JPWO2017099172A1 - Resin, slurry, laminate using them, and method for producing the same - Google Patents

Abstract

The present invention can be cured at low temperature, has high strength, high elasticity, high adhesion, and low linear expansion, and can obtain a good capacity retention rate during charge and discharge in a binder for lithium ion batteries and capacitor electrodes. It is another object of the present invention to provide a resin capable of producing a semiconductor package, a display, and a multilayer wiring board with low warpage of the device substrate.
The present invention provides a resin having a structural unit represented by the general formula (1) and / or a structural unit represented by the general formula (2) as defined in claim 1, wherein R is contained in the resin. ¹ and R ⁴ each independently provide a resin including at least part of the structure represented by the following general formula (3) and the structure represented by the general formula (4).

Description

  Lithium ion secondary battery, capacitor electrode binder and semiconductor package, multilayer wiring board, resin, slurry, and conductive base material suitably used as display insulating film, base material with conductive wiring, and their laminates and their It relates to a manufacturing method.

  In recent years, with the explosive spread of notebook personal computers and small portable terminals, there has been an increasing demand for rechargeable secondary batteries having a small size, light weight, high capacity, high energy density, and high reliability.

  In the automobile industry, there are high expectations for reducing carbon dioxide emissions by introducing electric vehicles (EVs) and hybrid electric vehicles (HEVs), and the development of secondary batteries for motor drives that hold the key to their practical application. It is actively done.

  In particular, lithium ion secondary 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. 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.

  In order to further increase the capacity of a lithium ion battery, it has been studied to use silicon, germanium, or tin as a negative electrode active material (see, for example, Patent Document 1). In this way, since the negative electrode active material using silicon, germanium, tin, etc. can receive a large amount of lithium ions, the change in volume when fully charged and fully discharged However, since the conventional binder cannot follow the volume change of the active material, the capacity maintenance rate in the charge / discharge cycle is lowered. For this reason, a binder for a negative electrode having a large volume expansion has been studied (for example, see Patent Documents 2, 3, and 4).

  Furthermore, 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. There are concerns about adverse effects on device reliability. For this reason, the resin is also required to be imparted with characteristics that reduce the warpage of the substrate.

  As a method for reducing the warpage of the device substrate, it is possible to reduce the difference in thermal linear expansion coefficient between the resin formed on the substrate and the substrate itself, thereby reducing the stress generated by the thermal expansion difference. 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 (for example, see Patent Documents 5 to 9) having a small thermal linear expansion coefficient including a rigid structure in the main chain 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 Application Laid-Open No. 8-253854 Japanese Patent Laid-Open No. 11-158279 JP 2002-363283 A

  However, the sodium salt of carboxymethyl cellulose described as a specific binder for a negative electrode having a large volume expansion in Patent Document 1 is still insufficient in strength and cannot obtain a sufficient capacity maintenance ratio in a charge / discharge cycle. There was a problem.

  In the polyimide binder described in Patent Document 2, although the binder has high strength, there is a problem such as oxidative deterioration of the electrode because a high temperature treatment of 300 ° C. or more must be performed at the time of electrode preparation in order to convert it into a polyimide structure.

  In the binders described in Patent Documents 3 and 4, the strength of the binder is high and the processing temperature can be lowered. However, in order to obtain a high capacity retention rate by suppressing the deterioration of the electrode due to the volume change at the time of charge and discharge, the film physical properties are not yet obtained. There was a problem of insufficient.

  Moreover, since the polyimides described in Patent Documents 5 to 9 must be subjected to a high-temperature treatment at 300 ° C. or higher in order to convert them into a polyimide structure, there are problems such as oxidative deterioration of the device.

  Therefore, 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.

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 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.

（一般式（１）中、Ｒ^１は炭素数２〜５０の２価の有機基を示す。Ｒ^２は炭素数２〜５０の３価または４価の有機基を示す。Ｒ^３は水素原子、または炭素数１〜１０の有機基を示す。ｍ^１は１または２の整数である。）

(In General Formula (1), 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.)

（一般式（２）中、Ｒ^４は炭素数２〜５０の２価の有機基を示す。Ｒ^５は炭素数２〜５０の３価または４価の有機基を示す。ｍ^２は０または１の整数、ｃ^１は０または１の整数であり、ｍ^２＝０のときｃ^１＝１、ｍ^２＝１のときｃ^１＝０である。）

(In General Formula (2), R ⁴ represents a divalent organic group having 2 to 50 carbon atoms. R ⁵ represents a trivalent or tetravalent organic group having 2 to 50 carbon atoms. M ² is 0 or 1 integer, ^{c 1} is an integer of 0 or ^1, and ^c 1 = 0 when ^c 1 = ^{1, m} 2 = 1 when ^m 2 = 0.)

（一般式（３）中、Ｒ^６、Ｒ^７は各々独立にハロゲン原子または炭素数１〜３の１価の有機基を示す。ｂ^１およびｂ^２は各々独立に０〜３の整数である。）

(In 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 are each independently an integer of 0 to 3. .)

（一般式（４）中、Ｒ^８は各々独立にハロゲン原子または炭素数１〜３の１価の有機基を示す。ｂ^３は０〜４の整数である。）

(In General Formula (4), each R ⁸ 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.)

  According to the resin of the present invention, it 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. In addition, 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).

（一般式（１）中、Ｒ^１は炭素数２〜５０の２価の有機基を示す。Ｒ^２は炭素数２〜５０の３価または４価の有機基を示す。Ｒ^３は水素原子、または炭素数１〜１０の有機基を示す。ｍ^１は１または２の整数である。）

(In General Formula (1), 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.)

（一般式（２）中、Ｒ^４は炭素数２〜５０の２価の有機基を示す。Ｒ^５は炭素数２〜５０の３価または４価の有機基を示す。ｍ^２は０または１の整数、ｃ^１は０または１の整数であり、ｍ^２＝０のときｃ^１＝１、ｍ^２＝１のときｃ^１＝０である。）

(In General Formula (2), R ⁴ represents a divalent organic group having 2 to 50 carbon atoms. R ⁵ represents a trivalent or tetravalent organic group having 2 to 50 carbon atoms. M ² is 0 or 1 integer, ^{c 1} is an integer of 0 or ^1, and ^c 1 = 0 when ^c 1 = ^{1, m} 2 = 1 when ^m 2 = 0.)

From the viewpoint that it can be processed at a lower temperature, 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.

In 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 include a structure represented by the general formula (3) and a structure represented by the general formula (4).

In 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. 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 or fluoroalkyl group having 1 to 3 carbon atoms 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.

  In general formula (3), 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.

From the standpoint of both solubility in a solvent and low linear expansion, 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.

In General Formula (4), each R ⁸ 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 or fluoroalkyl group having 1 to 3 carbon atoms is more preferable. b ³ is an integer of 0 to 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.

  In general formula (4), it is preferable that the benzene ring is connected by the meta bond from the viewpoint of compatibility with the 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) in terms of both solubility in a solvent and low linear expansion. Preferably it is 25-35 mol%.

  The diamine residue may contain a diamine residue other than the structure represented by the general formulas (3) and (4). Examples of the amine component that gives such a diamine residue include 3,5-diaminobenzoic acid, carboxyl group-containing diamines such as 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, bis {4- (4-aminophenoxy) phenyl} ether, 1,4 -Bis (4-aminophenoxy) benzene or a compound in which a part of hydrogen atoms of these aromatic rings are substituted with an alkyl group or a halogen atom, or an aliphatic diamine such as cyclohexyldiamine or methylenebiscyclohexylamine. Although it can, it is not limited to these.

  In addition to the diamine, 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.

  In the case of a resin having the structural unit represented by the general formula (2) as a main component, a diisocyanate compound is preferably used in that there is no by-product water.

In 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 preferable tricarboxylic acid that gives an acid residue include trimellitic acid, trimesic acid, diphenyl ether tricarboxylic acid, and biphenyl tricarboxylic acid.

  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-dicarboxyphenyl) methane, bis (3,4-dicarboxy) Phenyl) sulfone, bis (3,4-dicarboxyphenyl) ether, 1,2,5,6-naphthalenetetracarboxylic acid, 2,3,6,7-naphthalenetetracarboxylic acid, 2,3,5,6- Aromatic tetracarboxylic acids such as pyridinetetracarboxylic acid, 3,4,9,10-perylenetetracarboxylic acid, cyclobutanetetracarboxylic acid, 1,2,3,4-cyclopentanetetracarboxylic acid, cyclohexanetetracarboxylic acid, Bicyclo [2.2.1. ] 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.

From the viewpoint of low linear expansion of the resin, 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.

In 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. 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 or fluoroalkyl group having 1 to 3 carbon atoms is more preferable. b ⁴ and b ⁵ are integers of 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.

また本発明の樹脂は、さらに、高強度、高弾性とするために、下記一般式（７）で表される構造単位を５〜３０モル％含むことが好ましい。

The resin of the present invention preferably further contains 5 to 30 mol% of a 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 C 2-50 valent organic group. Examples of 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. Sulfonic acid-containing diamine, dithiohydroxyphenylenediamine, 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′-diaminodiphenylsulfide, 1,4-bis (4-aminophenoxy) benzene, m-phenylenediamine, p-phenylenediamine 1,5-naphth Talenediamine, 2,6-naphthalenediamine, bis (4-aminophenoxyphenyl) sulfone, bis (3-aminophenoxyphenyl) sulfone, bis (4-aminophenoxy) biphenyl, bis {4- (4-aminophenoxy) phenyl } Ether, 1,4-bis (4-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, Compounds in which part of the hydrogen atoms of the aromatic ring are substituted with alkyl groups or halogen atoms, structures represented by the general formulas (3) and (4), aliphatic diamines such as cyclohexyl diamine and methylene bis cyclohexyl amine, etc. It can mention, but it is not limited to these.

  These 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. 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 or fluoroalkyl group having 1 to 3 carbon atoms is more preferable. b ⁶ is an integer of 0 to 4. From the viewpoint of low linear expansion, it is preferably 0.

  In general formula (7), the benzene rings are preferably linked by a para bond from the viewpoint of low linear expansion characteristics.

In general formulas (1), (2), and (7), resistance to oxygen plasma and UV ozone treatment for improving the adhesion of the heat-treated film to the silicon-based substrate and glass substrate or for cleaning. In order to increase the heat resistance, 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. Specific examples of R ¹ , R ⁴ and R ¹¹ include residues such as bis (3-aminopropyl) tetramethyldisiloxane and bis (p-amino-phenyl) octamethylpentasiloxane. These are preferably copolymerized in an amount of 1 to 10 mol% of R ¹ , R ⁴ and R ¹¹ as a whole. Specific examples of R ² and R ⁵ include dimethylsilane diphthalic dianhydride, 1,3-bis (phthalic acid) tetramethyldisiloxane dianhydride, 1- (p-carboxyphenyl) 3-phthalic acid. Examples include 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.

In the general formulas (1), (2), and (7), in order to improve the adhesion of the heat-treated film to the metal substrate, 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. As specific structures, “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 alone 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.

Although these resin is synthesize | combined by the method quoted below, it is not limited to these.
That is, in the case of the polyamic acid represented by the general formula (1), 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.

  In the case of the polyamic acid ester represented by the general formula (1), a tetracarboxylic dianhydride is mixed with an alcohol such as ethanol, propanol or butanol and a base catalyst such as pyridine or triethylamine, and from 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 the dropwise addition, a polyamic acid ester is obtained by reacting at -20 ° C to 50 ° C for 1 hour to 100 hours. Since 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.

  In the case of the polyimide represented by the general formula (2), the polyimide precursor can be obtained by imide ring closure by heat treatment or chemical treatment. Examples of 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.

  In the case of the polyamideimide represented by the general formula (2), a method is generally used in which a diamine is dissolved in a solvent such as NMP, DMF, DMAC, GBL, DMSO, and a reaction is performed by adding a tricarboxylic acid. 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. As a general reaction, there is a method in which tricarboxylic acid chloride is allowed to act on a diamine solution, and then a heat treatment at 100 ° C. to 300 ° C. is performed for 1 minute to 24 hours to obtain polyamideimide. In this case, 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. Also, polyamic acid amide is polymerized with 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. Thus, polyamideimide can be obtained.

  In the case of the polyimide and polyamideimide represented by the general formula (2), 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.

  In the polymerization reaction of these resins, 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 less than mol%. When there are more diamines or diisocyanates, 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. By reprecipitation, 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 includes a structure in which the resin terminal is represented by the following general formula (8).

In general formula (8), R < ¹³ > -R < ¹⁶ > shows a halogen atom or a C1-C5 monovalent organic group each independently.

  When these terminal structures are included, the protecting group is eliminated during the heat treatment to regenerate the isocyanate group. 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.

  A 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.

  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 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-methoxy Acetates such as butyl acetate, methyl lactate, ethyl lactate and butyl lactate, ketones such as acetylacetone, methyl propyl ketone, methyl butyl ketone, methyl isobutyl ketone, cyclopentanone and 2-heptanone, butyl alcohol, isobutyl alcohol, pentano , 4-methyl-2-pentanol, 3-methyl-2-butanol, 3-methyl-3-methoxybutanol, alcohols such as diacetone alcohol, aromatic hydrocarbons such as toluene and xylene, N-methyl -2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, γ-butyrolactone and the like. These can be used alone or in combination.

The range of the concentration and viscosity of the resin solution is preferably 1 mPa · sec to 1000 Pa · sec at a concentration of 1 to 50 wt%, more preferably 100 mPa · sec to 100 Pa · sec at a concentration of 5 to 30 wt%. . 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).

In the 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.
3-aminopropyltriethoxysilane, 3-aminopropylmethyldiethoxysilane, 3-aminopropyldimethylethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropyldimethylmethoxysilane, 3 -Aminopropylphenyldiethoxysilane, 3-aminopropylphenyldimethoxysilane, 3-hydroxypropyltriethoxysilane, 3-hydroxypropylmethyldiethoxysilane, 3-hydroxypropyldimethylethoxysilane, 3-hydroxypropyltrimethoxysilane, 3 -Hydroxypropylmethyldimethoxysilane, 3-hydroxypropyldimethylmethoxysilane, 3-hydroxypropylphenyldiethoxysilane, 3-hydroxypro Ruphenyldimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldiethoxysilane, 3-mercaptopropyldimethylethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyl Dimethylmethoxysilane, 3-mercaptopropylphenyldiethoxysilane, 3-mercaptopropylphenyldimethoxysilane, 3-acryloxypropyltriethoxysilane, 3-acryloxypropylmethyldiethoxysilane, 3-acryloxypropyldimethylethoxysilane, 3 -Acryloxypropyltrimethoxysilane, 3-acryloxypropylmethyldimethoxysilane, 3-acryloxypropyldimethylmethoxy Lan, 3-acryloxypropylphenyldiethoxysilane, 3-acryloxypropylphenyldimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyldimethylethoxysilane, 3 -Methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyldimethylmethoxysilane, 3-methacryloxypropylphenyldiethoxysilane, 3-methacryloxypropylphenyldimethoxysilane, N-phenylaminoethyl Trimethoxysilane, N-phenylaminoethyltriethoxysilane, N-phenylaminopropyltrimethoxysilane, N-phenylaminopropyltri Examples include, but are not limited to, ethoxysilane, N-phenylaminobutyltrimethoxysilane, N-phenylaminobutyltriethoxysilane, and the like.
The content of these silane compounds is preferably 0.01 to 15 parts by weight with respect to 100 parts by weight of the resin.

  When these silane compounds are contained, there is an advantage that adhesion with silicon, titanium, and zirconium is improved, and it can be suitably used as a binder for a negative electrode containing silicon and titanium. In particular, when a resin is synthesized from the reaction of a diisocyanate and a divalent or higher acid that reacts with it, it reacts with the isocyanate present at the end of the polymer to form a polymer having an adhesion improving component bonded to the end, resulting in a better adhesion improving effect. There is an advantage of increasing.

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. Examples of 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. Although all the functional groups of these polyhydroxy compounds and polyamino compounds may not be substituted with quinonediazide, it is preferable that 50 mol% or more of the entire functional groups are substituted with 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. By using such a quinonediazide compound, 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-BP, TML-HQ , TML-pp-BPF, TML-BPA, TMOM-BP, HML-TPPHBA, HML-TPHAP (above, trade name, manufactured by Honshu Chemical Industry Co., Ltd.), BIR-OC, BIP-PC, BIR-PC, BIR -PTBP, BIR-PCHP, BIP-BIOC-F, 4PC, BIR-BIPC-F, TEP-BIP-A, 46DMOC, 46DMOEP, TM-BIP-A (above, trade name, manufactured by Asahi Organic Materials Co., Ltd.) ), 2,6-dimethoxymethyl-4-t-butylphenol, 2,6-dimethoxymethyl-p-cresol, 2,6-diacetoxymethyl-p-cresol, naphthol, tetrahydroxybenzophenone, gallic acid methyl ester, bisphenol A, bisphenol E, methylene bisphenol, BisP-AP (trade name, book Chemical Industries Co.), and the like, but not limited to.

  Polyamino compounds are 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 and 3,3'-dihydroxybenzidine, but are not limited thereto.

  In the present invention, 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-naphthoquinone diazide sulfonyl 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 or 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-naphthoquinone diazide sulfonyl group and a 5-naphthoquinone diazide sulfonyl group are used in the same molecule can be obtained, or a 4-naphthoquinone diazide sulfonyl ester compound and a 5-naphthoquinone diazide sulfonyl ester can be obtained. A compound can also be used in combination.

  Further, the molecular weight of the quinonediazide compound is preferably 300 or more, and 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.

  As a whole, 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. In addition, 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-naphthoquinonediazide sulfonyl chloride and a phenol compound in the presence of triethylamine. Examples of the method for synthesizing a phenol compound include a method in which an α- (hydroxyphenyl) styrene derivative is reacted with a polyhydric phenol compound under an acid catalyst.

  Among the photoacid generators, as the sulfonium salt compound, phosphonium salt compound, and diazonium salt compound, 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. Among these, 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. Moreover, in order to improve the photosensitive performance of the resin composition, a photopolymerizable compound may be included. As photopolymerizable compounds, 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.

  Furthermore, when giving negative photosensitivity to the resin composition of this invention, you may contain a photoinitiator. Suitable photopolymerization initiators 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. Compounds, chain oxime compounds typified by 1-phenylpropanedione-2- (o-ethoxycarbonyl) oxime, benzophenone, benzophenone derivatives such as methyl o-benzoylbenzoate, dibenzylketone, fluorenone, thioxanthone, 2-methyl Examples thereof 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.

  Furthermore, it is more preferable to contain a photosensitizer in order to improve the negative photosensitive characteristics. Examples of 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. , BisP-MZ, BisP-EZ, Bis26X-CP, BisP-PZ, BisP-IPZ, BisCR-IPZ, BisOCP-IPZ, BisOIPP-CP, Bis26X-IPZ, BisOTBP-CP, TekP-4HBPA (Tetrakis P-DO- BPA), TrisP-HAP, TrisP-PA, BisOFP-Z, BisRS-2P, BisPG-26X, BisRS-3P, BisOC-OCHP, BisPC-OCHP, Bis25X-OCHP, Bis26X-OCH , BisOCHP-OC, Bis236T-OCHP, Methylenetris-FR-CR, BisRS-26X, BisRS-OCHP (trade name, manufactured by Honshu Chemical Industry Co., Ltd.), BIR-OC, BIP-PC, BIR-PC, BIR-PTBP, BIR-PCHP, BIP-BIOC-F, 4PC, BIR-BIPC-F, TEP-BIP-A (above, trade name, manufactured by Asahi Organic Materials Co., Ltd.) can be mentioned.

  Among these, 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. Among these, particularly preferable 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. 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 and 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. In order to enhance the resistance to UV ozone treatment, 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. Specific examples of preferable silane coupling agents include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrichlorosilane, vinyltris (β-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.

  Moreover, it is also possible to further improve the adhesiveness by pretreating the substrate surface to which the resin composition is applied. Examples of the pretreatment method include the following methods. A solution obtained by dissolving 0.5-20 parts by weight of the above-described adhesion improver in a solvent such as isopropanol, ethanol, methanol, water, tetrahydrofuran, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, diethyl adipate Is subjected to surface treatment by spin coating, dipping, spray coating, steam treatment or the like. Further, hexamethyldisilazane vapor may be directly sprayed for treatment. Thereafter, a vacuum 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.
As surfactants, "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.) And acrylic polymer surfactants.

  A filler may be added to the resin solution of the present invention to be used as a slurry. When used for semiconductors, displays, and multilayer wiring boards, the addition of fillers can be expected to further reduce linear expansion, increase strength, and control refractive index, dielectric constant, and magnetic permeability. When used for 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, and multilayer wiring boards include, but are not limited to, silicon oxide, titanium oxide, alumina, barium titanate, aluminum nitride, zirconium oxide, silicon nitride, and titanium nitride.

  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.

  When these compounds are used as a filler, 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 positive electrode filler include lithium iron phosphate, lithium cobaltate, lithium nickelate, lithium manganate, activated carbon, and carbon nanotube.

  Examples of the negative electrode filler include lithium titanate, hard carbon, soft carbon, activated carbon, carbon nanotube, silicon, tin, and a compound containing germanium atoms. In particular, since a storage battery using a compound containing silicon, tin, and germanium atoms as a filler has a large volume expansion of the active material during charging, it is preferable to use 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. Examples of 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 μm. Further, 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. 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.

In the slurry of the present invention, the content of the resin (in the case where an additive is added, resin + additive) 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.
When 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 the electrical resistance and increase the filling amount of the filler.

  When used for an electrode of a secondary battery or a capacitor, 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 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 optionally a solvent and other additives. In the case of mixing, put in a glass flask or stainless steel container, etc., 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. In the case of 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.

  Further, in order to remove foreign matters, the resin solution, resin composition, and slurry after mixing and kneading may be filtered through a filter having a pore size of 0.01 μm to 100 μm. Examples of the material for the filter include polypropylene (PP), polyethylene (PE), nylon (NY), polytetrafluoroethylene (PTFE), and polyethylene and nylon are preferable. Moreover, when a resin composition contains a filler and an organic pigment, it is preferable to use a filtration filter having a pore size larger than these particle sizes.

  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.

  As the base material, a conductive base material or an insulating base material on which conductive wiring is formed is used. 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.
First, the resin solution, resin composition, or slurry of the present invention is applied on a substrate.
Examples of 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. Moreover, although a coating film thickness changes with application methods, the solid content concentration of a composition, a viscosity, etc., it is preferable that the film thickness after drying is 0.1-150 micrometers normally.

  Next, 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.

  When the resin solution, resin composition, or slurry is photosensitive, the film is exposed to actinic radiation through a mask having a desired pattern. 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, i-ray (wavelength 365 nm), h-ray (wavelength 405 nm) of a mercury lamp. ), G-line (wavelength 436 nm) is preferably used.

  Further, when exposing a non-photosensitive resin solution, resin composition, or slurry, it is necessary to form another layer of a photoresist film on the resin film. For this photoresist, 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.

  When the resolution of the pattern at the time of development is improved or when the allowable range of development conditions is increased, a step of performing a baking process before development may be incorporated. As this temperature, the range of 50-180 degreeC is preferable, and the range of 60-150 degreeC is especially more preferable. 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.

  In order to form a pattern of the resin solution, the resin composition, or the slurry, development processing is performed. When the resin solution, resin composition, or slurry has negative photosensitivity, the unexposed area is removed with a developer. When 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. Ammonia, tetramethylammonium hydroxide aqueous solution, diethanolamine, diethylaminoethanol, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, triethylamine 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. In some cases, polar aqueous solvents such as N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, γ-butyrolactone, dimethylacrylamide, methanol, ethanol, isopropanol are used in these alkaline aqueous solutions. One or more kinds of 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.

  Further, N-methyl-2-pyrrolidone, N-acetyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, hexamethylphospho, which are good solvents for the resin of the present invention, are used as a developer. Rutriamide, 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 liquid mixture of propionate, ethyl-3-ethoxypropionate, 2-heptanone, cyclopentanone, cyclohexanone, ethyl acetate or the like alone or in combination with the above-mentioned good solvent can also be preferably used.

  The development can be performed 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.

  Then, it is preferable to wash the relief pattern formed by development with a rinse solution. As the rinse solution, water can be preferably used when an alkaline aqueous solution is used as the developer. At this time, 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.

  When rinsing with an organic solvent, methanol, ethanol, isopropyl alcohol, ethyl lactate, ethyl pyruvate, propylene glycol monomethyl ether acetate, methyl-3-methoxypropionate, ethyl-3-ethoxy, which are miscible with the developer Propionate, 2-heptanone, ethyl acetate and the like are preferably used.

  When photosensitivity is not imparted to the resin solution, resin composition, or slurry, the photoresist film formed on the resin film after development must be removed. This removal is often performed by dry etching or wet etching with a stripping solvent. As the peeling 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.

  In order to further improve the heat resistance, the film may be cured at a temperature of 150 ° C. to 500 ° C. after development. To convert to a heat resistant coating. 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. As an example, 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. Further, the heat treatment is preferably performed at 250 ° C. or lower because there is a fear that the electrical characteristics of the element may change due to high-temperature heating or repetition thereof, and the warpage of the substrate may increase. In particular, since 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.

  Next, an example is given and demonstrated about the manufacturing method of the lithium ion battery electrode of this invention, and an electric double layer capacitor electrode.

  In the case of a lithium ion battery negative electrode (hereinafter sometimes referred to as a negative electrode), the slurry of the present invention is applied on a metal foil with a thickness of 1 to 100 μm. A copper foil is generally used as the metal foil. For the application, methods such as screen printing, roll coating, and slit coating can be used.

  When a polyimide precursor is used as a binder, 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. Preferably, the treatment is 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. Moreover, when using a polyimide as a binder, after application | coating, it is preferable to remove a solvent by heat-processing at 80 to 500 degreeC for 1 minute-24 hours. 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.

  When the binder contains a low-temperature decomposition resin, a negative electrode having pores inside can be obtained by decomposing the low-temperature decomposition resin by heat treatment. In this case, 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. As such a temperature range, it is preferable to perform the treatment at 300 to 450 ° C. for 30 minutes to ˜20 hours. Examples of such thermally decomposable resins include polyethylene glycol and polypropylene glycol.

  In the case of a lithium battery positive electrode (hereinafter sometimes referred to as a positive electrode) and an electric double layer capacitor positive and negative electrode, the slurry of the present invention is applied on a metal foil in 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 heat treatment method are the same as those for 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.
About the positive electrode and negative electrode of this invention, what was laminated | stacked via the separator is put into exterior materials, such as a metal case, with an electrolyte solution, A secondary battery and an electric double layer capacitor can be obtained.

Examples of the separator include polyolefins such as polyethylene and polypropylene, microporous films such as cellulose, polyphenylene sulfide, aramid, and polyimide, and nonwoven fabrics.
In order to increase the heat resistance, the surface of the separator may be coated with ceramic 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 solvents include carbonate-based, ester-based, ether-based, ketone-based, alcohol-based and non-protonic solvents. Examples of 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. (EMC), ethylene carbonate (EC), propylene carbonate (PC), butylene carbonate (BC), and the like. Examples of the ester solvent include methyl acetate, ethyl acetate, n-propyl acetate, methyl propionate, ethyl propionate, γ-butyrolactone, tecanolide, valerolactone, mevalonolactone, caprolactone, and the like. Examples of the ether solvent include dibutyl ether, tetraglyme, diglyme, dimethoxyethane, 2-methyltetrahydrofuran, and tetrahydrofuran. Examples of the ketone solvent include cyclohexanone. Examples of the alcohol solvent include ethyl alcohol and isopropyl alcohol. Examples of the non-protonic solvent 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. For example, in the case of 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, and the performance of the electrolytic solution can be improved.

  Examples of the electrolyte used for the electrolyte 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 coating film formed from the slurry, and the laminate 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.

  EXAMPLES Hereinafter, although an Example etc. are given and this invention is demonstrated, this invention is not limited by these examples. In addition, the evaluation of the composition in an Example was performed with the following method.

1) Method for measuring film thickness of composition Using Lambda Ace STM-602 manufactured by Dainippon Screen Mfg. Co., Ltd., both the resin film and the heat-cured film were measured with a refractive index of 1.629.

2) Measuring method of mechanical properties of composition (strength (MPa), elastic modulus (GPa), elongation (%)) The composition solution was spin-coated on an 8-inch silicon wafer, and then a hot plate at 120 ° C. Baking was performed for 3 minutes using a coating and developing apparatus Act-8 manufactured by Tokyo Electron Ltd. to obtain a resin film.
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 a rate of 5 ° C./min, and then 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 μm.

  About the film after heat processing, what was cut into the strip shape of width 1cm and length about 9cm was used as the sample for a measurement. “Tensilon” (RTM-100; manufactured by Orientec) was used for the measurement, and the average value of the top 5 points was determined from the measurement results.

3) Method of measuring coefficient of thermal expansion (CTE) of composition The composition solution was spin-coated on an 8-inch silicon wafer, and then a 120 ° C hot plate (Coating and developing apparatus Act-8 manufactured by Tokyo Electron Ltd.) Use) for 3 minutes to obtain a resin film.

  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 a rate of 5 ° C./min, and then 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 μm.

  About the film after heat processing, it measured in nitrogen stream using the thermomechanical analyzer (SII nanotechnology Co., Ltd. product EXSTAR6000TMA / SS6000). 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 rising rate of 5 ° C./min, and the average value of the thermal linear expansion coefficients from 50 ° C. to 200 ° C. was obtained.

4) 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 on a 120 ° C. hot plate (using a coating and developing apparatus Act-8 manufactured by Tokyo Electron Co., Ltd.) for 3 minutes to obtain a resin film.

  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 a rate of 5 ° C./min, and then 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 μm.

  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.

5) 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 a rate of 5 ° C./min, and then 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 μm.
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.

6) 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.

b) 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. The ones fired into foil (made by Hosen Co., Ltd.) and punched out to a diameter of 16 mm are stacked one after the other, and 1 mL of MIRET1 (made by Mitsui Chemicals Co., Ltd.) is injected and sealed, and a lithium ion battery is inserted. Obtained.

The lithium-ion battery prepared as described above is charged with a constant current of 6 mA until the battery voltage reaches 4.2 V, and further charged with a constant voltage of 4.2 V until reaching a total of 2 hours 30 minutes from the start of charging. Then, the battery was paused for 30 minutes, and discharged at a constant current of 6 mA until the battery voltage reached 2.7 V, and charge / discharge of the first cycle was performed. Moreover, after that, charging / discharging was 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 formula.
Capacity maintenance ratio (%) = (discharge capacity at 20th cycle / discharge capacity at 1st cycle) × 100

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.

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

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 are 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 are 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. for 2 hours and at 140 ° C. for 2 hours. Thereafter, the temperature of the solution is lowered to 60 ° C., 1.73 g of 3-aminopropyltrimethoxysilane (5 wt. Relative to 100 wt. Of resin) is added, and the mixture is further stirred at 60 ° C. for 3 hours. A composition 12 having a concentration of% was obtained.

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.

Comparative Example 3
Under a dry nitrogen stream, 20.0 g (0.1 mol: 100 mol%) of 4,4′-diaminodiphenyl ether as an amine component was dissolved in 150 g of NMP. Here, 20.7 g (0.095 mol: 95 mol%) of pyromellitic anhydride as an acid component was added together with 12.9 g of NMP, and reacted at 40 ° C. for 6 hours to obtain a composition 17 having a resin concentration of 20%.

Comparative Example 4
In a dry nitrogen stream, 24.8 g (0.1 mol: 100 mol%) of 4,4′-diaminodiphenylsulfone as an amine component was dissolved in 180 g of NMP. Here, 30.4 g (0.98 mol: 98 mol%) of oxydiphthalic acid dianhydride as an acid component was added together with 26.4 g of NMP, and reacted at 200 ° C. for 6 hours to obtain a composition 18 having a resin concentration of 20%.

Synthesis Example 1 Synthesis of negative electrode active material 50 g of natural graphite having a median diameter of 10 μm (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 rotations 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 μm.
It shows in Table 1 as Examples 1-14 and Comparative Examples 1-4 about the composition and evaluation result of the compositions 1-18.

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 are each independently A resin containing at least a structure represented by the following general formula (3) and a structure represented by the following general formula (4).

(In General Formula (1), 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.)

(In General Formula (2), R ⁴ represents a divalent organic group having 2 to 50 carbon atoms. R ⁵ represents a trivalent or tetravalent organic group having 2 to 50 carbon atoms. M ² is 0 or 1 integer, ^{c 1} is an integer of 0 or ^1, and ^c 1 = 0 when ^c 1 = ^{1, m} 2 = 1 when ^m 2 = 0.)

(In 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 are each independently an integer of 0 to 3. .)

(In General Formula (4), each R ⁸ 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.) 2. The resin according to claim 1, wherein R ¹ and R ⁴ are each independently a structure in which 50 mol% or more thereof is represented by the general formula (3). The resin according to claim 1 or 2, wherein R ¹ and R ⁴ are each independently a structure represented by 10 to 40 mol% of the general formula (4). R ² and R ⁵ are each independently any one of claims 1 to 3, wherein 65 mol% or more thereof is a structure represented by the following general formula (5) or the following general formula (6). resin.

(In the general 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. is there.) Furthermore, resin in any one of Claims 1-4 which contains 5-30 mol% of structural units represented by following General formula (7).

(In General Formula (7), R ¹¹ represents a divalent organic group having 2 to 50 carbon atoms. R ¹² each independently represents a halogen atom or a monovalent organic group having 1 to 3 carbon atoms. B ⁶ Is an integer from 0 to 4.) 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 General formula (8), R < ¹³ > -R < ¹⁶ > shows a halogen atom or a C1-C5 monovalent organic group each independently. A method for producing the resin according to claim 1, wherein a resin having a structural unit represented by the general formula (2) is produced by reacting a diisocyanate and a divalent or higher acid that reacts with the diisocyanate. A production method in which a divalent or higher acid of 95 mol% or less is reacted with respect to 100 mol% of the isocyanate.   A resin solution comprising a) the resin according to claim 1 and b) a solvent. Furthermore, c) The resin solution of Claim 8 containing the silane compound represented by following General formula (9).

(In the general formula (9), 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, and R ¹⁹ is a divalent organic group having 1 to 4 carbon atoms. Z represents a functional group reactive with an isocyanate group.)   The slurry formed by making the resin solution of Claim 8 contain a filler.   The slurry according to claim 10, wherein the filler contains at least one 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 contains at least one element or compound selected from the group consisting of silicon, silicon oxide, and lithium titanate.   The laminated body which has a layer containing the resin in any one of Claims 1-8 in the at least single side | surface of the insulating base material which has a conductive base material or conductive wiring.   Applying the resin solution according to claim 8 or 9 or the slurry according to any of claims 10 to 12 to one or both sides of a substrate to form a coating film, and drying the coating film The manufacturing method of the laminated body including the process to do.   A high-order processed product comprising the laminate according to claim 13.   The high-order processed product according to claim 15, which is a multilayer wiring board, a display, a semiconductor package, an electrode for a secondary battery, or an electrode for an electric double layer capacitor.   A secondary battery comprising the secondary battery electrode according to claim 16.   The electric double layer capacitor which has an electrode for electric double layer capacitors of Claim 16.