KR20180090787A - Resin, slurry, laminate using them, and manufacturing method thereof - Google Patents

Abstract

Disclosure of the Invention The present invention is to provide a lithium ion battery and a capacitor electrode binder capable of achieving good capacity retention at the time of charge and discharge and capable of achieving low temperature curing and high strength, high elasticity, high adhesion and low linear expansion, It is an object of the present invention to provide a resin capable of producing a package, a display, and a multilayer wiring board. The present invention is a resin having a structural unit represented by the general formula (1) and / or a structural unit represented by the general formula (2) as described in claim 1, wherein R ¹ and R ⁴ , Independently of each other, a resin comprising at least a part of a structure represented by the general formula (3) and a structure represented by the general formula (4).

Description

Resin, slurry, laminate using them, and manufacturing method thereof

To a resin, a slurry and an electroconductive substrate suitably used as a lithium ion secondary battery, a binder for a capacitor electrode, a semiconductor package, a multilayer interconnection substrate, and an insulating film for a display, a conductive wiring-attached substrate, a laminate thereof and a method of manufacturing the same.

2. Description of the Related Art In recent years, with the explosion of notebook-type personal computers and small-sized portable terminals, there has been a strong demand for a rechargeable battery having a small size, light weight, high capacity, high energy density and high reliability.

In the automobile industry, development of electric vehicles (EV) and hybrid electric vehicles (HEV) is expected to reduce carbon dioxide emissions, and motor-driven rechargeable batteries having the key to practical use are being actively developed.

Particularly, lithium ion secondary batteries having the highest theoretical energy among the batteries are attracting attention, and development is progressing rapidly. A widely used lithium ion battery includes a positive electrode 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, A negative electrode formed by applying a paste containing a negative electrode active material capable of lithium ion intercalation and deintercalation and a binder such as PVDF or styrene-butadiene rubber (SBR) onto a copper foil such as a carbon-based active material is connected via a separator and an electrolyte layer , And a sealed configuration.

In order to further increase the capacity of the lithium ion battery, it has been studied to use silicon, germanium or tin as the negative electrode active material (see, for example, Patent Document 1). As described above, the negative electrode active material using silicon, germanium, tin, or the like can receive a large amount of lithium ions. Therefore, when the battery is adequately charged and discharged sufficiently, the volume change is large. The capacity retention rate in the charge / discharge cycle is lowered. For this reason, studies have been made on a binder for a negative electrode having a large volume expansion (see, for example, Patent Documents 2, 3 and 4).

In addition, high-speed and miniaturization of notebook-type personal computers and small-sized portable terminals have led to miniaturization and thinning of parts such as semiconductors, displays, and multilayer wiring boards, and consequently, deterioration of process yields due to warping of device substrates, There is a concern about the adverse effect on the environment. For this reason, it is required to give the resin a characteristic of reducing warping of the substrate.

As a method for reducing the warpage of the device substrate, there is a method in which the difference in thermal expansion coefficient between the resin deposited on the substrate and the substrate itself is reduced, and the stress caused by the thermal expansion difference is reduced. Since the thermal expansion coefficient of a general resin is 10 ppm or more larger than the thermal expansion coefficient of the substrate, it is effective to reduce the thermal expansion coefficient of the resin in order to reduce the stress described above. Polyimide-based resins (for example, see Patent Documents 5 to 9) having a structure with rigidity in the main chain and having a small thermal expansion coefficient have been reported in order to achieve this task.

Japanese Patent Application Laid-Open No. 2009-199761 Japanese Patent Laid-Open Publication No. 2009-245773 Japanese Patent Laid-Open Publication No. 2010-062041 Japanese Patent Application Laid-Open No. 2009-170384 Japanese Patent Application Laid-Open No. 2-283762 Japanese Patent Laid-Open No. 8-48773 Japanese Patent Application Laid-Open No. 8-253584 Japanese Patent Application Laid-Open No. 11-158279 Japanese Patent Laid-Open No. 2002-363283

However, in Patent Document 1, the sodium salt of carboxymethyl cellulose described as a specific binder for the negative electrode having a large volume expansion has a problem that the strength is still insufficient and a sufficient capacity retention rate can not be obtained in a charge-discharge cycle.

As the polyimide bonding agent disclosed in Patent Document 2, although the strength of the bonding agent is high, there is a problem in that the electrode is deteriorated in oxidation because the bonding process needs to be performed at a high temperature of 300 ° C or higher at the time of manufacturing an electrode in order to switch to a polyimide structure.

As the binder described in Patent Documents 3 and 4, the strength of the binder can be made high and the processing temperature can be made low. However, in order to suppress deterioration of the electrode due to volume change during charging and discharging and to obtain a high capacity retention rate, There was a problem that it was insufficient.

In addition, the polyimides described in Patent Documents 5 to 9 have to be subjected to a high-temperature treatment at 300 DEG C or more in order to convert to a polyimide structure.

SUMMARY OF THE INVENTION Accordingly, it is an object of the present invention to provide a laminate obtained by coating a resin, a slurry and a conductive base material, which have a high strength, a high elasticity, a high adhesion and a low heat linear expansion,

That is, 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 each independently Is a resin containing in part a structure represented by the following general formula (3) and a structure represented by the following general formula (4).

(In the general formula (1), R ¹ represents a divalent organic group having 2 to 50 carbon atoms, R ² represents a tricyclic 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.)

(Formula (2): R ⁴ represents a divalent organic group having 2 to 50. R ⁵ is a C2 to 50 trivalent or denotes a tetravalent organic group of a. M ² is an integer, c ¹ 0 or 1, Is an integer of 0 or 1, c ¹ = 1 when m ² = 0, and c ¹ = 0 when m ² = 1.)

(In the general formula (3), R ⁶ and R ⁷ each independently represent a halogen atom or a monovalent organic group having 1 to 3 carbon atoms, b ¹ and b ² each independently represent an integer of 0 to 3.)

(In the general formula (4), R ⁸ independently represents a halogen atom or a monovalent organic group having 1 to 3 carbon atoms, and b ³ is an integer of 0 to 4)

According to the resin of the present invention, it is possible to obtain a capacity retention rate at the time of good charging and discharging in a binder for a lithium ion battery and a capacitor electrode, which can be cured at a low temperature and has high strength, high elasticity, high adhesion and low linear expansion, A semiconductor package, a display, and a multilayer wiring board with low warpage can be manufactured.

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).

(In the general formula (1), R ¹ represents a divalent organic group having 2 to 50 carbon atoms, R ² represents a tricyclic 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.)

(Formula (2): R ⁴ represents a divalent organic group having 2 to 50. R ⁵ is a C2 to 50 trivalent or denotes a tetravalent organic group of a. M ² is an integer, c ¹ 0 or 1, Is an integer of 0 or 1, c ¹ = 1 when m ² = 0, and c ¹ = 0 when m ² = 1.)

From the viewpoint of being able to be treated at a lower temperature, it is preferably a resin containing a structural unit represented by the general formula (2) as a main component, more preferably a polyamideimide structure in which m ² is 0 in view of solubility in a solvent .

As used herein, the main component means at least 70 wt%, preferably at least 80 wt% of the total resin.

In the general formulas (1) and (2), 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 represent a structure represented by formula (3) and a structure represented by formula (4).

In the general formula (3), R ⁶ and R ⁷ each independently represent a halogen atom or a monovalent organic group having 1 to 3 carbon atoms. Preferably a fluorine atom, an alkyl group or a fluoroalkyl group having 1 to 3 carbon atoms, more preferably an alkyl group or a fluoroalkyl group having 1 to 3 carbon atoms in that the coefficient of linear expansion of the resin can be reduced.

b ¹ and b ² are each independently an integer of 0 to 3; And is preferably 1 or 2 in terms of compatibility with a solvent and low linear expansion property. From the viewpoint of low linear expansion property, it is preferable that R ⁶ and R ⁷ are bonded to the ortho position with respect to the polymer main chain.

From the viewpoint of the low linear expansion characteristic of the general formula (3), the benzene ring is preferably connected to a para bond. Specific examples include those having the structures shown below, but are not limited thereto.

From the viewpoint of compatibility between the solubility in the solvent and the low linear expansion property, R ¹ and R ⁴ each independently preferably have a structure represented by the formula (3) in which 50 mol% or more thereof is contained and 70 mol% or more Is more preferable.

In the general formula (4), R ⁸ independently represents a halogen atom or a monovalent organic group having 1 to 3 carbon atoms. Preferably a fluorine atom, an alkyl group or a fluoroalkyl group having 1 to 3 carbon atoms, more preferably an alkyl group or a fluoroalkyl group having 1 to 3 carbon atoms in that the coefficient of linear expansion of the resin can be reduced. b ³ is an integer of 0 to 4; But is preferably 1 or 2 in view of compatibility between solubility in solvents and low linear expansion properties. From the viewpoint of low linear expansion property, it is most preferable that R ⁸ is bonded to the ortho position with respect to the polymer main chain.

From the viewpoint of compatibility between the solubility in solvent and low linear expansion property in the general formula (4), it is preferable that the benzene ring is connected by a meta bond. Specific examples include those having the structures shown below, but are not limited thereto.

From the viewpoint of both compatibility with the solvent and low linear expansion property, it is preferable that R ¹ and R ⁴ each independently represent a structure represented by the general formula (4) in an amount of 10 to 40 mol%, more preferably 25 To 35 mol%.

The diamine residue may contain a diamine residue other than the structures represented by the general formulas (3) and (4). Examples of the amine component imparting such a diamine residue include a carboxyl group-containing diamine such as 3,5-diaminobenzoic acid and 3-carboxy-4,4'-diaminodiphenyl ether, a 3-sulfonic acid- Containing diamine such as phenyl ether, diethoxyphenylenediamine, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenylmethane, 4 , 4'-diaminodiphenylmethane, 3,4'-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfone, 3,4'-diaminodiphenylsulfide, 4,4'-dia (4-aminophenoxy) benzene, 1,5-naphthalene diamine, 2,6-naphthalene diamine, bis (4-aminophenoxyphenyl) sulfone, bis Bis (4-aminophenoxy) benzene or an aromatic ring thereof, or an aromatic ring thereof, A part of the hydrogen atoms may be substituted with an alkyl group or a halogen atom And the like, or a compound, cyclohexyl diamine, an aliphatic diamine such as methylene-bis-cyclohexyl amine, but not limited to these.

As a raw material for imparting these diamine residues, a diisocyanate compound having an isocyanate group bonded to the structure of the diamine residue instead of the amino group or a tetra-trimethylsilylated diamine in which two hydrogen atoms of the diamine amino group are substituted with trimethylsilyl groups may be used.

In the case of a resin containing a structural unit represented by the general formula (2) as a main component, a diisocyanate compound is preferably used because it is free from water as a by-product.

In the general formulas (1) and (2), R ² and R ⁵ represent a tri- or tetra-carboxylic acid residue (hereinafter referred to as "acid residue").

Examples of preferred tricarboxylic acids to which acid residues are imparted include trimellitic acid, trimesic acid, diphenyl ether tricarboxylic acid, and biphenyl tricarboxylic acid.

Examples of preferred tetracarboxylic acids for imparting acid residues include pyromellitic acid, 3,3 ', 4,4'-biphenyltetracarboxylic acid, 2,3,3', 4'-biphenyltetracarboxylic acid Acid, 2,2 ', 3,3'-biphenyltetracarboxylic acid, 3,3', 4,4'-benzophenonetetracarboxylic acid, 2,2 ', 3,3'-benzophenonetetracar (3,4-dicarboxyphenyl) hexafluoropropane, 2,2-bis (2,3-dicarboxyphenyl) hexafluoropropane, 1,1-bis Bis (2,3-dicarboxyphenyl) ethane, bis (2,3-dicarboxyphenyl) methane, bis , 4-dicarboxyphenyl) sulfone, bis (3,4-dicarboxyphenyl) ether, 1,2,5,6-naphthalenetetracarboxylic acid, 2,3,6,7-naphthalenetetracarboxylic acid, 2 , 3,5,6-pyridine tetracarboxylic acid, and 3,4,9,10-perylene tetracarboxylic acid; aromatic tetracarboxylic acids such as cyclobutanetetracarboxylic acid, 1,2,3,4 -city Cyclohexanetetracarboxylic acid, bicyclo [2.2.1.] Heptane tetracarboxylic acid, bicyclo [3.3.1.] Tetracarboxylic acid, bicyclo [3.1.1.] Hepto 2-ene tricarboxylic acid, bicyclo [2.2.2.] Octane tetracarboxylic acid, and adamantanetetracarboxylic acid. These acids may be used alone or in combination of two or more.

From the viewpoint of the low linear expansion property of the resin, it is preferable that R ² and R ⁵ each independently be a structure in which at least 65 mol% thereof is selected from at least one of the general formulas (5) and (6).

In the general formulas (5) and (6), R ⁹ and R ¹⁰ each independently represent a halogen atom or a monovalent organic group having 1 to 3 carbon atoms. Preferably a fluorine atom, an alkyl group or a fluoroalkyl group having 1 to 3 carbon atoms, more preferably an alkyl group or a fluoroalkyl group having 1 to 3 carbon atoms in that the coefficient of linear expansion of the resin can be reduced. and b ⁴ and b ⁵ are an integer of 0 to 4. And is preferably 0 in terms of low linear expansion. Specific examples include those having the structures shown below, but are not limited thereto.

The resin of the present invention preferably further contains 5 to 30 mol% of the structural unit represented by the following general formula (7) in order to obtain high strength and high elasticity.

In the general formula (7), R ¹¹ represents a diamine residue and represents a divalent organic group having 2 to 50 carbon atoms. Examples of the amine component that imparts the diamine residue 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 Dihydroxyphenylenediamine, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 4,4'- Diaminodiphenylmethane, 4'-diaminodiphenylmethane, 3,4'-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfone, 3,4'-diaminodiphenylsulfide, 4,4'-diamino (4-aminophenoxy) benzene, m-phenylenediamine, p-phenylenediamine, 1,5-naphthalenediamine, 2,6-naphthalenediamine, bis (4-aminophenoxy) phenyl} sulfone, bis (3-aminophenoxy) sulfone, bis -Aminophenoxy) benzene, 2,2'-dimethyl-4,4'-diaminobiphenyl, 2,2'-diethyl-4,4'- Diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 3,3'-diethyl-4,4'-diaminobiphenyl, 2,2 ', 3,3'- Tetramethyl-4,4'-diaminobiphenyl, 3,3 ', 4,4'-tetramethyl-4,4'-diaminobiphenyl, 2,2'-di (trifluoromethyl) -4 , 4'-diaminobiphenyl, or compounds obtained by substituting a part of the hydrogen atoms of these aromatic rings with an alkyl group or a halogen atom, a structure represented by the general formula (3) or (4), a cyclohexyldiamine, a methylenebiscyclohexylamine , And the like, but are not limited thereto.

These diamines may be used as such or as a corresponding diisocyanate compound or trimethylsilylated diamine. A diisocyanate compound is preferably used in that no water is produced as a by-product.

Each R ¹² independently represents a halogen atom or a monovalent organic group having 1 to 3 carbon atoms. Preferably a fluorine atom, an alkyl group or a fluoroalkyl group having 1 to 3 carbon atoms, more preferably an alkyl group or a fluoroalkyl group having 1 to 3 carbon atoms in that the coefficient of linear expansion of the resin can be reduced. and b ⁶ is an integer of 0 to 4. And is preferably 0 in terms of low linear expansion.

From the viewpoint of the low linear expansion characteristic of the general formula (7), the benzene ring is preferably connected to a para bond.

In the general formulas (1), (2) and (7), it is preferable to increase the resistance to oxygen plasma and UV ozone treatment used for improving the adhesiveness of the coating film after heat treatment with the silicone- , A siloxane structure may be copolymerized with R ¹ , R ⁴ , R ¹¹ , R ² and R ⁵ within a range not lowering the heat resistance. Specific examples of R ¹ , R ⁴ and R ¹¹ include residues such as bis (3-aminopropyl) tetramethyldisiloxane and bis (p-amino-phenyl) octamethylheptasiloxane. They are preferably copolymerized with 1 to 10 mol% of all of R ¹ , R ⁴ and R ¹¹ . Specific examples of R ² and R ⁵ include dimethylsilyldiphthalic dianhydride, 1,3-bis (phthalic acid) tetramethyldisiloxane dianhydride, 1- (p-carboxyphenyl) 3-phthalic acid- And residues such as tetramethyldisiloxane. These may be used singly or in combination of two or more, preferably 1 to 10 mol% of all R ² and R ⁵ .

R ¹ , R ⁴ , and R ¹¹ are bonded to the poly (alkylene oxide) of the poly (alkylene oxide) of the general formula (1), (2), and (7) An aliphatic structure having an alkylene oxide group may be copolymerized. As a specific structure, there may be mentioned "JEMPAMIN" (registered trademark) KH-511, JEMFAMINE ED-600, JEMPAMINE ED-900, JEMPAMINE ED- 200, Jeffamine D-400, Jeffamine D-2000 and Jeffamine D-4000 (trade names, manufactured by HUNTSMAN). These may be used singly or in combination of two or more, preferably 1 to 30 mol% of all of R ¹ , R ⁴ and R ¹¹ .

These resins are synthesized by the methods exemplified below, but are not limited thereto. Namely, in the case of the polyamic acid represented by the general formula (1), the diamine is reacted with N-methylpyrrolidone (NMP), N, N-dimethylformamide (DMF), N, N-dimethylacetamide (DMAC) Is dissolved in a solvent such as gamma-butyrolactone (GBL) or dimethylsulfoxide (DMSO), and then a tetracarboxylic acid dianhydride is added to react. The reaction temperature is generally -20 ° C to 100 ° C, and preferably 0 ° C to 50 ° C. The reaction time is generally 1 minute to 100 hours, preferably 2 hours to 24 hours. During the reaction, it is preferable to flow nitrogen to prevent moisture from entering the system.

In the case of the polyamic acid ester represented by the general formula (1), the tetracarboxylic acid dianhydride is mixed with an alcohol such as ethanol, propanol, and butanol and a base catalyst such as pyridine or triethylamine, For about 10 minutes to 10 hours to obtain a dicarboxylic acid diester compound. Alternatively, the tetracarboxylic dianhydride may be directly dispersed in the alcohol, or the tetracarboxylic dianhydride may be dissolved in a solvent such as NMP, DMAC, DMF, DMSO, GBL, or the like to effect the action of an alcohol and a base catalyst. The resulting dicarboxylic acid diester is subjected to a heat treatment in thionyl chloride or to act on oxalodichloride to obtain a dicarboxylic acid chloride diester. The obtained dicarboxylic acid chloride diester is recovered by a method such as distillation and is dropwise added to a solution in which diamine is dissolved in a solvent such as NMP, DMAC, DMF, DMSO or GBL in the presence of pyridine or triethylamine. Is preferably carried out at -20 캜 to 30 캜. After completion of the dropwise addition, the reaction is carried out at -20 캜 to 50 캜 for 1 hour to 100 hours to obtain a polyamic acid ester. In addition, when a dicarboxylic acid dichloride diester is used, a hydrochloride salt is produced as a by-product. Therefore, instead of heating the dicarboxylic acid diester in thionyl chloride or using oxalodichloride, dicyclohexylcarbodi It is preferable to react with a diamine by a condensing reagent for a peptide such as a peptide or a peptide. The polyamic acid ester can also be obtained by reacting the above-described polyamic acid with an acetal compound such as dimethylformamide dialkyl acetal. The esterification rate can be adjusted by the amount of the acetal compound added.

In the case of the polyimide represented by the general formula (2), the polyimide precursor can be obtained by subjecting the polyimide precursor to heat treatment or chemically treating the imide ring. Examples of the chemical treatment include treatment with acetic anhydride and pyridine, base treatment such as triethylamine and dodecyl undecene, and acid anhydride treatment with acetic anhydride and succinic anhydride.

In the case of the polyamideimide represented by the general formula (2), a method of dissolving the diamine in a solvent such as NMP, DMF, DMAC, GBL or DMSO and adding a tricarboxylic acid is generally used. The reaction temperature is generally -20 ° C to 100 ° C, and preferably 0 ° C to 50 ° C. The reaction time is generally from 1 minute to 100 hours, and therefore, it is preferably from 2 hours to 24 hours. During the reaction, it is preferable to flow nitrogen to prevent moisture from entering the system. As a general reaction, there is a method in which a diamine solution is reacted with tricarboxylic acid chloride, and then heat treatment at 100 ° C to 300 ° C is performed for 1 minute to 24 hours to obtain a polyamideimide. In this case, for the imidization, an acid anhydride such as acetic anhydride or a base such as triethylamine, pyridine, or picoline may be added as a catalyst in an amount of 0.1 to 10 wt% based on the amount of the polymer to accelerate the reaction. The diamine and trimellitic anhydride chloride are polymerized with a polyamide acid amide in the presence of pyridine, triethylamine, etc., and the polymer is taken out as a solid. Thereafter, the solid is heated at a temperature of 100 to 300 DEG C for 1 minute For 24 hours to obtain a polyamideimide.

In the case of the polyimide or polyamideimide represented by the general formula (2), the amino group of the diamine compound may be replaced by an acid having a valence of 2 or more such as tetracarboxylic acid dianhydride or tricarboxylic acid anhydride instead of isocyanate, In the presence of a catalyst or a base catalyst at a temperature ranging from room temperature to 200 ° C for 1 minute to 24 hours. This method is more preferable in that there is no by-produced water.

The molar ratio of the acid component to the diamine or diisocyanate in the polymerization reaction of these resins is 100 mol% or less, preferably 95 mol% or less, more preferably 90 mol% or less, based on 100 mol% of diamine or diisocyanate , And most preferably 85 mol% or less. When the amount of the diamine or the diisocyanate is larger, there is an effect that the terminal amine and the isocyanate group increase the adhesion between the resin and the filler, the conductive base and the conductive wiring.

After completion of the polymerization, the resin used in the present invention may be obtained by precipitating in a poor solvent for a resin such as methanol or water, followed by washing and drying. By repeating, the esterification agent used in the polymerization, the condensation agent, by-products of the acid chloride, and the low-molecular-weight component of the resin precursor can be removed, thereby improving the heat resistance.

The resin of the present invention preferably has a structure in which the terminal of the resin is represented by the following general formula (8).

In the 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.

When these terminal structures are included, the protecting group is eliminated during the heat treatment, and the isocyanate group is regenerated. This functional group and the amino group generated by hydrolysis of the functional group have the effect of enhancing the adhesion between the resin and the filler, the conductive base, and the conductive wiring.

In the resin having the terminal sealing agent, in the various known synthesis methods, when a reaction is carried out by selectively combining a diamine, a diisocyanate and an acid component, the resin is first reacted with a diamine, a diisocyanate or an acid, Or may be obtained by adding the end sealant at the same time as or after the diamine, the diisocyanate, and the acid.

The resin containing at least one of the structures represented by the general formulas (1) and (2) can be used as a resin solution dissolved in a solvent.

Specific examples of the solvent preferably used in the resin solution of the present invention include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether , Ethers such as ethylene glycol dibutyl ether, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, and diethylene glycol methyl ethyl ether, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propyl acetate, butyl acetate , Acetates such as isobutyl acetate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, methyl lactate, ethyl lactate and butyl lactate, acetyl acetone, methyl propyl ketone, methyl butyl ketone, methyl isobutyl Ketone, cyclopentanone, 2-heptanone, etc. Ketones, alcohols such as butyl alcohol, isobutyl alcohol, pentanol, 4-methyl-2-pentanol, 3-methyl-2-butanol, 3- N-dimethylformamide, N, N-dimethylacetamide, dimethylsulfoxide,? -Butyrolactone, and the like; aromatic hydrocarbons such as N-methyl-2-pyrrolidone, And lactones. These may be used alone or in combination.

The concentration and the viscosity of the resin solution are in the range of 1 to 50 wt% and the viscosity is preferably in the range of 1 mPa · sec to 1000 Pa · sec, more preferably 5 to 30 wt%, and the viscosity is 100 mPa · sec to 100 Pa · sec. With this range, it is possible to form a uniform film having no unevenness.

It is preferable that the resin solution of the present invention further comprises c) a silane compound represented by the following general formula (9).

In the general formula (9), R ¹⁷ represents an alkoxyl group having 1 to 4 carbon atoms. R ¹⁸ represents an alkoxyl group or an alkyl group having 1 to 4 carbon atoms; 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, ethoxy, propoxy, isopropoxy, butoxy and the like. Specific examples of preferred alkyl groups include, but are not limited to, methyl, ethyl, propyl, isopropyl, butyl and the like. Z represents a functional group reactive with an isocyanate group. Specific preferred examples include, but are not limited to, a hydroxyl group, an amino group, an epoxy group, an acryl group, a methacryl group, a maleimide group, a thiol group, a carboxyl group, an acid anhydride group and an isocyanate group.

Examples of particularly preferred compounds include, but are not limited to, those exemplified below.

Aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropylmethyldiethoxysilane, 3-aminopropyldimethylethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropyldiphenyldimethoxysilane, 3-aminopropylphenyldimethoxysilane, 3-hydroxypropyltriethoxysilane, 3-hydroxypropylmethyldiethoxysilane, 3-hydroxypropyldimethylethoxy Silane, 3-hydroxypropyltrimethoxysilane, 3-hydroxypropylmethyldimethoxysilane, 3-hydroxypropyldimethylmethoxysilane, 3-hydroxypropylphenyldiethoxysilane, 3-hydroxypropylphenyldimethoxy Silane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldiethoxysilane, 3-mercaptopropyldimethylethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxy Silane, 3-mercaptopropyldimeth 3-acryloxypropyltriethoxysilane, 3-acryloxypropylmethyldiethoxysilane, 3-acryloxypropyldimethylsilane, 3-mercaptopropyldimethoxysilane, 3-acryloxypropyltrimethoxysilane, Acryloxypropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropylmethyldimethoxysilane, 3-acryloxypropyldimethylmethoxysilane, 3-acryloxypropylphenyldiethoxysilane, 3-acryloxypropylphenyl 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyldimethylethoxysilane, 3- Methacryloxypropyldimethoxysilane, 3-methacryloxypropyldimethyloxymethoxysilane, 3-methacryloxypropylphenyldiethoxysilane, 3-methacryloxypropylphenyldimethoxysilane, N-phenylaminoethyltrimethoxy Silane, N-phenylaminoethyltriethoxysilane, N-phenylaminopropyltrimethoxysilane, N-phenylaminopropyltriethoxysilane, N-phenylaminobutyltrimethoxysilane, N-phenylaminobutyltriethoxysilane, etc. But are not limited to these.

The content of these silane compounds is preferably 0.01 to 15 parts by weight based on 100 parts by weight of the resin.

When these silane compounds are included, there is an advantage that adhesion of silicon, titanium, and zirconium is improved, and they can be suitably used as a binder for a negative electrode containing silicon and titanium. Particularly, when a resin is synthesized due to the reaction of a diisocyanate and a dihydric or higher acid reacting with the diisocyanate, the polymer reacts with the isocyanate present at the end of the polymer to form a polymer having a bonding modifying component bonded to its end, There is an advantage that it is increased.

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 may impart a positive photosensitivity. The photoacid generator may be a quinone diazide compound, a sulfonium salt compound, a phosphonium salt compound, a diazonium salt compound, or an iodonium salt compound, but it is preferably a quinone diazide compound, particularly an o-quinone diazide compound . As the quinone diazide compound, there may be mentioned a compound in which a sulfonic acid of quinone diazide is bonded to a polyhydroxy compound with an ester, a compound in which a sulfonic acid of quinone diazide is sulfonamide bonded to a polyamino compound, a sulfonic acid of quinone diazide in the polyhydroxypolyamino compound Ester bond and / or sulfonamide bond. Although not all the functional groups of the polyhydroxy compound and the polyamino compound may be substituted with quinone diazide, it is preferable that at least 50 mol% of the entire functional groups are substituted with quinone diazide. By substituting quinonediazide by not less than 50 mol%, the solubility in an alkali developing solution becomes good, and a fine pattern with high contrast with the unexposed portion can be obtained. By using such a quinone diazide compound, it is possible to obtain a resin composition having positive photosensitivity that is sensitive to i-line (365 nm), h-line (405 nm), and g-line (436 nm) of a general ultraviolet ray.

Bisp-PZ, BisP-IPZ, BisP-PZ, BisP-PZ, BisP-PZ, BisP-ZZ, BisP- DML-OCHP, DML-PCHP, DML-PCC, BisRSCP-IPZ, BisP-CP, BisRS-2P, BisRS-3P, BisP-OCHP, methylene tris- PML, TML-P PML, DML-PFP, DML-PSBP, DML-MTrisPC, TriML-P, TriML-35XL, TML-B PML, DML-PTBP, DML-34X, DML-EP, DML- OC, BIP-PC, BIR-PC (trade name, manufactured by Honshu Kagaku Kogyo K.K.), HML-TP-BP, TML-BP- , BIR-PTBP, BIR-PCHP, BIP-BIOC-F, 4PC, BIR-BIPC-F, TEP-BIP-A, 46DMOC, 46DMOEP, TM-BIP-A (trade name, manufactured by Asahi Yuki- 4-t-butylphenol, 2,6-dimethoxymethyl-p-cresol, 2,6-diacetoxymethyl-p-cresol, naphthol, tetrahydroxybenzophenone Bisphenol A, bisphenol E, methylene bisphenol, BisP-AP (trade name, manufactured by Honshu Kagaku Kogyo Co., Ltd.), and the like , But it is not limited to these.

Examples of the polyamino compound include 1,4-phenylenediamine, 1,3-phenylenediamine, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 4,4'-diamino Diphenyl sulfone, 4,4'-diaminodiphenyl sulfide, and the like, but are not limited thereto.

Examples of the polyhydroxypolyamino compound include, but are not limited to, 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane and 3,3'-dihydroxybenzidine. Do not.

In the present invention, quinone diazide is preferably a 5-naphthoquinone diazide sulfonyl group or a 4-naphthoquinone diazide sulfonyl group. The 4-naphthoquinone diazidesulfonyl ester compound has absorption in the i-line region of a mercury lamp and is suitable for i-line exposure. The 5-naphthoquinone diazidesulfonyl ester compound has absorption up to the g line region of a mercury lamp and is suitable for g-line exposure. In the present invention, it is preferable to select a 4-naphthoquinone diazide sulfonyl ester compound and a 5-naphthoquinone diazide sulfonyl ester compound depending on the wavelength to be exposed. Further, a naphthoquinone diazide sulfonyl ester compound in which a 4-naphthoquinonediazide sulfonyl group and a 5-naphthoquinone diazide sulfonyl group are used in the same molecule may be obtained, or 4-naphthoquinone diazide sulfonic acid ester A sulfonyl ester compound and a 5-naphthoquinone diazide sulfonyl ester compound may be used in combination.

The molecular weight of the quinone diazide compound is preferably 300 or more, more preferably 350 or more. Further, it is preferably 1500 or less, more preferably 1200 or less. When the molecular weight is 300 or more, the exposure sensitivity is high. When the molecular weight is 1500 or less, there is an advantage that the coating mechanical properties 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, based on 100 parts by weight of the resin as a whole. The amount is preferably 50 parts by weight or less, more preferably 40 parts by weight or less. The content of the quinone diazide compound is preferably at least 1 part by weight, more preferably at least 3 parts by weight based on 100 parts by weight of the resin. The amount is preferably 50 parts by weight or less, more preferably 40 parts by weight or less. Within this range, there is an advantage that the mechanical properties of the cured film become good.

The quinone diazide compound used in the present invention is synthesized from a specific phenol compound by the following method. For example, a method of reacting 5-naphthoquinone diazide sulfonyl chloride with a phenol compound in the presence of triethylamine. A method for synthesizing a phenol compound includes a method of reacting an? - (hydroxyphenyl) styrene derivative with a polyhydric phenol compound under an acid catalyst.

As the sulfonium salt compound, phosphonium salt compound and diazonium salt compound in the photoacid generator, since the film after the heat treatment obtained from the photosensitive resin composition of the present invention is used as a permanent film, it is not environmentally preferable that phosphorus, etc. remain, Among these, a sulfonium salt is preferably used because it is also necessary to consider the color tone of the film. Particularly preferred are triarylsulfonium salts.

In addition, the resin composition of the present invention may contain, as R ³ in the general formula (1), an ethyl methacrylate group, an ethyl acrylate group, a propyl methacrylate group, a propyl acrylate group, an ethyl methacrylamide group , A group having an ethylenically unsaturated double bond such as a propyl methacrylamide group, an ethyl acrylamide group and a propyl acrylamide group. In order to increase the photosensitive performance of the resin composition, a photopolymerizable compound may be included. Examples of the photopolymerizable compound include 2-hydroxyethyl methacrylate, trimethylolpropane trimethacrylate, trimethylolpropane triacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate Propylene glycol dimethacrylate, methylenebismethacrylamide, methylenebisacrylamide, and the like, but are not limited thereto. The photopolymerizable compound is preferably contained in an amount of 1 to 30 parts by weight based on 100 parts by weight of the resin. Within this range, a composition having high sensitivity and good film-forming properties after heat curing can be obtained. These photopolymerizable compounds may be used alone or in combination of two or more.

When a negative type photosensitive property is imparted to the resin composition of the present invention, a photopolymerization initiator may be contained. Examples of 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, cyclic oxime compounds represented by 3-phenyl-5-isoxazolone, 1- Chain oxime compounds represented by phenylpropanedione-2- (o-ethoxycarbonyl) oxime, benzophenone, benzophenone derivatives such as methyl o-benzoylbenzoate, dibenzyl ketone and fluorenone, thioxanthone, 2- Thioxanthone derivatives such as thioxanthone and 2-isopropylthioxanthone, and the like, but the present invention is not limited thereto.

The content of the photopolymerization initiator is preferably 0.01 parts by weight or more, more preferably 0.1 parts by weight or more, based on 100 parts by weight of the resin. The content is preferably 30 parts by weight or less, more preferably 20 parts by weight or less. Within this range, the composition is high in sensitivity and good in film mechanical properties after heat curing. These photoinitiators may be used alone or in combination of two or more.

Further, it is more preferable to include a photosensitizer in order to improve the negative type photosensitive characteristics. Examples of the photosensitizer suitable for the present invention include aromatic monoazides such as azide anthraquinone and azidobenzalacetophenone, 7-diethylaminobenzoyl coumarin, 3,3'-carbonylbis (diethylaminocoumarin) And aromatic ketones such as aminocoumarins, benzanthrone, phenanthrenequinone, and the like, which are generally used for photocurable resins. And may be preferably used if it is used as a charge transfer agent for other electrophotographic photosensitive members.

The content of the photosensitizer is preferably 0.01 parts by weight, more preferably 0.1 parts by weight or more, based on 100 parts by weight of the resin. The content is preferably 30 parts by weight or less, more preferably 20 parts by weight or less. Within this range, the composition becomes a composition having high sensitivity and good film-forming properties after the heat treatment. These photosensitizers may be used alone or in combination of two or more.

The resin composition of the present invention may contain a compound having a phenolic hydroxyl group for the purpose of controlling the alkali developability of the resin film formed of 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, BisOP-Z, BisP-CP, Bis26X-Z, BisOTBP-Z, BisOCHP- BisP-CP, BisP-PZ, BisP-IPZ, BisCR-IPZ, BisOCP-IPZ, BisOIPP-CP, Bis26X-IPZ, BisOTBP-CP, TekP-4HBPA (tetrakis P- BisPC-OCHP, Bis26-OCHP, BisOCHP-OC, Bis236T-OCHP, BisPC-OCHP, BisPC-OCHP, BisPC- BIR-PC, BIR-PCB, BIR-PCHP, BIP-PCB, and BIS-OCHP (all trade names, manufactured by Honshu Chemical Industries, Ltd.) -BIOC-F, 4PC, BIR-BIPC-F, and TEP-BIP-A (all trade names, manufactured by Asahi Yuki Kai Kogyo Co., Ltd.).

Among these, preferred compounds having a phenolic hydroxyl group include bis-Z, BisP-EZ, TekP-4HBPA, TrisP-HAP, TrisP-PA, BisOCHP-Z, BisP-MZ, BisP- BIP-PC, BIR-PC, BIR-PTBP, BIR-BIPC-F, and the like, as well as bisCOP-IPZ, BisP-CP, BisRS-2P, BisRS-3P, BisP-OCHP, methylene tris- . Among these compounds, particularly preferred compounds having a phenolic hydroxyl group are Bis-Z, TekP-4HBPA, TrisP-HAP, TrisP-PA, BisRS- -F. By containing the compound having a phenolic hydroxyl group, the resulting resin composition is easily dissolved in an alkaline developer before exposure, becomes unstable in an alkaline developer when exposed, has less film loss due to development, and is easy to develop in a short time It becomes.

The content of the compound having a phenolic hydroxyl group is preferably from 1 to 60 parts by weight, more preferably from 3 to 50 parts by weight, based on 100 parts by weight of the resin.

The resin composition of the present invention can be applied to a silicon substrate such as silicon, silicon nitride, silicon oxide and phosphoric silicate glass of a film after heat treatment, oxygen plasma used for cleaning or the like, adhesion to an ITO substrate, 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 may be contained in order to enhance the resistance to heat. Specific examples of preferred silane coupling agents include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrichlorosilane, vinyltris (? -Methoxyethoxy) silane, and the like.

The content of the adhesion improver is preferably 0.01 to 15 parts by weight based on 100 parts by weight of the resin.

It is also possible to further improve the adhesiveness by pretreating the surface of the substrate to which the resin composition is applied in advance. As a method of the pretreatment, for example, the following method can be mentioned. A solution prepared by dissolving 0.5 to 20 parts by weight of the above-described improving agent in a solvent such as isopropanol, ethanol, methanol, water, tetrahydrofuran, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate or diethyl adipate Is subjected to surface treatment by spin coating, dipping, spray application, steam treatment, or the like. Further, the hexamethyldisilazane vapor may be directly spray-treated. Thereafter, a vacuum drying treatment is carried out if necessary, and a temperature of 50 to 300 ° C is applied to advance the reaction between the surface of the silicon-based material and the above-mentioned adhesion improver.

The resin composition of the present invention may contain a surfactant, which can improve the wettability with the substrate.

Examples of the surfactant include fluoride (registered trademark) (trade name, manufactured by Sumitomo 3M Ltd.), megaface (registered trademark) (trade name, manufactured by DIC Corporation), sulfulfone (registered trademark) Fluorine surfactants such as KP341 (trade name, manufactured by Shin-Etsu Chemical Industry Co., Ltd.), DBE (trade name, manufactured by Chisso Co., Ltd.) (Trade name, produced by Kyoeisha Chemical Co., Ltd.) and BYK (manufactured by Big Chemie Co., Ltd.), and organic siloxane surfactants such as "Polyflow" And the like), and the like.

A filler may be added to the resin solution of the present invention and used as a slurry. When used in semiconductors, displays, and multilayer wiring boards, the addition of a filler makes it possible to achieve further lower linear expansion and higher strength, control of refractive index, permittivity and permeability. When used in a secondary battery or a capacitor, functionalization as a positive electrode and a negative electrode becomes possible.

Silicon oxide, titanium oxide, alumina, barium titanate, aluminum nitride, zirconium oxide, silicon nitride, titanium nitride, and the like are preferable fillers for use in semiconductors, displays, and multilayer wiring boards, but the present invention is not limited thereto.

Preferred fillers for use in secondary batteries and capacitors are those containing atoms such as carbon, silicon, tin, germanium, titanium, iron, cobalt, nickel, manganese, copper, silver, zinc, indium, bismuth, antimony or chromium Compounds. Preferably, a compound containing at least one atom of carbon, manganese, cobalt, nickel, iron, silicon, titanium, tin and germanium, more preferably a compound containing at least one atom of silicon and titanium to be.

When these compounds are used as a filler, the filler serves as an active material. As a result, the slurry can be used as a slurry for an electrode of a secondary battery or a capacitor by adding a filler to the resin of the present invention.

Examples of the positive electrode filler include lithium iron phosphate, lithium cobalt oxide, lithium nickel oxide, lithium manganese oxide, activated carbon, and carbon nanotubes.

Examples of the negative electrode filler include lithium titanate, hard carbon, soft carbon, activated carbon, carbon nanotubes, silicon, tin, and compounds containing germanium atoms. Particularly, a battery using a compound containing silicon, tin, and germanium atoms as a filler has a large volume expansion of the active material at the time of charging. Therefore, when a resin having high mechanical strength such as the resin of the present invention is used as a binder, And further, it is preferable to reduce the capacity deterioration at the time of charge / discharge.

Examples of the compound containing silicon atom include (1) silicon fine particles, (2) tin, nickel, copper, iron, cobalt, manganese, zinc, indium, silver, titanium, germanium, bismuth, antimony or chromium, (3) a compound of boron, nitrogen, oxygen, or carbon and silicon, and a metal further having a metal exemplified in (2). As an example of the alloy or compound of silicon, 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), or LiSiO.

Examples of the compound containing a tin atom include (1) an alloy of tin with silicon, nickel, copper, iron, cobalt, manganese, zinc, indium, silver, titanium, germanium, bismuth, antimony or chromium, ) Oxygen or a compound of carbon and tin, and those having a metal further exemplified in (1). Examples of alloys or compounds of tin 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 and tin and germanium.

The median diameter d50 in the particle size distribution of the filler is preferably 0.01 to 20 mu m. The surface of the filler may be treated with a silane coupling agent or the like.

Here, the median diameter was measured using a laser diffraction / scattering type particle size distribution measuring apparatus LA-920 manufactured by Horiba Seisakusho Co., Ltd. Before measurement, an appropriate amount of a sample was added to an aqueous solution of sodium hexametaphosphate and dispersed by an ultrasonic cleaner for about 10 minutes, and then measurement was carried out. As a result, in the sample in which the powder is agglomerated, the agglomeration is released and the precipitation of the powder having a large particle size is suppressed, and the accurate particle size distribution can be measured.

In the slurry of the present invention, the content of the resin (resin + additive in the case where the additive is added) is preferably 1 part by weight or more based on 100 parts by weight of the filler, and the adhesion can be further improved. More preferably 3 parts by weight or more, and still more preferably 5 parts by weight or more.

When it is used for an 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 electric resistance and increase the filling amount of the filler.

When used for an electrode of a secondary battery or a capacitor, conductive particles such as graphite, ketjen black, carbon nanotube, and acetylene black may be contained in the negative electrode paste of the present invention in order to lower the electrical resistance. The content thereof is preferably 0.1 parts by weight or more and 20 parts by weight or less based on 100 parts by weight of the negative electrode active material.

The resin solution, the resin composition and the slurry of the present invention can be obtained by mixing and kneading a resin, a solvent and other additives as required. Examples of the mixing method include a method of dissolving in a glass flask or a container made of stainless steel by means of a mechanical stirrer or the like, a method of dissolving by ultrasonic waves, a method of dissolving with stirring by a planetary stirring defoaming device, A rotary mixer, a three-axis roll, a ball mill, a homogenizer, and the like. The conditions of mixing and kneading are not particularly limited.

Further, the resin solution, the resin composition, and the slurry after mixing and kneading may be filtered with a pore size filter of 0.01 mu m to 100 mu m in order to remove foreign matter. Examples of the material of the filter include polypropylene (PP), polyethylene (PE), nylon (NY), and polytetrafluoroethylene (PTFE). Polyethylene and nylon are preferred. When the resin composition contains a filler or an organic pigment, it is preferable to use a filter having a pore diameter larger than the particle diameter.

A resin solution, a resin composition or a slurry of the present invention may be applied to one side or both sides of a substrate and dried to form a laminate.

As the substrate, a conductive substrate or an insulating substrate having a conductive wiring is used. Preferred examples of the conductive substrate and the wiring include copper, aluminum, stainless steel, nickel, gold, silver and alloys thereof, carbon, and the like, but are not limited thereto. Particularly, copper, aluminum, gold, nickel and alloys including them are more preferable. Examples of the insulating substrate include organic substrates such as PET, polyimide, polybenzoxazole, polyamide, polyamideimide and epoxy, silicon oxide, silicon nitride, titanium nitride, titanium oxide and a substrate formed on a coating surface thereof. .

The method for producing a laminate of the present invention will be described.

First, the resin solution, the resin composition or the slurry of the present invention is applied onto the substrate.

As a coating method, there can be mentioned a method using a roll coater, a slit die coater, a bar coater, a comma coater, a spin coater and the like. The thickness of the coating film is preferably from 0.1 to 150 mu m after drying, though it differs depending on the coating method, solid concentration of the composition, viscosity, and the like.

Next, the coated substrate is dried to obtain a resin composition film. The drying is preferably carried out in an oven, a hot plate, an infrared ray or the like at a temperature of 50 to 200 DEG C for 1 minute to several hours.

When the resin solution, the resin composition, or the slurry is photosensitive, the coating film is exposed to actinic rays through a mask having a desired pattern and exposed. Examples of the actinic rays used for exposure include ultraviolet rays, visible rays, electron beams, and X-rays. In the present invention, light having a wavelength of 350 nm or more and 450 nm or less is preferable, and an i-line (wavelength 365 nm) 405 nm) and g-line (wavelength: 436 nm) are preferably used.

When a resin solution, a resin composition or a slurry which is not photosensitive is exposed, it is necessary to further form one photoresist film on the resin film. As the photoresist, a typical novolac-based resist such as OFPR-800 (manufactured by Tokyo Ohka Kogyo Co., Ltd.) is preferably used. The formation of the photoresist coating is carried out in the same manner as the formation of the resin composition coating.

In the case where the resolution of the pattern at the time of development is improved and the allowable width of the developing condition is increased, the step of baking before development may be introduced. The temperature is preferably in the range of 50 to 180 占 폚, more preferably in the range of 60 to 150 占 폚. The time is preferably 10 seconds to several hours. Within this range, the reaction proceeds well and the development time can be shortened.

In order to form a pattern of the resin solution, the resin composition or the slurry, development processing is performed. In the case where the resin solution, the resin composition or the slurry has a negative type photosensitive property, the unexposed portion is removed with a developer, and in the case of having a positive type photosensitive, the relief pattern is obtained by removing the exposed portion with a developer.

The developing solution may be selected appropriately in accordance with the structure of the resin, but it is preferable to use an aqueous solution of ammonia, tetramethylammonium hydroxide, diethanolamine, diethylaminoethanol, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, triethylamine, An aqueous solution of an alkaline compound such as methylamine, dimethylamine, dimethylaminoethyl acetate, dimethylaminoethanol, dimethylaminoethyl methacrylate, cyclohexylamine, ethylenediamine, hexamethylenediamine and the like can be preferably used. In some cases, these alkaline aqueous solutions may be mixed with an aqueous solution of an alkali such as N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethylsulfoxide, Polar solvents, alcohols such as methanol, ethanol and isopropanol, esters such as ethyl lactate and propylene glycol monomethyl ether acetate, ketones such as cyclopentanone, cyclohexanone, isobutyl ketone and methyl isobutyl ketone, Or more.

Further, as a developing solution, there may be used a solution prepared by dissolving N-methyl-2-pyrrolidone, N-acetyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethylsulfoxide, Hexamethylphosphoric triamide, and hexamethylphosphoric triamide; or a poor solvent of resins such as methanol, ethanol, isopropyl alcohol, water, methylcarbitol, ethylcarbitol, toluene, xylene, ethyl lactate, ethyl pyruvate, propylene glycol monomethyl ether acetate, methyl 3-methoxypropionate, ethyl-3-ethoxypropionate, 2-heptanone, cyclopentanone, cyclohexanone, and ethyl acetate alone or in combination with the above- Can be used.

The development can be carried out by a method such as irradiating the above developer directly on the coated film surface, as a misty state, immersing in a developer, or applying ultrasonic waves while dipping.

It is then preferable to clean the relief pattern formed by the development with the rinsing liquid. As the rinse liquid, when an alkali aqueous solution is used for the developer, water can be preferably used. At this time, esters such as ethanol, isopropyl alcohol, and propylene glycol monomethyl ether acetate, acid such as carbonic acid gas, hydrochloric acid, and acetic acid may be added to water and rinsed.

In case of rinsing with an organic solvent, it is preferable to use methanol, ethanol, isopropyl alcohol, ethyl lactate, ethyl pyruvate, propyleneglycol monomethyl ether acetate, methyl-3-methoxypropionate, ethyl- Ethoxypropionate, 2-heptanone, ethyl acetate and the like are preferably used.

If the resin solution, the resin composition or the slurry is not provided with photosensitivity, the photoresist film formed on the resin film after development should be removed. This removal is often performed by removal by dry etching or wet etching by a peeling solvent. Examples of the peeling solvent include organic solvents such as acetone, butyl acetate, ethyl lactate, propylene glycol monomethyl ether acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, 2-heptanone, A solvent, an aqueous solution of sodium hydroxide, potassium hydroxide, or the like is used, but is not limited thereto.

In order to further improve the heat resistance, it may be cured at a temperature of 150 ° C to 500 ° C after development. To the heat-resistant film. This heat treatment is preferably carried out by selecting the temperature, raising the temperature stepwise, or selecting the temperature range and continuously raising the temperature for 5 minutes to 5 hours. As an example, there are a method of performing heat treatment at 130 ° C, 200 ° C, and 350 ° C for 30 minutes each, and a method of linearly raising the temperature from room temperature to 320 ° C over 2 hours. In addition, since the electrical characteristics of the device may be changed by heating at high temperature or by repetition thereof, and the warpage of the substrate may increase, the heat treatment is preferably performed at 250 캜 or lower. In particular, since the resin represented by the general formula (2) already has a cyclic structure, it is not necessary to carry out dehydration cyclization at a high temperature for the heat treatment.

Next, a method of manufacturing the lithium ion battery electrode and the electric double layer capacitor electrode of the present invention will be described by way of example.

In the case of a lithium ion battery negative electrode (hereinafter sometimes referred to as negative electrode), the slurry of the present invention is applied on the metal foil to a thickness of 1 to 100 mu m. As the metal foil, copper foil is generally used. Screen printing, roll coating, slit coating, and the like can be used for coating.

When a polyimide precursor is used as the binder, the polyimide precursor is converted into polyimide by heat treatment at 100 to 500 ° C for 1 minute to 24 hours after application, thereby obtaining a reliable negative electrode. Preferably at a temperature of 200 ° C or more to 450 ° C or less for 30 minutes to 20 hours or less. Further, in order to suppress the incorporation of moisture, it is preferable to heat in an inert gas such as nitrogen gas or in a vacuum. When polyimide is used as the binder, it is preferable to remove the solvent by applying a heat treatment at 80 to 500 캜 for 1 minute to 24 hours after application. It is more preferable to carry out the treatment at 100 ° C to 250 ° C for 10 minutes to 24 hours since there is no need for imidization. In any case, it is preferable to heat in an inert gas such as nitrogen gas or in a vacuum to suppress the incorporation of moisture.

When the binder contains a low-temperature decomposition resin, the low-temperature decomposition resin is decomposed by heat treatment to obtain a negative electrode having pores therein. In this case, it is preferable to perform the heat treatment at a temperature higher than the decomposition temperature of the low-temperature decomposition resin and lower than the decomposition temperature of the binder. Such a temperature range is preferably treated at 300 캜 to 450 캜 for 30 minutes to 20 hours. Examples of such thermally decomposable resins include polyethylene glycol, polypropylene glycol, and the like.

In the case of a lithium battery positive electrode (hereinafter sometimes referred to as a positive electrode) and an electric double layer capacitor negative electrode, the slurry of the present invention is applied on the metal foil to a thickness of 1 to 500 μm. Examples of the metal foil include aluminum foil, nickel foil, titanium foil and copper foil, and aluminum foil is generally used. The application method and the heat treatment method are the same as those of the lithium battery negative electrode.

Next, a lithium ion battery and an electric double layer capacitor using the positive electrode and the negative electrode of the present invention will be described.

A secondary battery or an electric double-layer capacitor can be obtained by putting a plurality of positive electrodes and negative electrodes of the present invention, which are laminated with a separator interposed therebetween, together with an electrolyte in a casing such as a metal case and sealing them.

Examples of the separator include polyolefins such as polyethylene and polypropylene, and microporous films and nonwoven fabrics such as cellulose, polyphenylene sulfide, aramid and polyimide.

In order to increase heat resistance, the surface of the separator may be coated with ceramics or the like.

The solvent used for the electrolytic solution serves as a medium through which ions involved in the electrochemical reaction of the battery can move. Preferred examples of the solvent include a carbonate-based, ester-based, ether-based, ketone-based, alcohol-based, and aprotic solvent. Examples of the carbonate solvent include dimethyl carbonate (DMC), diethyl carbonate (DEC), dipropyl carbonate (DPC), methyl propyl carbonate (MPC), ethyl propyl carbonate ), Methyl ethyl carbonate (MEC), ethyl methyl carbonate (EMC), ethylene carbonate (EC), propylene carbonate (PC), and butylene carbonate (BC). Examples of the ester solvent include methyl acetate, ethyl acetate, n-propyl acetate, methyl propionate, ethyl propionate,? -Butyrolactone, decanol, valerolactone, mevalonolactone and caprolactone. have. Examples of the ether solvent include dibutyl ether, tetraglyme, diglyme, dimethoxyethane, 2-methyltetrahydrofuran, tetrahydrofuran and the like. Examples of the ketone-based solvent include cyclohexanone and the like. Examples of the alcohol-based solvent include ethyl alcohol, isopropyl alcohol and the like. Examples of the aprotic solvent include amides such as tolyl and 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 performance of the intended battery. For example, in the case of the above-mentioned carbonate-based solvent, it is preferable to use cyclic carbonate and chain carbonate in a volume ratio of 1: 1 to 1: 9, thereby improving the performance of the electrolytic solution.

Examples of the electrolyte used in 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.

The resin, the resin composition, the film and the laminate formed by the slurry of the present invention can be used for electronic parts such as a semiconductor package and a multilayer wiring board. Specifically, it is suitably used for a passivation film of a semiconductor, a surface protective film of a semiconductor element, an interlayer insulating film, an interlayer insulating film of a multilayer interconnection for high density mounting, an insulating layer of an organic electroluminescent element, Structure can be taken. When the resin composition contains an electrically conductive filler, it may be used as a wiring material.

Example

Hereinafter, the present invention will be described by way of examples and the like, but the present invention is not limited to these examples. The compositions in Examples were evaluated by the following methods.

1) Method of measuring film thickness of composition

Using a Lambda Ace STM-602 manufactured by Dainippon Screen Co., Ltd., the resin film and the film after heat curing were measured with a refractive index of 1.629.

2) Method of measuring the mechanical properties (strength (MPa), elastic modulus (㎬), elongation (%)) of the composition

The composition solution was spin-coated on an 8-inch silicon wafer, and then baked for 3 minutes using a 120 占 폚 hot plate (using a coating and developing apparatus Act-8 manufactured by Tokyo Electron Limited) 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 / minute using an inner oven CLH-21CD-S (manufactured by Koyo Thermo System Co., Ltd.), and heat treatment was performed at 200 ° C for 1 hour , And cooled to 50 DEG C at 5 DEG C / min. Subsequently, the film was immersed in hydrofluoric acid for 1 to 4 minutes to peel off the film from the substrate and air-dried to obtain a film after heat treatment. The number of revolutions at the time of spin coating was adjusted so that the thickness of the resin film after the heat treatment became 10 mu m.

The coating film after the heat treatment was cut into a rectangular shape having a width of 1 cm and a length of about 9 cm. The average value of the top five points was obtained from the measurement results using "Tensilon" (RTM-100; Orientech).

3) Method of measuring the thermal expansion coefficient (CTE) of the composition

The composition solution was spin-coated on an 8-inch silicon wafer, and then baked for 3 minutes using a 120 占 폚 hot plate (using a coating and developing apparatus Act-8 manufactured by Tokyo Electron Limited) 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 / minute using an inner oven CLH-21CD-S (manufactured by Koyo Thermo System Co., Ltd.), and heat treatment was performed at 200 ° C for 1 hour , And cooled to 50 DEG C at 5 DEG C / min. Subsequently, the film was immersed in hydrofluoric acid for 1 to 4 minutes to peel off the film from the substrate and air-dried to obtain a film after heat treatment. The number of revolutions at the time of spin coating was adjusted so that the thickness of the resin film after the heat treatment became 10 mu m.

The film after the heat treatment was subjected to measurement under a nitrogen stream using a thermomechanical analyzer (EXSTAR6000 TMA / SS6000, manufactured by SII Co., Ltd., Nanotechnology Co., Ltd.). The temperature rising method was performed under the following conditions. In the first step, the temperature of the sample was raised to 200 ° C at a heating rate of 5 ° C / min to remove the adsorbed water of the sample, and then cooled to room temperature at a cooling rate of 5 ° C / min in the second step. In the third step, this measurement was carried out at a heating rate of 5 캜 / min to obtain an average value of the thermal expansion coefficient at 50 캜 to 200 캜.

4) Adhesion to copper

A copper substrate formed to a thickness of 500 nm on an 8-inch silicon wafer was prepared. The composition was spin-coated on the substrate, and then baked for 3 minutes with a 120 占 폚 hot plate (using a coating and developing apparatus Act-8 manufactured by Tokyo Electron Limited) 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 / minute using an inner oven CLH-21CD-S (manufactured by Koyo Thermo System Co., Ltd.), and heat treatment was performed at 200 ° C for 1 hour , And cooled to 50 DEG C at 5 DEG C / min. The number of revolutions at the time of spin coating was adjusted so that the thickness of the resin film after the heat treatment became 10 mu m.

The heat-treated film was subjected to heating and humidifying treatment at 121 캜 under a saturated condition of 2 atmospheres for 400 hours, followed by inserting a checkerboard-shaped indentation of 10 rows and 10 columns at intervals of 2 mm and peeling off with a cellophane tape (registered trademark) The adhesion of copper to copper was evaluated according to how many of the 100 squares remained.

5) Adhesion of silicone

The composition was spin-coated on an 8-inch silicon wafer, and then baked for 3 minutes with a 120 占 폚 hot plate (using a coating and developing apparatus Act-8 manufactured by Tokyo Electron Limited) 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 / minute using an inner oven CLH-21CD-S (manufactured by Koyo Thermo System Co., Ltd.), and heat treatment was performed at 200 ° C for 1 hour , And cooled to 50 DEG C at 5 DEG C / min. The number of revolutions at the time of spin coating was adjusted so that the thickness of the resin film after the heat treatment became 10 mu m.

The heat-treated film was subjected to heating and humidifying treatment at 121 캜 under a saturated condition of 2 atmospheres for 400 hours, followed by inserting a checkerboard-shaped indentation of 10 rows and 10 columns at intervals of 2 mm and peeling off with a cellophane tape (registered trademark) The adhesion of silicon was evaluated based on how many of the 100 squares remained.

6) Capacity retention rate

Using the composition of the present invention, the following procedure was followed.

a) Production 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 concentration of 20% and 5 parts by weight of acetylene black as a conductive auxiliary agent were dissolved in an appropriate amount of NMP and stirred to obtain a slurry-like paste. The obtained paste was applied on the electrolytic copper foil using a doctor blade, dried at 110 DEG C for 30 minutes, and pressed by a roll press machine to form an electrode. Further, the coated portion of the electrode was punched into a circle having a diameter of 16 mm, and vacuum drying was performed at 200 캜 for 24 hours to produce a negative electrode.

b) Evaluation of electrode characteristics

In the measurement of the charge-discharge characteristics, the assembly of the lithium ion battery was performed in a nitrogen atmosphere using an HS cell (manufactured by Hoso Corporation). A negative electrode prepared in the cell was punched in a circular shape having a diameter of 16 mm and a porous film (manufactured by Hoso Corporation) serving as a separator was punched to a diameter of 24 mm. The positive electrode was obtained by mixing an active material made of lithium cobalt oxide with an aluminum foil (Manufactured by Hosene Corporation) was poured in a diameter of 16 mm, and 1 mL of MIRET1 (manufactured by Mitsui Chemicals, Inc.) was injected as an electrolytic solution and sealed to obtain a lithium ion battery.

The lithium ion battery prepared as described above was charged at a constant current of 6 mA until the battery voltage reached 4.2 V and was further charged to a constant voltage of 4.2 V until reaching a total of 2 hours and 30 minutes Thereafter, the battery was stopped for 30 minutes, discharged at a constant current of 6 mA until the battery voltage reached 2.7 V, and charged and discharged in the first cycle. Charging and discharging were repeated 19 times under the same conditions, and the charging capacity and discharging capacity of each cycle were measured for a total of 20 cycles.

The capacity retention rate was calculated according to the following equation.

Capacity Retention Rate (%) = (Discharge Capacity at the 20th Cycle / Discharge Capacity at the First Cycle) × 100

Example 1

(0.04 mol: 40 mol%) of o-tolylene diisocyanate, 3.48 g (0.02 mol: 20 mol%) of 2,4-tolylene diisocyanate as an amine component, and 4,4'-diphenyl 10.0 g (0.04 mol: 40 mol%) of methane diisocyanate was dissolved in 120 g of N-methyl-2-pyrrolidone (NMP). 19.9 g (0.1 mol: 100 mol%) of trimellitic anhydride as an acid component was added together with 17.9 g of NMP, followed by reaction at 120 ° C for 2 hours and at 140 ° C for 2 hours to obtain a composition 1 having a resin concentration of 20% .

Examples 2 to 9, 14, Comparative Examples 1 and 2

Compositions 2 to 9 and 14 to 16 having a resin concentration of 20% were obtained in the same manner as in Example 1, using the amine component and the acid component shown in Table 1.

Example 10

18.5 g (0.07 mol: 70 mol%) of o-tolylidine diisocyanate and 5.22 g (0.03 mol: 30 mol%) of 2,4-tolylene diisocyanate as an amine component were dissolved in 120 g of NMP under a dry nitrogen stream. Then, 0.871 g (0.01 mol: 10 mol%) of 2-butanone oxime as a terminal sealing agent was added together with 10 g of NMP, and the reaction was carried out at 70 DEG C for 2 hours. Then, 18.3 g (0.095 mol) of anhydrous trimellitic acid : 95 mol%) was added together with 8.12 g of NMP, and the mixture was reacted at 120 占 폚 for 2 hours and at 140 占 폚 for 2 hours to obtain a composition 10 having a resin concentration of 20%.

Example 11

Composition 11 having a resin concentration of 20% was obtained in the same manner as in Example 10 by using the amine component, the acid component and the terminal sealing material shown in Table 1.

Example 12

18.5 g (0.07 mol: 70 mol%) of o-tolylidine diisocyanate and 5.22 g (0.03 mol: 30 mol%) of 2,4-tolylene diisocyanate as an amine component were dissolved in 120 g of NMP under a dry nitrogen stream. Then, 0.871 g (0.01 mol: 10 mol%) of 2-butanone oxime as a terminal sealing agent was added together with 10 g of NMP, and the reaction was carried out at 70 DEG C for 2 hours. Then, 18.3 g (0.095 mol) of anhydrous trimellitic acid : 95 mol%) was added together with 15.0 g of NMP, and the mixture was reacted at 120 캜 for 2 hours and at 140 캜 for 2 hours. Thereafter, the temperature of the solution was lowered to 60 캜, 1.73 g of 3-aminopropyltrimethoxysilane (5 weight% based on 100 weight of the resin) was added and the mixture was stirred at 60 캜 for 3 hours to obtain a resin- &Lt; / RTI &gt;

Example 13

Using the amine component, the acid component, the terminal sealing material and the silane compound shown in Table 1, a composition 13 in which the sum of the resin and the silane compound was 20% was obtained in the same manner as in Example 12. [

Comparative Example 3

20.0 g (0.1 mol: 100 mol%) of 4,4'-diaminodiphenyl ether as an amine component was dissolved in 150 g of NMP under a dry nitrogen flow. 20.7 g (0.095 mol: 95 mol%) of anhydrous pyromellitic acid as an acid component was added together with 12.9 g of NMP and reacted at 40 DEG C for 6 hours to obtain a composition 17 having a resin concentration of 20%.

Comparative Example 4

24.8 g (0.1 mol: 100 mol%) of 4,4'-diaminodiphenyl sulfone as an amine component was dissolved in 180 g of NMP under a dry nitrogen flow. Thereto was added 30.4 g (0.98 mol: 98 mol%) of oxydiphthalic dianhydride as an acid component together with 26.4 g of NMP and reacted at 200 DEG C for 6 hours to obtain a composition 18 having a resin concentration of 20%.

Synthesis Example 1 Synthesis of negative electrode active material

(CBF1 manufactured by Fuji Graphite Co., Ltd.), 60 g of nano silicon powder (manufactured by Aldrich) and 10 g of carbon black (manufactured by Mitsubishi Chemical Co., Ltd., 3050) having a median diameter of 10 탆 were mixed, Well dispersion at 600 rpm for 12 hours and then vacuum drying at 80 캜 for 12 hours to obtain a Si-C negative electrode active material. The median diameter was 10 占 퐉.

The composition 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.

Claims (18)

A resin having a structural unit represented by the following 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 each independently represent, A resin comprising a structure represented by the formula (3) and a structure represented by the following formula (4).

(In the general formula (1), R ¹ represents a divalent organic group having 2 to 50 carbon atoms, R ² represents a tricyclic 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 &lt; ¹ &gt; is an integer of 1 or 2.)

(Formula (2): R ⁴ represents a divalent organic group having 2 to 50. R ⁵ is a C2 to 50 trivalent or denotes a tetravalent organic group of a. M ² is an integer, c ¹ 0 or 1, Is an integer of 0 or 1, c ¹ = 1 when m ² = 0, and c ¹ = 0 when m ² = 1.)

(In the general formula (3), R ⁶ and R ⁷ each independently represent a halogen atom or a monovalent organic group having 1 to 3 carbon atoms, and b ¹ and b ² each independently represent an integer of 0 to 3.)

(In the general formula (4), R ⁸ independently represents a halogen atom or a monovalent organic group having 1 to 3 carbon atoms, and b ³ is an integer of 0 to 4) The resin according to claim 1, wherein R ¹ and R ⁴ are each independently, wherein at least 50 mol% thereof is a structure represented by the general formula (3). The resin according to any ^one of claims 1 to 3, wherein R ¹ and R ⁴ each independently represent a structure represented by the general formula (4) in an amount of 10 to 40 mol%. 4. The compound according to any one of claims 1 to 3, wherein R ² and R ⁵ each independently represent a structure represented by the following general formula (5) or (6) Suzy.

(In the formulas (5) to (6), R ⁹ and R ¹⁰ each independently represent a halogen atom or a monovalent organic group having 1 to 3 carbon atoms, b ⁴ and b ⁵ are integers of 0 to 4) The resin according to any one of claims 1 to 4, further comprising 5 to 30 mol% of a structural unit represented by the following general formula (7).

(7), R ¹¹ represents a divalent organic group having 2 to 50 carbon atoms, R ¹² independently represents a halogen atom or a monovalent organic group having 1 to 3 carbon atoms, b ⁶ is an integer of 0 to 4 .) 6. The resin according to any one of claims 1 to 5, wherein the terminal structure has a structure represented by the following general formula (8).

(In the 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.) A process for producing a resin according to any one of claims 1 to 6, which comprises reacting a diisocyanate with a divalent or more acid reactive therewith to prepare a resin having a structural unit represented by the general formula (2) , 95 mol% or less of bivalent or higher valent acid is reacted with 100 mol% of isocyanate. A resin solution comprising a) a resin according to any one of claims 1 to 6 and b) a solvent. The resin solution according to claim 8, further comprising c) a silane compound represented by the following general formula (9).

(Wherein R ¹⁷ is an alkoxyl group having 1 to 4 carbon atoms, R ¹⁸ is an alkoxyl group or alkyl group having 1 to 4 carbon atoms, R ¹⁹ is a divalent organic group having 1 to 4 carbon atoms, Z is a reactive group having an isocyanate group Represents a functional group having a hydroxyl group. A slurry obtained by adding a filler to the resin solution according to claim 8. The slurry according to claim 10, wherein the filler comprises at least one kind of atom selected from the group consisting of carbon, manganese, cobalt, nickel, iron, silicon, titanium, tin and germanium. The slurry according to claim 10 or 11, wherein the filler comprises at least one element or compound selected from the group consisting of silicon, silicon oxide, and lithium titanate. A laminate having a layer containing a resin according to any one of claims 1 to 8 on at least one side of an electrically conductive substrate or an insulating substrate having an electrically conductive wiring. A step of applying a resin solution according to claim 8 or 9 or the slurry according to any one of claims 10 to 12 to one side or both sides of a substrate to form a coating film and a step of drying the coating film By weight. A higher-order processed article having the laminate according to claim 13. The high-order processed product according to claim 15, which is an electrode for a multilayer wiring board, a display, a semiconductor package, an electrode for a secondary battery or an electric double-layer capacitor. A secondary battery having the electrode for a secondary battery according to claim 16. An electric double-layer capacitor having an electrode for an electric double-layer capacitor according to claim 16.