilayer wiring boards, and the resulting deterioration in process yield due to warping of device boards.
  • the resin is also required to be imparted with characteristics that reduce the warpage of the substrate.
  • Measures for reducing the warpage of the device substrate include reducing the difference in the coefficient of thermal expansion between the resin formed on the substrate and the substrate itself to reduce the stress generated by the difference in thermal expansion. Since the thermal linear expansion coefficient of a general resin is 10 ppm or more larger than the thermal linear expansion coefficient of the substrate, it is effective to reduce the thermal linear expansion coefficient of the resin in order to reduce the stress described above. In order to achieve this object, a polyimide resin having a small thermal linear expansion coefficient including a rigid structure in the main chain (see, for example, Patent Documents 5 to 9) has been reported.
  • JP 2009-199761 A Japanese Unexamined Patent Publication No. 2009-245773 JP 2010-062041 PR JP 2009-170384 A JP-A-2-283762 JP-A-8-48773 Japanese Patent Laid-Open No. 8-253854 JP-A-11-158279 JP 2002-363283 A
  • the polyimides described in Patent Documents 5 to 9 have problems such as oxidative deterioration of the device because they must be treated at a high temperature of 300 ° C. or higher in order to convert them into a polyimide structure.
  • the present invention provides a resin, slurry, and a conductive substrate and a substrate with a conductive wiring, which can be processed at a low temperature and whose processed film has high strength, high elasticity, high adhesion, and low thermal linear expansion. It is an object of the present invention to provide a laminate formed into a film.
  • the present invention is a resin having a structural unit represented by the general formula (1) and / or a structural unit represented by the following general formula (2), wherein R 1 and R 4 contained in the resin are:
  • R 1 and R 4 contained in the resin are:
  • Each of them is a resin including a structure represented by the following general formula (3) and a structure represented by the following general formula (4) at least partially.
  • R 1 represents a divalent organic group having 2 to 50 carbon atoms.
  • R 2 represents a trivalent or tetravalent organic group having 2 to 50 carbon atoms.
  • R 3 represents a hydrogen atom. Or an organic group having 1 to 10 carbon atoms, m 1 is an integer of 1 or 2.
  • R 6, R 7 are each .b 1 and b 2 represents a monovalent organic group of a halogen atom or a C 1-3 independently are each independently an integer of 0 to 3 .
  • R 8 each independently represents a halogen atom or a monovalent organic group having 1 to 3 carbon atoms.
  • B 3 is an integer of 0 to 4.
  • the resin of the present invention can be cured at low temperature and has high strength, high elasticity, high adhesion, and low linear expansion, and obtains a good capacity maintenance ratio during charge and discharge in a binder for a lithium ion battery and a capacitor electrode.
  • it is possible to manufacture a semiconductor package, a display, and a multilayer wiring board with low warpage of the device substrate.
  • the resin of the present invention is a resin having a structural unit selected from at least one of the following general formulas (1) and (2).
  • R 1 represents a divalent organic group having 2 to 50 carbon atoms.
  • R 2 represents a trivalent or tetravalent organic group having 2 to 50 carbon atoms.
  • R 3 represents a hydrogen atom. Or an organic group having 1 to 10 carbon atoms, m 1 is an integer of 1 or 2.
  • the resin is preferably a resin having the structural unit represented by the general formula (2) as a main component, and m 2 has a polyamideimide structure of 0 from the viewpoint of solubility in a solvent. More preferably it is.
  • the main component as used herein refers to 70% by weight or more, preferably 80% by weight or more of the total resin.
  • R 1 and R 4 represent a diamine residue and represent a divalent organic group having 2 to 50 carbon atoms.
  • R 1 and R 4 each independently include a structure represented by the general formula (3) and a structure represented by the general formula (4).
  • R 6 and R 7 each independently represents a halogen atom or a monovalent organic group having 1 to 3 carbon atoms. From the viewpoint that the linear expansion coefficient of the resin can be reduced, a fluorine atom, an alkyl group having 1 to 3 carbon atoms or a fluoroalkyl group is preferable, and an alkyl group having 1 to 3 carbon atoms or a fluoroalkyl group is more preferable.
  • b 1 and b 2 are each independently an integer of 0 to 3. It is preferably 1 or 2 from the viewpoint of compatibility with the solvent and low linear expansion. Furthermore, R 6 and R 7 are preferably bonded to the ortho position with respect to the polymer main chain from the viewpoint of low linear expansion.
  • the benzene rings are preferably linked by a para bond from the viewpoint of low linear expansion characteristics.
  • Specific examples include the structures shown below, but are not limited thereto.
  • each of R 1 and R 4 is preferably independently a structure in which 50 mol% or more thereof is represented by the general formula (3). % Or more is more preferable.
  • each R 8 independently represents a halogen atom or a monovalent organic group having 1 to 3 carbon atoms.
  • a fluorine atom an alkyl group having 1 to 3 carbon atoms or a fluoroalkyl group is preferable, and an alkyl group having 1 to 3 carbon atoms or a fluoroalkyl group is more preferable.
  • b 3 is an integer of 0-4. It is preferably 1 or 2 from the viewpoint of compatibility with the solvent and low linear expansion. Further, from the viewpoint of low linear expansion, it is most preferable that R 8 is bonded to the ortho position with respect to the polymer main chain.
  • the benzene rings are linked by a meta bond from the viewpoint of compatibility with a solvent and low linear expansion.
  • Specific examples include the structures shown below, but are not limited thereto.
  • R 1 and R 4 are each independently preferably 10 to 40 mol% of a structure represented by the general formula (4). Preferably, it is 25 to 35 mol%.
  • the diamine residue may contain a diamine residue other than the structure represented by the general formulas (3) and (4).
  • amine components that give such diamine residues include carboxyl group-containing diamines such as 3,5-diaminobenzoic acid, 3-carboxy-4,4′-diaminodiphenyl ether, and 3-sulfonic acid-4,4′-diamino.
  • Sulfonic acid-containing diamines such as diphenyl ether, dithiohydroxyphenylenediamine, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 3,4'- Diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfide, 1,4-bis (4-aminophenoxy) benzene, 1,5-naphthalenediamine 2,6- Phthalenediamine, bis (4-aminophenoxyphenyl) sulfone, bis (3-aminophenoxyphenyl) sulfone, bis (4-aminophenoxy) biphenyl,
  • the raw materials that give these diamine residues include diisocyanate compounds in which an isocyanate group is bonded to the structure of the diamine residue instead of an amino group, and two hydrogen atoms of the amino group of the diamine are substituted with a trimethylsilyl group. Tetratrimethylsilylated diamines made can also be used.
  • a diisocyanate compound is preferably used in that there is no by-product water.
  • R 2 and R 5 represent tri- or tetra-carboxylic acid residues (hereinafter referred to as “acid residues”).
  • Examples of preferable tricarboxylic acid that gives an acid residue include trimellitic acid, trimesic acid, diphenyl ether tricarboxylic acid, biphenyltricarboxylic acid, and the like.
  • Examples of preferred tetracarboxylic acids that give acid residues include pyromellitic acid, 3,3 ′, 4,4′-biphenyltetracarboxylic acid, 2,3,3 ′, 4′-biphenyltetracarboxylic acid, 2,2 ', 3,3'-biphenyltetracarboxylic acid, 3,3', 4,4'-benzophenone tetracarboxylic acid, 2,2 ', 3,3'-benzophenone tetracarboxylic acid, 2,2-bis (3 4-dicarboxyphenyl) hexafluoropropane, 2,2-bis (2,3-dicarboxyphenyl) hexafluoropropane, 1,1-bis (3,4-dicarboxyphenyl) ethane, 1,1-bis ( 2,3-dicarboxyphenyl) ethane, bis (3,4-dicarboxyphenyl) methane, bis (2,3-
  • Heptanetetracarboxylic acid bicyclo [3.3.1. ] Tetracarboxylic acid, bicyclo [3.1.1. ] Hept-2-enetetracarboxylic acid, bicyclo [2.2.2.
  • An aliphatic tetracarboxylic acid such as octanetetracarboxylic acid or adamatanetetracarboxylic acid can be used. These acids can be used alone or in combination of two or more.
  • R 2 and R 5 each independently have a structure in which 65 mol% or more thereof is selected from at least one of the general formulas (5) and (6). preferable.
  • R 9 and R 10 each independently represent a halogen atom or a monovalent organic group having 1 to 3 carbon atoms.
  • a fluorine atom an alkyl group having 1 to 3 carbon atoms or a fluoroalkyl group is preferable, and an alkyl group having 1 to 3 carbon atoms or a fluoroalkyl group is more preferable.
  • b 4 and b 5 are integers from 0 to 4. From the viewpoint of low linear expansion, it is preferably 0. Specific examples include the structures shown below, but are not limited thereto.
  • the resin of the present invention preferably contains 5 to 30 mol% of a structural unit represented by the following general formula (7) in order to achieve high strength and high elasticity.
  • R 11 represents a diamine residue and represents a C 2-50 valent organic group.
  • amine components that give diamine residues include carboxyl group-containing diamines such as 3,5-diaminobenzoic acid and 3-carboxy-4,4′-diaminodiphenyl ether, and 3-sulfonic acid-4,4′-diaminodiphenyl ether.
  • diamines can be used as they are or as corresponding diisocyanate compounds or trimethylsilylated diamines.
  • a diisocyanate compound is preferably used in that there is no water generated as a by-product.
  • R 12 each independently represents a halogen atom or a monovalent organic group having 1 to 3 carbon atoms.
  • a fluorine atom an alkyl group having 1 to 3 carbon atoms or a fluoroalkyl group is preferable, and an alkyl group having 1 to 3 carbon atoms or a fluoroalkyl group is more preferable.
  • b 6 is an integer of 0-4. From the viewpoint of low linear expansion, it is preferably 0.
  • the benzene rings are preferably linked by a para bond from the viewpoint of low linear expansion characteristics.
  • a siloxane structure may be copolymerized with R 1 , R 4 , R 11 , R 2 , and R 5 within a range that does not decrease the heat resistance.
  • R 1 , R 4 and R 11 include residues such as bis (3-aminopropyl) tetramethyldisiloxane and bis (p-amino-phenyl) octamethylpentasiloxane.
  • R 2 and R 5 include dimethylsilane diphthalic dianhydride, 1,3-bis (phthalic acid) tetramethyldisiloxane dianhydride, 1- (p-carboxyphenyl) 3-phthalic acid And residues such as -1,1,3,3-tetramethyldisiloxane. These may be used alone or in combination of two or more, and are preferably copolymerized in an amount of 1 to 10 mol% of R 2 and R 5 as a whole.
  • R 1 , R 4 , and R 11 may be made of poly in the range that does not decrease the heat resistance.
  • An aliphatic structure having an alkylene oxide group may be copolymerized.
  • Specific structures include “Jeffamine” (registered trademark) KH-511, Jeffamine ED-600, Jeffamine ED-900, Jeffamine ED-2003, Jeffamine EDR-148, Jeffamine EDR-176, Jeffamine Residues such as D-200, Jeffamine D-400, Jeffamine D-2000, and Jeffamine D-4000 (trade name, manufactured by HUNTSMAN Co., Ltd.) can be mentioned. These may be used singly or in combination of two or more, and are preferably copolymerized in an amount of 1 to 30 mol% of R 1 , R 4 and R 11 as a whole.
  • the diamine is N-methylpyrrolidone (NMP), N, N-dimethylformamide (DMF), N, N-dimethylacetamide (DMAC), gamma butyrolactone (GBL). ),
  • a solvent such as dimethyl sulfoxide (DMSO), etc., and a method of adding tetracarboxylic dianhydride to react is generally used.
  • the reaction temperature is generally ⁇ 20 ° C. to 100 ° C., preferably 0 ° C. to 50 ° C.
  • the reaction time is generally 1 minute to 100 hours, preferably 2 hours to 24 hours. It is preferable to prevent moisture from entering the system by flowing nitrogen during the reaction.
  • a tetracarboxylic dianhydride is mixed with an alcohol such as ethanol, propanol, or butanol and a base catalyst such as pyridine or triethylamine, and then at room temperature to 100 ° C. for several minutes to The reaction is carried out for about 10 hours to obtain a dicarboxylic acid diester compound.
  • Tetracarboxylic dianhydride may be directly dispersed in alcohol, or tetracarboxylic dianhydride is dissolved in a solvent such as NMP, DMAC, DMF, DMSO, GBL, and alcohol and a base catalyst are allowed to act. Also good.
  • the obtained dicarboxylic acid diester is subjected to heat treatment in thionyl chloride or oxalodichloride is reacted to form dicarboxylic acid chloride diester.
  • the obtained dicarboxylic acid chloride diester is recovered by a technique such as distillation and added dropwise to a solution in which diamine is dissolved in a solvent such as NMP, DMAC, DMF, DMSO, GBL in the presence of pyridine or triethylamine.
  • the dropping is preferably performed at -20 ° C to 30 ° C. After completion of dropping, the reaction is carried out at ⁇ 20 ° C. to 50 ° C. for 1 to 100 hours to obtain a polyamic acid ester.
  • dicarboxylic acid dichloride diester can be converted into hydrochloride as a by-product, instead of heat treating dicarboxylic acid diester in thionyl chloride or reacting with oxalodichloride, condensation of peptides such as dicyclohexylcarbodiimide It is preferable to react with diamine with a reagent.
  • the polyamic acid ester can also be obtained by reacting the polyamic acid described above with an acetal compound such as dimethylformamide dialkyl acetal. The esterification rate can be adjusted by the amount of the acetal compound added.
  • the polyimide precursor can be obtained by imide ring closure by heat treatment or chemical treatment.
  • the chemical treatment include treatment with acetic anhydride and pyridine, base treatment such as triethylamine and dodecylundecene, and acid anhydride treatment such as acetic anhydride and succinic anhydride.
  • the reaction temperature is generally ⁇ 20 ° C. to 100 ° C., preferably 0 ° C. to 50 ° C.
  • the reaction time is generally 1 minute to 100 hours, preferably 2 hours to 24 hours. It is preferable to prevent moisture from entering the system by flowing nitrogen during the reaction.
  • a general reaction there is a method in which tricarboxylic acid chloride is allowed to act on a diamine solution, followed by heat treatment at 100 ° C. to 300 ° C.
  • polyamideimide for 1 minute to 24 hours to obtain polyamideimide.
  • an acid anhydride such as acetic anhydride or a base such as triethylamine, pyridine or picoline is used as a catalyst for imidization to a polymer amount of 0.
  • the reaction can be promoted by adding 1 to 10% by weight.
  • polyamic acid amide is polymerized from diamine and trimellitic anhydride chloride in the presence of pyridine, triethylamine, etc., this polymer is taken out as a solid, and then the solid is heated at a temperature of 100 to 300 ° C. for 1 minute to 24 hours.
  • polyamideimide can be obtained.
  • the amino group of the diamine compound is further changed to isocyanate, and a divalent or higher acid such as tetracarboxylic dianhydride or tricarboxylic anhydride, and in some cases It can also be obtained by reacting in the temperature range of room temperature to 200 ° C. for 1 minute to 24 hours in the presence of a tin-based catalyst or a base catalyst.
  • This method can be said to be a more preferable method in that there is no by-produced water.
  • the molar ratio of the acid component to the diamine or diisocyanate is 100 mol% or less, preferably 95 mol% or less, more preferably 90 mol% or less, most preferably 85 mol based on 100 mol% of the diamine or diisocyanate. It is below mol%.
  • terminal amines and isocyanate groups have the effect of enhancing the adhesion between the resin and filler, the conductive substrate, and the conductive wiring.
  • the resin used in the present invention may be obtained by precipitating in a poor solvent for the resin such as methanol or water after completion of polymerization, and then washing and drying.
  • a poor solvent for the resin such as methanol or water
  • the esterification agent, condensing agent, and by-product produced by acid chloride, the low molecular weight component of the resin precursor, and the like can be removed, which has the advantage of improving heat resistance.
  • the resin of the present invention preferably contains a structure having a resin terminal represented by the following general formula (8).
  • R 13 to R 16 each independently represent a halogen atom or a monovalent organic group having 1 to 5 carbon atoms.
  • the protecting group is eliminated during the heat treatment and the isocyanate group is regenerated.
  • This functional group and the amino group formed by hydrolyzing this functional group have the effect of enhancing the adhesion between the resin and the filler, the conductive substrate, and the conductive wiring.
  • the resin having an end-capping agent is reacted with diamine, diisocyanate, or acid in advance in the various known synthesis methods described above when the diamine, diisocyanate and acid component are selectively combined. Then, the polymerization reaction may be started, or it can be obtained by adding the end-capping agent simultaneously with diamine, diisocyanate, acid or slightly delayed from them.
  • the resin containing at least one structure represented by any one of the general formulas (1) and (2) can be used as a resin solution dissolved in a solvent.
  • the solvent preferably used in the resin solution of the present invention include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ale, propylene glycol monoethyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene Glycol dibutyl ether, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, ethers such as diethylene glycol methyl ethyl ether, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propyl acetate, butyl acetate, isobutyl acetate, 3-methoxybutyl acetate, 3- Methyl-3-meth Acetates such as sibutyl acetate, methyl lactate, ethyl lactate and butyl lactate, ketones such as acetylacetone, methyl propyl ketone,
  • the concentration and viscosity range of the resin solution is preferably in the range of 1 mPa ⁇ sec to 1000 Pa ⁇ sec at a concentration of 1 to 50% by weight, more preferably in the range of 100 mPa ⁇ sec to 100 Pa ⁇ sec at a concentration of 5 to 30% by weight. . By being in this range, a uniform film without unevenness can be formed.
  • the resin solution of the present invention preferably further includes c) a silane compound represented by the following general formula (9).
  • R 17 represents an alkoxyl group having 1 to 4 carbon atoms.
  • R 18 represents an alkoxyl group having 1 to 4 carbon atoms or an alkyl group, and
  • R 19 represents a divalent organic group having 1 to 4 carbon atoms.
  • Specific examples of preferred alkoxy groups include, but are not limited to, methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group and the like.
  • Specific examples of preferable alkyl groups include, but are not limited to, methyl group, ethyl group, propyl group, isopropyl group, and butyl group.
  • Z represents a functional group reactive with an isocyanate group.
  • Preferable specific examples include, but are not limited to, a hydroxyl group, amino group, epoxy group, acrylic group, methacryl group, maleimide group, thiol group, carboxyl group, acid anhydride group, and isocyanate group.
  • Examples of particularly preferred compounds include, but are not limited to, those listed below.
  • the resin solution of the present invention may be a resin composition containing an additive for functionalization.
  • the resin composition of the present invention may contain a photoacid generator, and can impart positive photosensitivity.
  • the photoacid generator include a quinonediazide compound, a sulfonium salt compound, a phosphonium salt compound, a diazonium salt compound, an iodonium salt compound, and the like.
  • a quinonediazide compound is preferable, and an o-quinonediazide compound is particularly preferable.
  • the quinonediazide compound includes a polyhydroxy compound in which a sulfonic acid of quinonediazide is bonded with an ester, a polyamino compound in which a sulfonic acid of quinonediazide is bonded to a sulfonamide, and a sulfonic acid of quinonediazide in an ester bond and / or sulfone.
  • Examples include amide-bonded ones.
  • quinonediazide When 50 mol% or more is substituted with quinonediazide, there is an advantage that the solubility in an alkali developer is improved and a fine pattern having a high contrast with the unexposed portion can be obtained.
  • a positive photosensitive resin composition sensitive to i-line (365 nm), h-line (405 nm), and g-line (436 nm) of a mercury lamp which is a general ultraviolet ray is obtained. be able to.
  • Polyhydroxy compounds include Bis-Z, BisP-EZ, TekP-4HBPA, TrisP-HAP, TrisP-PA, TrisP-SA, TrisOCR-PA, BisOCHP-Z, BisP-MZ, BisP-PZ, BisP-IPZ, BisOCP -IPZ, BisP-CP, BisRS-2P, BisRS-3P, BisP-OCHP, Methylenetris-FR-CR, BisRS-26X, DML-MBPC, DML-MBOC, DML-OCHP, DML-PCHP, DML-PC, DML-PTBP, DML-34X, DML-EP, DML-POP, dimethylol-BisOC-P, DML-PFP, DML-PSBP, DML-MTrisPC, TriML-P, TriML-35XL, TML-B P, TML- Q, TML-pp-BPF, TML-BPA, TMOM-BP, HML-TPPHBA, HML-TPHAP (
  • Polyamino compounds include 1,4-phenylenediamine, 1,3-phenylenediamine, 4,4′-diaminodiphenyl ether, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylsulfone, 4,4′-diaminodiphenyl Examples thereof include, but are not limited to, sulfhydrides.
  • examples of the polyhydroxypolyamino compound include 2,2-bis (3-amino-4-) hydroxyphenyl) hexafluoropropane, 3,3′-dihydroxybenzidine, and the like, but are not limited thereto.
  • quinonediazide is preferably a 5-naphthoquinonediazidesulfonyl group or a 4-naphthoquinonediazidesulfonyl group.
  • the 4-naphthoquinonediazide sulfonyl ester compound has absorption in the i-line region of a mercury lamp and is suitable for i-line exposure.
  • the 5-naphthoquinonediazide sulfonyl ester compound has absorption up to the g-line region of a mercury lamp and is suitable for g-line exposure.
  • a naphthoquinone diazide sulfonyl ester compound can be obtained by using a 4-naphthoquinone diazide sulfonyl group and a 5-naphthoquinone diazide sulfonyl group in the same molecule, or a 4-naphthoquinone diazide sulfonyl ester compound and a 5-naphthoquinone diazide sulfonyl ester.
  • a compound can also be used in combination.
  • the molecular weight of the quinonediazide compound is preferably 300 or more, more preferably 350 or more. Moreover, 1500 or less is preferable and 1200 or less is more preferable. When the molecular weight is 300 or more, the exposure sensitivity is high, and when it is 1500 or less, there is an advantage that the mechanical properties of the film after the heat treatment are improved.
  • the content of the photoacid generator is preferably 1 part by weight or more, more preferably 3 parts by weight or more with respect to 100 parts by weight of the resin. Moreover, 50 weight part or less is preferable and 40 weight part or less is more preferable.
  • the content in the case of the quinonediazide compound is preferably 1 part by weight or more and more preferably 3 parts by weight or more with respect to 100 parts by weight of the resin. Moreover, 50 weight part or less is preferable and 40 weight part or less is more preferable. Within this range, there is an advantage that the mechanical properties of the cured film are improved.
  • the quinonediazide compound used in the present invention is synthesized from a specific phenol compound by the following method. For example, there is a method of reacting 5-naphthoquinonediazidesulfonyl chloride with a phenol compound in the presence of triethylamine. As a method for synthesizing a phenol compound, there is a method in which an ⁇ - (hydroxyphenyl) styrene derivative is reacted with a polyhydric phenol compound under an acid catalyst.
  • the heat-treated film obtained from the photosensitive resin composition of the present invention is used as a permanent film, so that phosphorus or the like remains. This is unfavorable for the environment, and it is necessary to consider the color tone of the membrane.
  • a sulfonium salt is preferably used. Particularly preferred is a triarylsulfonium salt.
  • the resin composition of the present invention has an ethyl methacrylate group, an ethyl acrylate group, a propyl methacrylate group, a propyl acrylate group as R 3 in the general formula (1) in order to impart negative photosensitivity.
  • a group having an ethylenically unsaturated double bond such as an ethyl methacrylamide group, a propyl methacrylamide group, an ethyl acrylamide group, or a propyl acrylamide group can be used.
  • a photopolymerizable compound may be included.
  • photopolymerizable compounds examples include 2-hydroxyethyl methacrylate, trimethylolpropane trimethacrylate, trimethylolpropane triacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, propylene glycol dimethacrylate. , Methylene bismethacrylamide, methylene bisacrylamide and the like, but are not limited thereto.
  • the photopolymerizable compound is preferably contained in the range of 1 to 30 parts by weight with respect to 100 parts by weight of the resin. Within this range, the sensitivity is high, and the film has a good mechanical property after thermosetting. These photopolymerizable compounds can be used alone or in combination of two or more.
  • a photopolymerization initiator when imparting negative photosensitivity to the resin composition of the present invention, a photopolymerization initiator may be contained.
  • the photopolymerization initiator suitable for the present invention include aromatic amines such as N-phenyldiethanolamine and N-phenylglycine, aromatic ketones such as Michler's ketone, and cyclic oximes represented by 3-phenyl-5-isoxazolone.
  • Chain oxime compounds typified by 1-phenylpropanedione-2- (o-ethoxycarbonyl) oxime, benzophenone, benzophenone derivatives such as methyl o-benzoylbenzoate, dibenzylketone, fluorenone, thioxanthone, 2-methyl
  • benzophenone benzophenone derivatives such as methyl o-benzoylbenzoate, dibenzylketone, fluorenone, thioxanthone, 2-methyl
  • Examples include, but are not limited to, thioxanthone derivatives such as thioxanthone and 2-isopropylthioxanthone.
  • the content of the photopolymerization initiator is preferably 0.01 parts by weight or more and more preferably 0.1 parts by weight or more with respect to 100 parts by weight of the resin. Moreover, 30 weight part or less is preferable and 20 weight part or less is more preferable. Within this range, the sensitivity is high, and the film has a good mechanical property after thermosetting.
  • These photoinitiators can be used alone or in combination of two or more.
  • Photosensitizers suitable for the present invention include aromatic monoazides such as azidoanthraquinone and azidobenzalacetophenone, aminocoumarins such as 7-diethylaminobenzoylcoumarin, 3,3′-carbonylbis (diethylaminocoumarin), and benzanthrone. And aromatic ketones such as phenanthrenequinone, which are generally used for photocurable resins. In addition, it may be preferably used as long as it is used as a charge transfer agent for an electrophotographic photoreceptor.
  • the content of the photosensitizer is preferably 0.01 parts by weight and more preferably 0.1 parts by weight or more with respect to 100 parts by weight of the resin. Moreover, 30 weight part or less is preferable and 20 weight part or less is more preferable. Within this range, the sensitivity is high, and the film has a good mechanical property after the heat treatment.
  • These photosensitizers can be used alone or in combination of two or more.
  • the resin composition of the present invention can contain a compound having a phenolic hydroxyl group for the purpose of controlling the alkali developability of a resin film formed from the resin composition.
  • Examples of the compound having a phenolic hydroxyl group that can be used in the present invention include Bis-Z, BisOC-Z, BisOPP-Z, BisP-CP, Bis26X-Z, BisOTBP-Z, BisOCHP-Z, and BisOCR-CP.
  • preferred compounds having a phenolic hydroxyl group include, for example, Bis-Z, BisP-EZ, TekP-4HBPA, TrisP-HAP, TrisP-PA, BisOCHP-Z, BisP-MZ, BisP-PZ, BisP- IPZ, BisOCP-IPZ, BisP-CP, BisRS-2P, BisRS-3P, BisP-OCHP, Methylenetris-FR-CR, BisRS-26X, BIP-PC, BIR-PC, BIR-PTBP, BIR-BIPC-F Etc.
  • particularly preferred compounds having a phenolic hydroxyl group include, for example, Bis-Z, TekP-4HBPA, TrisP-HAP, TrisP-PA, BisRS-2P, BisRS-3P, BIR-PC, BIR-PTBP, BIR -BIPC-F.
  • this compound having a phenolic hydroxyl group By containing this compound having a phenolic hydroxyl group, the resulting resin composition is easily dissolved in an alkali developer before exposure, becomes insoluble in an alkali developer upon exposure, and film loss due to development is reduced. Less development and easy development in a short time.
  • the content of such a compound having a phenolic hydroxyl group is preferably 1 to 60 parts by weight, more preferably 3 to 50 parts by weight with respect to 100 parts by weight of the resin.
  • the resin composition of the present invention can be applied to a silicon-based substrate such as silicon, silicon nitride, silicon oxide, and phosphorous silicate glass of the heat-treated film, oxygen plasma used for further enhancement of adhesion to an ITO substrate, cleaning, etc.
  • a silane coupling agent other than the silane compound represented by the general formula (8), a titanium chelating agent, an aluminum chelating agent, and the like can also be contained.
  • preferable silane coupling agents include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrichlorosilane, vinyltris ( ⁇ -methoxyethoxy) silane, and the like.
  • the content of these adhesion improvers is preferably 0.01 to 15 parts by weight with respect to 100 parts by weight of the resin.
  • the pretreatment method include the following methods.
  • a solvent such as isopropanol, ethanol, methanol, water, tetrahydrofuran, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, diethyl adipate, etc.
  • hexamethyldisilazane vapor may be directly sprayed for treatment.
  • a reduced-pressure drying treatment is performed as necessary, and the reaction between the surface of the silicon-based material and the adhesion improving agent is advanced by applying a temperature of 50 to 300 ° C.
  • the resin composition of the present invention may contain a surfactant and can improve the wettability with the substrate.
  • a surfactant "Florard” (registered trademark) (trade name, manufactured by Sumitomo 3M Co., Ltd.), "Megafuck” (registered trademark) (trade name, manufactured by DIC Corporation), "Sulfuron” (registered trademark) ) (Trade name, manufactured by Asahi Glass Co., Ltd.) and other fluorosurfactants, KP341 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.), DBE (trade name, manufactured by Chisso Corp.), “Granol” (registered) Trademark) (trade name, manufactured by Kyoeisha Chemical Co., Ltd.), BYK (manufactured by Big Chemie Co., Ltd.) and other organic siloxane surfactants, “Polyflow” (registered trademark) (trade name, manufactured by Kyoeisha Chemical Co., Ltd.)
  • filler it is also possible to add a filler to the resin solution of the present invention and use it as a slurry.
  • the addition of fillers can be expected to further reduce linear expansion, increase strength, and control refractive index, dielectric constant, and magnetic permeability.
  • a secondary battery or a capacitor it can be functionalized as a positive electrode and a negative electrode.
  • Preferred fillers for use in semiconductors, displays, multilayer wiring boards include, but are not limited to, silicon oxide, titanium oxide, alumina, barium titanate, aluminum nitride, zirconium oxide, silicon nitride, titanium nitride and the like.
  • Preferred fillers for use in secondary batteries and capacitors include atoms such as carbon, silicon, tin, germanium, titanium, iron, cobalt, nickel, manganese, copper, silver, zinc, indium, bismuth, antimony or chromium.
  • Compounds Preferably, it is a compound containing at least one atom among carbon, manganese, cobalt, nickel, iron, silicon, titanium, tin, and germanium, and more preferably a compound containing at least one atom among silicon and titanium. It is.
  • the filler plays a role as an active material. For this reason, it can use as a slurry for electrodes of a secondary battery or a capacitor by adding a filler to the resin of the present invention to form a slurry.
  • examples of the filler for the positive electrode include lithium iron phosphate, lithium cobaltate, lithium nickelate, lithium manganate, activated carbon, and carbon nanotube.
  • examples of the filler for the negative electrode include lithium titanate, hard carbon, soft carbon, activated carbon, carbon nanotube, silicon, tin, and a compound containing germanium atoms.
  • a resin having high mechanical strength such as the resin of the present invention as a binder. This is preferable for reducing the deterioration of the capacity, that is, the capacity deterioration during charging and discharging.
  • Examples of the compound containing a silicon atom include (1) silicon fine particles, (2) tin, nickel, copper, iron, cobalt, manganese, zinc, indium, silver, titanium, germanium, bismuth, antimony or chromium, and silicon. (3) Boron, nitrogen, oxygen, or a compound of carbon and silicon, and those having the metal exemplified in (2) above.
  • silicon alloys or compounds include SiB 4 , SiB 6 , Mg 2 Si, Ni 2 Si, TiSi 2 , MoSi 2 , CoSi 2 , NiSi 2 , CaSi 2 , CrSi 2 , Cu 5 Si, FeSi 2 , MnSi 2 , NbSi 2 , TaSi 2 , VSi 2 , WSi 2 , ZnSi 2 , SiC, Si 3 N 4 , Si 2 N 2 O, SiOv (0 ⁇ v ⁇ 2), LiSiO, or the like.
  • Examples of the compound containing a tin atom include (1) an alloy of silicon, nickel, copper, iron, cobalt, manganese, zinc, indium, silver, titanium, germanium, bismuth, antimony or chromium and tin, (2) Examples thereof include compounds of oxygen or carbon and tin, and those having the metal exemplified in (1).
  • Examples of tin alloys or compounds include SnOw (0 ⁇ w ⁇ 2), SnSiO 3 , LiSnO, Mg 2 Sn, and the like.
  • Examples of the compound containing a germanium atom include an alloy of silicon, tin, and germanium.
  • the median diameter (d50) in the particle size distribution of the filler is preferably 0.01 to 20 ⁇ m. Further, the surface of the filler may be treated with a silane coupling agent or the like.
  • the median diameter was measured using a laser diffraction / scattering particle size distribution analyzer LA-920 manufactured by Horiba. Prior to the measurement, an appropriate amount of the sample was added to the aqueous solution of sodium hexametaphosphate and dispersed with an ultrasonic cleaner for about 10 minutes, and then the measurement was performed. This makes it possible to accurately measure the particle size distribution by agglomerating a sample in which the powder is agglomerated and suppressing the precipitation of powder having a large particle size.
  • the content of the resin is preferably 1 part by weight or more with respect to 100 parts by weight of the filler, and the adhesiveness can be further improved. . 3 parts by weight or more is more preferable, and 5 parts by weight or more is more preferable.
  • the electrode of a secondary battery or a capacitor it is preferably 20 parts by weight or less, more preferably 15 parts by weight or less, and most preferably 12 parts by weight or less in order to reduce the electrical resistance and increase the filling amount of the filler.
  • the negative electrode paste of the present invention may contain conductive particles such as graphite, ketjen black, carbon nanotube, and acetylene black in order to reduce the electric resistance. These contents are preferably 0.1 parts by weight or more and 20 parts by weight or less with respect to 100 parts by weight of the negative electrode active material.
  • the resin solution, resin composition, and slurry of the present invention can be obtained by mixing and kneading a resin, and if necessary, a solvent and other additives.
  • a method of stirring and dissolving with a mechanical stirrer, etc. a method of dissolving with ultrasonic waves, a method of stirring and dissolving with a planetary stirring deaerator, etc.
  • kneading a method using a planetary mixer, three rolls, a ball mill, a homogenizer and the like can be mentioned.
  • the mixing / kneading conditions are not particularly limited.
  • the resin solution, resin composition, and slurry after mixing and kneading may be filtered through a filter having a pore size of 0.01 ⁇ m to 100 ⁇ m.
  • a filter having a pore size of 0.01 ⁇ m to 100 ⁇ m examples include polypropylene (PP), polyethylene (PE), nylon (NY), polytetrafluoroethylene (PTFE), and polyethylene and nylon are preferable.
  • PP polypropylene
  • PE polyethylene
  • nylon NY
  • PTFE polytetrafluoroethylene
  • polyethylene and nylon are preferable.
  • a resin composition contains a filler and an organic pigment
  • a laminate can also be made by applying the resin solution, resin composition, or slurry of the present invention to one or both sides of a substrate and drying.
  • a conductive base material or an insulating base material on which conductive wiring is formed is used as the base material.
  • Preferred examples of the conductive substrate and wiring include copper, aluminum, stainless steel, nickel, gold, silver, alloys thereof, and carbon, but are not limited thereto. In particular, copper, aluminum, gold, nickel and alloys containing them are more preferable.
  • Insulating base materials include organic base materials such as PET, polyimide, polybenzoxazole, polyamide, polyamideimide, and epoxy, silicon oxide, silicon nitride, titanium nitride, titanium oxide, and base materials on which they are formed. Although it is mentioned, it is not limited to these.
  • the manufacturing method of the laminated body of this invention is demonstrated.
  • the resin solution, resin composition, or slurry of the present invention is applied on a substrate.
  • 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 coating film thickness varies depending on the coating method, the solid content concentration of the composition, the viscosity, and the like, but it is usually preferable that the film thickness after drying is 0.1 to 150 ⁇ m.
  • the coated substrate is dried to obtain a resin composition film. Drying is preferably performed using an oven, a hot plate, infrared rays, or the like in the range of 50 ° C. to 200 ° C. for 1 minute to several hours.
  • Actinic rays used for exposure include ultraviolet rays, visible rays, electron beams, and X-rays.
  • light having a wavelength of 350 nm or more and 450 nm or less is preferable, i-ray (wavelength 365 nm), h-ray (wavelength 405 nm) of a mercury lamp. ), G-line (wavelength 436 nm) is preferably used.
  • photoresist film when exposing a non-photosensitive resin solution, resin composition, or slurry, it is necessary to form another photoresist film on the resin film.
  • a general novolak resist such as OFPR-800 (manufactured by Tokyo Ohka Co., Ltd.) is preferably used.
  • the formation of the photoresist film is performed by the same method as the formation of the resin composition film.
  • This temperature is preferably in the range of 50 to 180 ° C, more preferably in the range of 60 to 150 ° C.
  • the time is preferably 10 seconds to several hours. Within this range, there are advantages that the reaction proceeds satisfactorily and the development time can be shortened.
  • Develop processing is performed to form a resin solution, resin composition, or slurry pattern.
  • the resin solution, resin composition, or slurry has negative photosensitivity, the unexposed area is removed with a developer.
  • the resin solution has positive photosensitivity, the exposed area is removed with a developer. A pattern is obtained.
  • a suitable developer can be selected according to the resin structure.
  • An aqueous solution of an alkaline compound such as diethylamine, methylamine, dimethylamine, dimethylaminoethyl acetate, dimethylaminoethanol, dimethylaminoethyl methacrylate, cyclohexylamine, ethylenediamine, and hexamethylenediamine can be preferably used.
  • polar aqueous solutions such as N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, ⁇ -butyrolactone, dimethylacrylamide, methanol, ethanol, isopropanol are used in these alkaline aqueous solutions.
  • alcohols such as ethyl lactate, esters such as propylene glycol monomethyl ether acetate, ketones such as cyclopentanone, cyclohexanone, isobutyl ketone, and methyl isobutyl ketone may be added.
  • N-methyl-2-pyrrolidone, N-acetyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, hexamethylphosphonate, which are good solvents for the resin of the present invention, are used.
  • Lutriamide, etc. and the poor solvents for resins such as methanol, ethanol, isopropyl alcohol, water, methyl carbitol, ethyl carbitol, toluene, xylene, ethyl lactate, ethyl pyruvate, propylene glycol monomethyl ether acetate, methyl-3-methoxy
  • a mixture of propionate, ethyl-3-ethoxypropionate, 2-heptanone, cyclopentanone, cyclohexanone, ethyl acetate, etc. alone or in combination with the above good solvent can also be preferably used.
  • the development can be carried out by a method such as irradiating the developer on the coating film as it is or in the form of a mist, immersing in the developer, or applying ultrasonic waves while immersing.
  • rinse solution water can be preferably used when an alkaline aqueous solution is used as the developer.
  • rinse treatment may be performed by adding an ester such as ethanol, isopropyl alcohol, propylene glycol monomethyl ether acetate, an acid such as carbon dioxide, hydrochloric acid, or acetic acid to water.
  • the photoresist film formed on the resin film must be removed after development. This removal is often performed by dry etching or wet etching with a stripping solvent.
  • a stripping solvent organic solvents such as acetone, butyl acetate, ethyl lactate, propylene glycol monomethyl ether acetate, methyl-3-methoxypropionate, ethyl-3-ethoxypropionate, 2-heptanone, ethyl acetate, An aqueous solution of sodium hydroxide or potassium hydroxide is used, but not limited thereto.
  • the heat resistance may be cured at a temperature of 150 ° C. to 500 ° C. after development.
  • This heat treatment is preferably carried out for 5 minutes to 5 hours by selecting the temperature and raising the temperature stepwise, or selecting a certain temperature range and continuously raising the temperature.
  • a method of performing heat treatment at 130 ° C., 200 ° C., and 350 ° C. for 30 minutes each, a method of linearly raising the temperature from room temperature to 320 ° C. over 2 hours, and the like can be mentioned.
  • the heat treatment is preferably performed at 250 ° C.
  • the resin represented by the general formula (2) already has a cyclic structure, it is not necessary to perform dehydration and ring closure at a high heat treatment temperature. Is an advantage.
  • the slurry of the present invention is applied on a metal foil in a thickness of 1 to 100 ⁇ m.
  • a copper foil is generally used as the metal foil.
  • methods such as screen printing, roll coating, and slit coating can be used.
  • the polyimide precursor is converted into polyimide by heat treatment at 100 to 500 ° C. for 1 minute to 24 hours after coating, and a reliable negative electrode can be obtained.
  • the treatment is preferably performed at 200 ° C. to 450 ° C. at the following temperature for 30 minutes to 20 hours. Further, it is preferable to heat in an inert gas such as nitrogen gas or in vacuum in order to suppress the mixing of moisture.
  • polyimide is used as the binder, it is preferable to remove the solvent by heat treatment at 80 ° C. to 500 ° C. for 1 minute to 24 hours after coating. In particular, since it is not necessary to imidize, it is more preferable to treat at 100 ° C. to 250 ° C. for 10 minutes to 24 hours. In any case, it is preferable to heat in an inert gas such as nitrogen gas or in a vacuum in order to suppress the mixing of moisture.
  • a negative electrode having pores inside can be obtained by decomposing the low-temperature decomposition resin by heat treatment.
  • heat treatment is preferably performed at a temperature higher than the decomposition temperature of the low-temperature decomposition resin and lower than the decomposition temperature of the binder.
  • a temperature range it is preferable to perform the treatment at 300 to 450 ° C. for 30 minutes to 20 hours.
  • thermally decomposable resins include polyethylene glycol and polypropylene glycol.
  • the slurry of the present invention is applied on a metal foil in a thickness of 1 to 500 ⁇ m.
  • the metal foil include aluminum foil, nickel foil, titanium foil, and copper foil, and aluminum foil is generally used.
  • the application method and heat treatment method are the same as those for the lithium battery negative electrode.
  • the separator examples include polyolefins such as polyethylene and polypropylene, microporous films such as cellulose, polyphenylene sulfide, aramid, and polyimide, and nonwoven fabrics.
  • the surface of the separator may be coated with ceramic or the like.
  • the solvent used in the electrolytic solution serves as a medium through which ions involved in the electrochemical reaction of the battery can move.
  • Preferred solvents include carbonate-based, ester-based, ether-based, ketone-based, alcohol-based and non-protonic solvents.
  • the carbonate solvent include dimethyl carbonate (DMC), diethyl carbonate (DEC), dipropyl carbonate (DPC), methyl propyl carbonate (MPC), ethyl propyl carbonate (EPC), methyl ethyl carbonate (MEC), and ethyl methyl carbonate.
  • DMC dimethyl carbonate
  • DEC diethyl carbonate
  • DPC dipropyl carbonate
  • MPC methyl propyl carbonate
  • EPC ethyl propyl carbonate
  • MEC methyl ethyl carbonate
  • EMC ethyl methyl carbonate
  • EMC ethylene carbonate
  • EC propylene carbonate
  • BC buty
  • ester solvent examples include methyl acetate, ethyl acetate, n-propyl acetate, methyl propionate, ethyl propionate, ⁇ -butyrolactone, tecanolide, valerolactone, mevalonolactone, caprolactone and the like.
  • ether solvent examples include dibutyl ether, tetraglyme, diglyme, dimethoxyethane, 2-methyltetrahydrofuran, and tetrahydrofuran.
  • ketone solvent examples include cyclohexanone.
  • the alcohol solvent examples include ethyl alcohol and isopropyl alcohol.
  • non-protonic solvent examples include tolyls, amides such as dimethylformamide, dioxolanes such as 1,3-dioxolane, and sulfolanes. Two or more of these may be used, and the content ratio can be appropriately selected according to the intended battery performance.
  • the carbonate-based solvent it is preferable to use a combination of a cyclic carbonate and a chain carbonate in a volume ratio of 1: 1 to 1: 9, which can improve the performance of the electrolytic solution.
  • Examples of the electrolyte used for the electrolytic solution 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.
  • the film, laminate formed of the resin, resin composition, slurry of the present invention can be used for electronic parts such as semiconductor packages and multilayer wiring boards. Specifically, it is suitably used for applications such as a semiconductor passivation film, a semiconductor element surface protective film, an interlayer insulating film, an interlayer insulating film of a multilayer wiring for high-density mounting, and an insulating layer of an organic electroluminescent element. It is not limited to this, and various structures can be taken. Moreover, when a resin composition contains a conductive filler, it can also be used as a wiring material.
  • composition solution was spin-coated on an 8-inch silicon wafer, and then a hot plate at 120 ° C.
  • the resin film was obtained by baking for 3 minutes using a coating and developing apparatus Act-8 (manufactured by Tokyo Electron Ltd.).
  • a coating and developing apparatus Act-8 manufactured by Tokyo Electron Ltd.
  • CLH-21CD-S manufactured by Koyo Thermo System Co., Ltd.
  • the resin film was heated to 200 ° C. at an oxygen concentration of 20 ppm or less at 5 ° C./min, and was heat-treated at 200 ° C. for 1 hour. Then, it was cooled to 50 ° C.
  • composition solution was spin-coated on an 8-inch silicon wafer, and then a hot plate at 120 ° C. (Coating and developing apparatus Act-8 manufactured by Tokyo Electron Ltd.) Use) for 3 minutes to obtain a resin film.
  • the resin film was heated to 200 ° C. at an oxygen concentration of 20 ppm or less at 5 ° C./min, and was heat-treated at 200 ° C. for 1 hour. Then, it was cooled to 50 ° C. at 5 ° C./min. Subsequently, it was immersed in hydrofluoric acid for 1 to 4 minutes to peel the film from the substrate and air-dried to obtain a heat-treated film. The number of rotations during spin coating was adjusted so that the resin film thickness after the heat treatment was 10 ⁇ m.
  • the film after the heat treatment was measured under a nitrogen stream using a thermomechanical analyzer (EXSTAR6000 TMA / SS6000 manufactured by SII Nanotechnology Co., Ltd.).
  • the temperature raising method was performed under the following conditions. In the first stage, the temperature was raised to 200 ° C. at a temperature rising rate of 5 ° C./min to remove adsorbed water from the sample, and in the second stage, air cooling was performed to a room temperature at a temperature lowering rate of 5 ° C./min. In the third stage, the main measurement was performed at a temperature elevation rate of 5 ° C./min, and the average value of the thermal linear expansion coefficient from 50 ° C. to 200 ° C. was obtained.
  • Adhesiveness with copper A copper substrate formed with a thickness of 500 nm on an 8-inch silicon wafer was prepared. The composition was spin-coated on this substrate and then baked for 3 minutes on a 120 ° C. hot plate (using a coating and developing apparatus Act-8 manufactured by Tokyo Electron Ltd.) to obtain a resin film.
  • the resin film was heated to 200 ° C. at an oxygen concentration of 20 ppm or less at 5 ° C./min, and was heat-treated at 200 ° C. for 1 hour. Then, it was cooled to 50 ° C. at 5 ° C./min. The number of rotations during spin coating was adjusted so that the resin film thickness after the heat treatment was 10 ⁇ m.
  • the heat-treated film was heated and humidified at 121 ° C. and 2 atm for 400 hours, then cut into 10 rows and 10 columns at 2 mm intervals, and peeled off with cello tape (registered trademark).
  • the adhesiveness with copper was evaluated by how many squares remained in 100 squares.
  • Adhesiveness with silicon The composition was spin-coated on an 8-inch silicon wafer, and then baked for 3 minutes on a 120 ° C. hot plate (using a coating and developing apparatus Act-8 manufactured by Tokyo Electron Ltd.). A resin film was obtained. Using an inert oven CLH-21CD-S (manufactured by Koyo Thermo System Co., Ltd.), the resin film was heated to 200 ° C. at an oxygen concentration of 20 ppm or less at 5 ° C./min, and was heat-treated at 200 ° C. for 1 hour. Then, it was cooled to 50 ° C. at 5 ° C./min.
  • the number of rotations during spin coating was adjusted so that the resin film thickness after the heat treatment was 10 ⁇ m.
  • the heat-treated film was heated and humidified at 121 ° C. and 2 atm for 400 hours, then cut into 10 rows and 10 columns at 2 mm intervals, and peeled off with cello tape (registered trademark).
  • the adhesion with silicon was evaluated based on how many of the 100 cells remained.
  • Capacity maintenance rate It carried out according to the following procedures using the composition of this invention. a) Preparation of Negative Electrode 80 parts by weight of the negative electrode active material obtained in Synthesis Example 1, 75 parts by weight of a composition having a solid content concentration of 20%, and 5 parts by weight of acetylene black as a conductive assistant were dissolved in an appropriate amount of NMP and stirred. After that, a slurry-like paste was obtained. The obtained paste was applied onto an electrolytic copper foil using a doctor blade, dried at 110 ° C. for 30 minutes, and pressed with a roll press to obtain an electrode. Further, the coated part of this electrode was punched out into a circle having a diameter of 16 mm and vacuum-dried at 200 ° C. for 24 hours to produce a negative electrode.
  • Electrode characteristic evaluation In measuring the charge / discharge characteristics, an HS cell (manufactured by Hosen Co., Ltd.) was used, and the lithium ion battery was assembled in a nitrogen atmosphere. The negative electrode made in the cell is punched into a circle with a diameter of 16 mm, the separator porous film (made by Hosen Co., Ltd.) is punched into a diameter of 24 mm, and the positive electrode is made of an active material made of lithium cobalt oxide.
  • Example 1 Under a dry nitrogen stream, 10.6 g (0.04 mol: 40 mol%) of o-tolidine diisocyanate as an amine component, 3.48 g (0.02 mol: 20 mol%) of 2,4-tolylene diisocyanate, and 4, 10.0 g (0.04 mol: 40 mol%) of 4′-diphenylmethane diisocyanate was dissolved in 120 g of N-methyl-2-pyrrolidone (NMP). To this, 19.2 g (0.1 mol: 100 mol%) of trimellitic anhydride was added as an acid component together with 17.9 g of NMP and reacted at 120 ° C. for 2 hours and at 140 ° C. for 2 hours to give a resin concentration of 20%. 1 was obtained.
  • NMP N-methyl-2-pyrrolidone
  • Example 10 Under a dry nitrogen stream, 18.5 g (0.07 mol: 70 mol%) of o-tolidine diisocyanate and 5.22 g (0.03 mol: 30 mol%) of 2,4-tolylene diisocyanate were dissolved in 120 g of NMP as amine components. I let you. To this, 0.871 g (0.01 mol: 10 mol%) of 2-butanone oxime as an end-capping agent was added together with 10 g of NMP, reacted at 70 ° C. for 2 hours, and further 18.3 g of trimellitic anhydride as an acid component. (0.095 mol: 95 mol%) was added together with 8.12 g of NMP and reacted at 120 ° C. for 2 hours and at 140 ° C. for 2 hours to obtain a composition 10 having a resin concentration of 20%.
  • Example 11 A composition 11 having a resin concentration of 20% was obtained in the same manner as in Example 10 using the amine component, acid component, and terminal blocker shown in Table 1.
  • Example 12 Under a dry nitrogen stream, 18.5 g (0.07 mol: 70 mol%) of o-tolidine diisocyanate and 5.22 g (0.03 mol: 30 mol%) of 2,4-tolylene diisocyanate were dissolved in 120 g of NMP as amine components. I let you. To this, 0.871 g (0.01 mol: 10 mol%) of 2-butanone oxime as an end-capping agent was added together with 10 g of NMP, reacted at 70 ° C. for 2 hours, and further 18.3 g of trimellitic anhydride as an acid component. (0.095 mol: 95 mol%) was added together with 15.0 g of NMP and reacted at 120 ° C.
  • Example 13 Using the amine component, acid component, end-capping material and silane compound shown in Table 1, composition 13 having a total concentration of resin and silane compound of 20% was obtained in the same manner as in Example 12.
  • Synthesis Example 1 Synthesis of negative electrode active material 50 g of natural graphite having a median diameter of 10 ⁇ m (manufactured by Fuji Graphite Co., Ltd., CBF1), 60 g of nanosilicon powder (manufactured by Aldrich), and 10 g of carbon black (manufactured by Mitsubishi Chemical Co., Ltd., 3050) Were mixed well in a ball mill at 600 rpm for 12 hours, and then vacuum-dried at 80 ° C. for 12 hours to obtain a Si—C-based negative electrode active material. The median diameter was 10 ⁇ m.
  • the compositions and evaluation results of the compositions 1 to 18 are shown in Table 1 as Examples 1 to 14 and Comparative Examples 1 to 4.

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CN108519407A (zh) * 2018-05-28 2018-09-11 湖北金泉新材料有限责任公司 一种评估锂离子电池导电浆料分散性的方法
KR20200027517A (ko) * 2017-07-07 2020-03-12 도레이 카부시키가이샤 수지 조성물, 적층체 및 그의 제조 방법, 전극, 이차 전지 그리고 전기 이중층 캐패시터
JP7038443B1 (ja) 2021-02-10 2022-03-18 ユニチカ株式会社 ベルト成形用ポリアミドイミド溶液およびポリアミドイミドベルトの製造方法

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CN111384209B (zh) * 2019-12-12 2021-06-18 横店集团东磁股份有限公司 Ald方式perc电池降低污染和提升转换效率的方法
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