CN101569036B - Negative electrode base member - Google Patents

Abstract

The present invention can realize a battery having high output voltage and high energy density and excellent charge-discharge cycle characteristics by utilizing a configuration different from that of the prior art. The present invention uses the following negative electrode substrate as the negative electrode substrate for lithium-ion secondary batteries: it is characterized in that a negative electrode substrate with a metal film is formed on a support with an organic film; it is characterized in that the surface layer of the organic film is oxidized by a metal The negative electrode base material covered by the material film; it is characterized in that on the support body with the composite film formed by the composite film forming material comprising organic components and inorganic components, the negative electrode base material of metal film is formed; or it is characterized in that it is formed on On the support body of the photoresist pattern, a silicon dioxide-based coating film formed of a coating liquid for forming a silicon dioxide-based coating film is formed, and a metal film is formed on the support body from which the photoresist pattern is removed. Negative base material.

Description

Negative electrode substrate

technical field

The present invention relates to a negative electrode substrate, a secondary battery using the negative electrode substrate, a photoresist composition for forming the negative electrode substrate, a metal oxide film forming material, a composite film forming material, and the negative electrode substrate Manufacturing method, in particular, relates to a negative electrode substrate capable of providing a battery with excellent charge-discharge cycle characteristics, a secondary battery using the negative electrode substrate, a photoresist composition for forming and manufacturing the negative electrode substrate, and a metal oxide A film-forming material, a composite film-forming material, and a method for producing the negative electrode substrate. the

Background technique

In the past, the research and development of batteries with high output voltage and high energy density has been very popular. In particular, a secondary battery having a low internal resistance, a small drop in battery capacity due to charging/discharging, and excellent charge-discharge cycle characteristics has been sought. For example, there is known a lithium secondary battery using thin-film amorphous silicon or microcrystalline silicon as a negative electrode material (negative electrode active material) (see Patent Document 1). Specifically, it discloses a lithium secondary battery using a negative electrode in which a negative electrode material layer including a silicon thin film is formed on a current collector. Plating method) or sputtering method and other thin film forming methods. the

Among them, it is generally believed that materials such as silicon expand/shrink repeatedly as lithium is stored/released. In the negative electrode in which the silicon thin film is formed on the current collector, since the adhesion between the current collector and the negative electrode material layer is high, the current collector frequently expands/shrinks along with the expansion/shrinkage of the negative electrode material. Therefore, as charging/discharging proceeds, the negative electrode material layer and the current collector may undergo irreversible deformation such as wrinkles. In particular, when a ductile metal foil such as copper foil is used for the current collector, the degree of deformation increases. Deformation of the negative electrode will increase the volume of the electrode and make the electrochemical reaction uneven, so the energy density of the battery may decrease. In addition, during repeated expansion/contraction with charging/discharging, the negative electrode material may be pulverized and detached from the current collector, or may detach from the current collector in a thin film state in some cases. This is a major factor causing the deterioration of the charge-discharge cycle characteristics of the battery. the

As a method of suppressing deformation of the negative electrode, a method of using a material having high mechanical strength such as tensile strength and tensile modulus as a current collector is mentioned. However, when a negative electrode material layer formed of a thin-film negative electrode material is formed on a current collector formed of such a material, there is a possibility that the adhesion between the negative electrode material layer and the current collector is insufficient, and sufficient Charge-discharge cycle characteristics. Therefore, Patent Document 1 discloses a technology in which an intermediate layer formed of a material that will alloy with the negative electrode material is placed between the current collector and the negative electrode material layer, and a current collector having a higher mechanical strength than the intermediate layer is used. Body, in order to suppress the detachment of the negative electrode material during charging/discharging, and suppress the occurrence of wrinkles and the like. Specifically, a copper layer was used as an intermediate layer, and a nickel foil was used as a current collector. the

Documents other than the above-mentioned Patent Document 1 also disclose techniques for suppressing the amount of lithium occlusion by using a thin film obtained by solid-solving copper on silicon as a negative electrode material layer, thereby suppressing the amount of lithium occlusion. Expansion of negative electrode material (see Patent Document 2). In addition, the following technology has been disclosed: using an alloy thin film containing a metal that alloys with lithium and a metal that does not alloy with lithium as a negative electrode material layer to suppress the amount of lithium storage, thereby suppressing the time when lithium is stored. The expansion of the negative electrode material (see Patent Document 3). Specifically, tin (Sn), germanium (Ge), aluminum (Al), indium (In), magnesium (Mg), and silicon ( Si), etc., copper (Cu), iron (Fe), nickel (Ni), cobalt (Co), molybdenum (Mo), tungsten (W), tantalum (Ta) are used as metals that do not alloy with lithium And manganese (Mn), etc. the

In addition, a technique has been disclosed for suppressing deformation of the electrode accompanying charging/discharging by using a current collector in which 10 or more deformations in the thickness direction are formed per 1 cm ² of the current collector The amount of the deformed portion is 5 μm to 20 μm, and the numerical aperture of the deformed portion is 4% or less (see Patent Document 4). In addition, a technique has been disclosed in which a lithium non-storage material is arranged on at least one of the surface and the inside of a thin-film negative electrode material layer capable of reversibly storing/releasing lithium (see Patent Document 5).

[Patent Document 1] Japanese Patent Application Laid-Open No. 2002-083594

[Patent Document 2] Japanese Patent Laid-Open No. 2002-289177

[Patent Document 3] Japanese Patent Application Laid-Open No. 2002-373647

[Patent Document 4] Japanese Patent Application Laid-Open No. 2003-017069

[Patent Document 5] Japanese Patent Application Laid-Open No. 2005-196971

Contents of the invention

[Problem to be solved by the invention] 

However, the present situation is that a battery having sufficient output voltage, energy density, and charge-discharge cycle characteristics cannot be obtained using any of the above-mentioned various negative electrode materials. Therefore, the object of the present invention is to provide a negative electrode base material that can realize a battery having a high output voltage and a high energy density and excellent charge-discharge cycle characteristics by using a structure different from that of the prior art. secondary battery, the manufacturing method of the negative electrode base material, the composite film forming material used to form the negative electrode base material, the metal oxide film forming material used to form the negative electrode base material, the positive electrode material used to form the negative electrode base material Type photoresist composition, and the photoresist composition used to form the negative electrode substrate. the

[Technical means to solve the problem] 

The present inventors have repeatedly studied intensively in view of the above situation, and found that a battery with high output voltage and high energy density and excellent charge-discharge cycle characteristics can be provided by using the negative electrode base material as described below, thereby completing the present invention: A negative electrode substrate that forms a metal film on an organic film; a negative electrode substrate that forms a metal film on a composite film composed of an organic component and an inorganic component; forms a metal film on an organic film whose surface is covered with a metal oxide film negative electrode substrate; a negative electrode substrate in which a metal film is formed on a patterned silicon dioxide-based coating film; On the organic film formed by the photoresist composition, the metal film is formed as the negative electrode base material. the

That is, the present invention provides a negative electrode base material characterized in that a metal film is formed on a support having an organic film. In addition, the present invention provides: a negative electrode base material characterized in that the organic film is formed of a photoresist film; or a negative electrode base material characterized in that the photoresist film is patterned into a predetermined shape by pattern exposure. In addition, the present invention provides a secondary battery having the negative electrode substrate, a method for manufacturing the negative electrode substrate, and a photoresist composition for manufacturing the negative electrode substrate. the

The present invention provides a negative electrode base material characterized in that a metal film is formed on a support having an organic film whose surface layer is covered with a metal oxide film. In addition, there are provided: a negative electrode substrate in which the organic film is formed of a photoresist film; a negative electrode substrate in which the photoresist film is patterned into a predetermined shape by pattern exposure; and the metal oxide film is a silicon dioxide-based coating. The negative electrode substrate of the membrane. In addition, the present invention provides a secondary battery using a negative electrode substrate, a metal oxide film forming material and a photoresist composition for forming the negative electrode substrate, and a method for manufacturing the negative electrode substrate. the

The present invention provides a negative electrode base material characterized in that a metal film is formed on a support body having a composite film formed of a composite film forming material comprising an organic component and an inorganic component, and a secondary battery using the negative electrode base material is used for A composite film-forming material forming the negative electrode substrate, and a method for manufacturing the negative electrode substrate. the

The present invention provides a film characterized in that a silicon dioxide-based coating film formed of a coating liquid for forming a silicon dioxide-based coating film is formed on a support on which a photoresist pattern is formed, and the photoresist is removed. Negative electrode substrate with metal film formed on patterned support, secondary battery using the negative electrode substrate, photoresist composition for forming the negative electrode substrate, and manufacturing method of the negative electrode substrate. the

[Invention effect]

According to the present invention, it is possible to provide a negative electrode base material capable of realizing a battery with high output voltage and high energy density and excellent charge-discharge cycle characteristics, a secondary battery with the negative electrode base material, a method for manufacturing the negative electrode base material, A composite film-forming material for forming the negative electrode substrate, a metal oxide film-forming composition for forming the negative electrode substrate, and a photoresist composition for forming the negative electrode substrate. the

Description of drawings

FIG. 1 is a schematic diagram of a negative electrode substrate in Example 1 of the present invention. the

FIG. 2 is a schematic diagram of the negative electrode substrate of Example 2 of the present invention. the

FIG. 3 is a schematic diagram of a negative electrode substrate in Example 3 of the present invention. the

FIG. 4 is a schematic diagram of the negative electrode substrate of Example 4 of the present invention. the

[Description of symbols]

10, 20, 30, 40 negative electrode substrate

11, 21, 31, 41 supports

12, 22 organic film

13, 24, 33, 43 metal film

23 metal oxide film

32 composite film

42 Silica-based coating film

Detailed ways

Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings. the

(first embodiment)

<Negative electrode substrate> 

FIG. 1 shows a schematic view of a negative electrode substrate 10 of the present embodiment. As shown in FIG. 1 , the negative electrode substrate 10 of this embodiment includes: a support 11 , an organic film 12 and a metal film 13 . More specifically, the negative electrode substrate 10 of the present embodiment is characterized in that the metal film 13 is formed by performing a plating process on the support body 11 provided with the organic film 12 . the

<support>

The support 11 used in the negative electrode substrate 10 of the present embodiment is not particularly limited as long as the organic film 12 can be formed on the surface thereof. For example, conventionally well-known supports such as substrates for electronic components can be used. Specifically, a silicon wafer, a silicon wafer provided with an organic or inorganic antireflection film, a silicon wafer formed with a magnetic film, a substrate made of metal such as copper, chromium, iron, or aluminum, or a glass substrate, etc. may be mentioned. In addition, these supports can also serve as current collectors such as materials containing at least one element selected from copper, nickel, stainless steel, molybdenum, tungsten, titanium, and tantalum, metal foils, non-woven fabrics, and metal collectors with three-dimensional structures. It can also be formed on these current collectors. the

<Organic film>

The organic film 12 in the negative electrode substrate 10 of the present embodiment is formed of conventionally known organic compounds or organic resins, and is not particularly limited. The organic film 12 formed of the photoresist composition described below is preferable, and a photoresist pattern patterned into a predetermined shape by pattern exposure is more preferable. the

[Photoresist composition]

The photoresist composition used to form the negative electrode substrate 10 of this embodiment is not particularly limited, and conventionally known photoresist compositions can be used. Photoresist compositions having hydrophilic groups are preferred. As long as the photoresist pattern is formed of a photoresist composition having a hydrophilic group, as described above, a metal oxide that is firmly adhered to the photoresist pattern, has a high density, and has a high mechanical strength can be formed. film13. the

[Positive Photoresist Composition]

As a positive chemically amplified photoresist composition, it is preferable to use a photoresist composition mainly composed of the following components: an acid generator component (hereinafter referred to as (A) component) that generates an acid when irradiated with actinic light or radiation, And the resin component (henceforth (B) component) whose solubility to alkaline aqueous solution changes by the action of an acid. (B) As a component, the hydroxyl group of an alkali-soluble resin is protected by the acid-dissociative dissolution inhibitory group, and the alkali-insoluble resin is used. By using such (B) component in combination with the said (A) component, an acid is generated in an exposed part, and this generated acid dissociates the protection of the said acid-dissociative dissolution inhibitory group. As a result, the exposed portion is alkali-soluble, and only the exposed portion is selectively removed during development to obtain a photoresist pattern of a predetermined shape. the

(Acid Generator Component (A)) 

The (A) component is a substance that generates acid directly or indirectly by irradiating active rays or radiation. the

Examples of the first form of such an acid generator include: 2,4-bis(trichloromethyl)-6-piperonyl-1,3,5-triazine, 2,4-bis(trichloromethyl)- 6-[2-(2-furyl)vinyl]-s-triazine, 2,4-bis(trichloromethyl)-6-[2-(5-methyl-2-furyl)vinyl] -S-triazine, 2,4-bis(trichloromethyl)-6-[2-(5-ethyl-2-furyl)vinyl]-s-triazine, 2,4-bis(trichloromethyl) Base)-6-[2-(5-propyl-2-furyl)vinyl]-s-triazine, 2,4-bis(trichloromethyl)-6-[2-(3,5-di Methoxyphenyl)vinyl]-s-triazine, 2,4-bis(trichloromethyl)-6-[2-(3,5-diethoxyphenyl)vinyl]-s-triazine , 2,4-bis(trichloromethyl)-6-[2-(3,5-dipropoxyphenyl)vinyl]-s-triazine, 2,4-bis(trichloromethyl)- 6-[2-(3-methoxy-5-ethoxyphenyl)vinyl]-s-triazine, 2,4-bis(trichloromethyl)-6-[2-(3-methoxy Base-5-propoxyphenyl)vinyl]-s-triazine, 2,4-bis(trichloromethyl)-6-[2-(3,4-methylenedioxyphenyl)ethenyl ]-triazine, 2,4-bis(trichloromethyl)-6-(3,4-methylenedioxyphenyl)-s-triazine, 2,4-bis-trichloromethyl-6 -(3-bromo-4-methoxy)phenyl-s-triazine, 2,4-bis-trichloromethyl-6-(2-bromo-4-methoxy)phenyl-s-triazine, 2,4-bis-trichloromethyl-6-(2-bromo-4-methoxy)styrylphenyl-s-triazine, 2,4-bis-trichloromethyl-6-(3- Bromo-4-methoxy)styrylphenyl-s-triazine, 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-1,3,5-triazine , 2-(4-methoxynaphthyl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-[2-(2-furyl)vinyl]-4 , 6-bis(trichloromethyl)-1,3,5-triazine, 2-[2-(5-methyl-2-furyl)vinyl]-4,6-bis(trichloromethyl )-1,3,5-triazine, 2-[2-(3,5-dimethoxyphenyl) vinyl]-4,6-bis(trichloromethyl)-1,3,5- Triazine, 2-[2-(3,4-dimethoxyphenyl)vinyl]-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(3, 4-methylenedioxyphenyl)-4,6-bis(trichloromethyl)-1,3,5-triazine, tris(1,3-dibromopropyl)-1,3,5- Halogen-containing triazine compounds such as triazine and tris(2,3-dibromopropyl)-1,3,5-triazine, and tris(2,3-dibromopropyl)isocyanurate, etc. A halogen-containing triazine compound represented by the general formula (a1). the

[chemical 1]

In the general formula (a1), R ^1a , R ^2a , and R ^3a are independent haloalkyl groups, and the number of carbon atoms in the alkyl group is 1-6.

In addition, examples of the second form of the acid generator include α-(p-toluenesulfonyloxyimino)-phenylacetonitrile, α-(benzenesulfonyloxyimino)-2,4-dichlorophenylacetonitrile , α-(benzenesulfonyloxyimino)-2,6-dichlorophenylacetonitrile, α-(2-chlorobenzenesulfonyloxyimino)-4-methoxyphenylacetonitrile, α-( (Ethylsulfonyloxyimino)-1-cyclopentenylacetonitrile, and a compound represented by the following general formula (a2) containing an oximesulfonate group. the

[chemical 2]

In the general formula (a2), R ^4a is a monovalent, divalent or trivalent organic group, in addition, R ^5a is a substituted or unsubstituted saturated hydrocarbon group, an unsaturated hydrocarbon group, or an aromatic compound group, and n is An integer of 1 to 6.

In the general formula (a2), R ^4a is particularly preferably an aromatic compound group. Examples of such aromatic compound groups include aromatic hydrocarbon groups such as phenyl and naphthyl, or heterocyclic groups such as furyl and thienyl. The rings of these groups may have one or more suitable substituents, such as halogen atoms, alkyl groups, alkoxy groups, nitro groups and the like. In addition, R ^5a is particularly preferably a lower alkyl group having 1 to 6 carbon atoms, examples of which include methyl, ethyl, propyl, and butyl.

The acid generator represented by the general formula (a2) is when n=1, R ^4a is any group in phenyl, methylphenyl, methoxyphenyl, R ^5a is methyl Compounds, specifically, α-(methylsulfonyloxyimino)-1-phenylacetonitrile, α-(methylsulfonyloxyimino)-1-(p-methylphenyl)acetonitrile , α-(methylsulfonyloxyimino)-1-(p-methoxyphenyl)acetonitrile, [2-(propylsulfonyloxyimino)-2,3-dihydroxythiophene-3- Subunit] (o-tolyl) acetonitrile, etc. When n=2, specific examples of the acid generator represented by the general formula include acid generators represented by the following chemical formulas (a2-1) to (a2-8).

[chemical 3]

In addition, as the third aspect of the acid generator, an onium salt having a naphthalene ring in the cationic portion can be used. The term "having a naphthalene ring" means having a structure derived from naphthalene, which means a structure including at least two rings, and these rings maintain aromaticity. The naphthalene ring may have a substituent such as a linear or branched alkyl group having 1 to 6 carbon atoms, a hydroxyl group, or a linear or branched alkoxy group having 1 to 6 carbon atoms. The structure derived from the naphthalene ring may be a monovalent group (1 free valence) or a divalent group (2 free valences), and is ideally a monovalent group (however, in this case, it will be combined with the substituent Bonded parts are excluded from counting free valences). The number of naphthalene rings is preferably 1-3. the

The cationic part of the onium salt having a naphthalene ring in such a cationic part preferably has a structure represented by the following general formula (a3). the

[chemical 4]

In the general formula (a3), at least one of R ^6a , R ^7a , and R ^8a is a group represented by the following general formula (a4), and the rest are linear or branched groups with 1 to 6 carbon atoms. A chained alkyl group, an optionally substituted phenyl group, a hydroxyl group, or a linear or branched alkoxy group having 1 to 6 carbon atoms. Alternatively, one of R ^6a , R ^7a , and R ^8a is a group represented by the following general formula (a4), and the remaining two are independently linear or branched chains with 1 to 6 carbon atoms. In the alkylene group, the terminals of these groups may be bonded to form a ring.

[Chemical 5]

In the general formula (a4), R ^9a and R ^10a are each independently a hydroxyl group, a linear or branched alkoxy group with 1 to 6 carbon atoms, or a straight chain with 1 to 6 carbon atoms. A straight-chain or branched-chain alkyl group, R ^11a is a single bond or a straight-chain or branched-chain alkylene group with 1 to 6 carbon atoms that may have a substituent, and p and q are independently 0 or 1 to 2 Integer, p+q is 3 or less. Wherein, when there are a plurality of R ^10a , these R ^10a may be the same as or different from each other. In addition, when a plurality of R ^9a exists, these R ^9a may be the same as or different from each other.

Considering the stability of the compound, among the R ^6a , R ^7a , and R ^8a , the number of groups represented by the general formula (a4) is preferably one, and the rest are groups with 1 to 6 carbon atoms. A straight-chain or branched alkyl group and a phenyl group which may have a substituent may be cyclically bonded at the terminals of these groups. In this case, the two alkylenes contain a sulfur atom to constitute a 3-9 membered ring. The number of atoms (including sulfur atoms) constituting the ring is preferably 5-6.

In addition, examples of the substituent that the alkylene may have include an oxygen atom (in this case, it forms a carbonyl group together with carbon atoms constituting the alkylene), a hydroxyl group, and the like. the

In addition, the substituent that the phenyl group may have includes: a hydroxyl group, a straight-chain or branched alkoxy group having 1 to 6 carbon atoms, or a straight-chain or branched alkoxy group having 1 to 6 carbon atoms. of alkyl etc. the

Among these cation moieties, preferable cation moieties include structures represented by the following chemical formulas (a5) and (a6), and the structure represented by chemical formula (a6) is particularly preferable. the

[chemical 6]

The cationic portion may be an iodonium salt or a sulfonium salt, but is preferably a sulfonium salt from the viewpoint of acid generation efficiency. the

Therefore, an anion that can form a sulfonium salt is more desirable for the anion portion of an onium salt having a naphthalene ring in the preferable cation portion. the

The anion portion of such a photoacid generator is preferably a fluoroalkylsulfonate ion or an arylsulfonate ion in which some or all of the hydrogen atoms are fluorinated. the

The alkyl group in the fluoroalkyl sulfonate ion can be a straight chain, branched chain or ring with 1 to 20 carbon atoms. Considering the volume of the acid produced and its diffusion distance, the alkyl group is preferably The number of carbon atoms is 1-10. In particular, when the alkyl group is branched or cyclic, the diffusion distance is short, so it is preferably used. Specifically, a methyl group, an ethyl group, a propyl group, a butyl group, an octyl group etc. are mentioned as a preferable alkyl group from the point which can synthesize|combine inexpensively. the

The aryl group in the arylsulfonate ion is an aryl group with 6 to 20 carbon atoms, and examples thereof include phenyl and naphthyl groups that may be substituted or unsubstituted by alkyl groups and halogen atoms, and can be synthesized cheaply. , preferably an aryl group having 6 to 10 carbon atoms. Specifically, preferable aryl groups include phenyl, tosyl, ethylphenyl, naphthyl, methylnaphthyl and the like. the

For the fluoroalkylsulfonate ion or arylsulfonate ion, when a part or all of the hydrogen atoms are fluorinated, the fluorination rate is preferably 10 to 100%, more preferably 50 to 100%, especially when all the hydrogen atoms are fluorinated When a fluorine atom is substituted, the strength of the acid becomes stronger, so it is preferably used. Specifically, examples of such fluoroalkylsulfonate ions or arylsulfonate ions include triflate, perfluorobutanesulfonate, perfluorooctylsulfonate, perfluorobenzenesulfonate, and the like. the

Among these, a structure represented by the following general formula (a7) is mentioned as a preferable anion part. the

[chemical 7]

R ^12a SO ₃ ^- (a7)

In the general formula (a7), examples of R ^12a include structures represented by the following general formulas (a8) and (a9), or structures represented by the chemical formula (a10).

[chemical 8]

-C ₁ F _2l+1

(a8) (a9) (a10)

In the general formula (a8), 1 is an integer of 1 to 4, and in the general formula (a9), R ^13a represents a hydrogen atom, a hydroxyl group, a linear or branched alkyl group with 1 to 6 carbon atoms , or a linear or branched alkoxy group having 1 to 6 carbon atoms, m is an integer of 1 to 3. Among them, triflate and perfluorobutanesulfonate are preferable from the viewpoint of safety.

In addition, nitrogen-containing structures represented by the following chemical formulas (a11) and (a12) can also be used for the anion portion. the

[Chemical 9]

In the formulas (a11) and (a12), X ^a1 is a linear or branched alkylene in which at least one hydrogen atom is substituted by a fluorine atom, and the number of carbon atoms in this alkylene is 2 to 6, preferably 3 to 6. 5, the most preferred number of carbon atoms is 3. In addition, X ^a2 and X ^a3 are each independently a linear or branched alkyl group in which at least one hydrogen atom is replaced by a fluorine atom, and the number of carbon atoms in the alkyl group is 1 to 10, preferably 1 to 7, more preferably 1 ~3.

The smaller the number of carbon atoms of the alkylene of X ^a1 or the number of carbon atoms of the alkyl groups of X ^a2 and X ^a3 is, the better the solubility in photoresist solvents is, so it is preferably used.

In addition, the greater the number of hydrogen atoms substituted by fluorine atoms in the alkylene of ^Xa1 or the alkylene of ^Xa2 and ^Xa3 , the stronger the strength of the acid, so it is preferably used. The proportion of fluorine atoms in the alkylene or alkyl group, that is, the fluorination rate, is preferably 70 to 100%, more preferably 90 to 100%, most preferably a perfluoroalkylene or perfluoroalkyl group in which all hydrogen atoms are substituted by fluorine atoms .

Such an onium salt having a naphthalene ring in its cationic portion is preferably a compound of the following chemical formulas (a13) and (a14). the

[chemical 10]

In addition, other forms of the acid generator include: bis(p-toluenesulfonyl)diazomethane, bis(1,1-dimethylethylsulfonyl)diazomethane, bis(cyclohexylsulfonyl)diazomethane , bis(2,4-dimethylphenylsulfonyl)diazomethane and other bissulfonyl diazomethanes; p-toluenesulfonic acid-2-nitrobenzyl ester, p-toluenesulfonic acid-2,6-dinitrate nitrobenzyl ester, nitrobenzyl toluenesulfonate, dinitrobenzyl toluenesulfonate, nitrobenzyl sulfonate, nitrobenzyl carbonate, dinitrobenzyl carbonate and other nitrobenzyl derivatives; Trisphenol Trimesylate, Pyrogallol Trimesylate, Benzyl Tosylate, Benzyl Sulfonate, N-Methylsulfonyloxysuccinimide, N-Trichloromethylsulfonyl Sulfonate such as oxysuccinimide, N-phenylsulfonyloxymaleimide, N-methylsulfonyloxyphthalimide, etc.; N-hydroxyphthaloimide Trifluoromethanesulfonate esters such as formimide and N-hydroxynaphthalimide; diphenyliodonium hexafluorophosphate, (4-methoxyphenyl)phenyliodonium trifluoromethanesulfonate bis(p-tert-butylphenyl)iodonium trifluoromethanesulfonate, triphenylsulfonium hexafluoromethanesulfonate, (4-methoxyphenyl)diphenylsulfonium trifluoromethanesulfonate, Onium salts such as (p-tert-butylphenyl)diphenylsulfonium trifluoromethanesulfonate; benzoin tosylate, α-methylbenzoin tosylate and other benzoin tosylate; other diphenyl iodides Onium salt, triphenylsulfonium salt, phenyldiazonium salt, benzyl carbonate, etc. the

In addition, as the fourth aspect of the acid generator, a compound represented by the following general formula (a15) can be used. the

[chemical 11]

In the formula (a15), X ^a4 represents a sulfur atom or an iodine atom with an atomic valence of s, and s is 1 or 2. n represents a repeating unit of the structure enclosed in parentheses. R ^14a is an organic group bonded to X ^a4 , and represents an aryl group with 6 to 30 carbon atoms, a heterocyclic group with 4 to 30 carbon atoms, an alkyl group with 1 to 30 carbon atoms, or an alkyl group with 1 to 30 carbon atoms. is an alkenyl group with 2 to 30 carbon atoms, or an alkynyl group with 2 to 30 carbon atoms, and R ^14a may be substituted by at least one member selected from the group consisting of the following groups: alkyl, hydroxyl, alkane Oxy, alkylcarbonyl, arylcarbonyl, alkoxycarbonyl, aryloxycarbonyl, arylthiocarbonyl, acyloxy, arylthio, alkylthio, aryl, heterocycle, aryloxy, alkyl Each of sulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, epoxyalkyl group, amino group, cyano group, nitro group, and halogen. The number of R ^14a is s+n(s-1)+1, and R ^14a may be the same as or different from each other. In addition, two or more R ^14a may be directly or via -O-, -S-, -SO-, -SO ₂ -, -NH-, -NR ^15a -, -CO-, -COO-, -CONH -, an alkylene or phenylene group having 1 to 3 carbon atoms is bonded to form a ring structure including ^Xa4 . R ^15a is an alkyl group having 1 to 5 carbon atoms or an aryl group having 6 to 10 carbon atoms.

X ^a5 is a structure represented by the following general formula (a16).

[chemical 12]

In the formula (a16), X ^a7 represents an alkylene group having 1 to 8 carbon atoms, an arylene group having 6 to 20 carbon atoms, or a divalent group of a heterocyclic compound having 8 to 20 carbon atoms , X ^a7 can be selected from an alkyl group with 1 to 8 carbon atoms, an alkoxy group with 1 to 8 carbon atoms, an aryl group with 6 to 10 carbon atoms, a hydroxyl group, a cyano group, and a nitro group. Substituted by at least one of the group consisting of a group and a halogen. X ^a8 represents -O-, -S-, -SO-, -SO ₂ -, -NH-, -NR ^15a -, -CO-, -COO-, -CONH-, alkylene with 1 to 3 carbons or phenylene. n represents the number of repeating units of the structure enclosed in parentheses. The n+1 pieces of X ^a7 and the n pieces of X ^a8 may be the same or different. R ^15a is as defined above.

X ^a6- is the counter ion of onium. The number thereof is n+1 per molecule, at least one of which is a fluorinated alkylfluorophosphate anion represented by the following general formula (a17), and the rest may be other anions.

[chemical 13]

|(R ^16a ) _t PF _6-t | ^- (a17)

In the formula (a17), R ^16a represents an alkyl group in which 80% or more of hydrogen atoms are substituted with fluorine atoms. t represents the number of R ^16a and is an integer of 1-5. The t R ^16a may be the same or different.

Preferred specific examples of the onium ion of the general formula (a15) can be listed: triphenylsulfonium, tri-p-tolylsulfonium, 4-(phenylthio)phenyldiphenylsulfonium, bis[4-(diphenylsulfonium) Sulfonium-yl)phenyl]sulfide, bis[4-{bis[4-(2-hydroxyethoxy)phenyl]sulfonium}phenyl]sulfide, bis{4-[bis(4-fluorobenzene Base)sulfonyl]phenyl}sulfide, 4-(4-benzoyl-2-chlorophenylthio)phenylbis(4-fluorophenyl)sulfonium, 4-(4-benzoylphenylthio ) phenyldiphenylsulfonium, 7-isopropyl-9-oxo-10-thia-9,10-dihydroanthracene-2-yl two-p-tolylsulfonium, 7-isopropyl-9- Oxo-10-thia-9,10-dihydroanthracen-2-yldiphenylsulfonium, 2-[(diphenyl)sulfonyl]thioxanthone, 4-[4-(4-tert-butyl Benzoyl)phenylthio]phenyldi-p-tolylsulfonium, 4-(4-benzoylphenylthio)phenyldiphenylsulfonium, diphenylphenacylsulfonium, 4-hydroxybenzene phenylmethylbenzylsulfonium, 2-naphthylmethyl(1-ethoxycarbonyl)ethylsulfonium, 4-hydroxyphenylmethylphenacylsulfonium, octadecylmethylphenacylsulfonium Sulfonium, diphenyliodonium, bis(p-tolyl)iodonium, bis(4-dodecylphenyl)iodonium, bis(4-methoxyphenyl)iodonium, (4-octyloxy Phenyl)phenyliodonium, bis(4-decyloxy)phenyliodonium, 4-(2-hydroxytetradecyloxy)phenylphenyliodonium, 4-isopropylphenyl(p-toluene base) iodonium, or 4-isobutylphenyl (p-tolyl) iodonium. the

The anion component of the general formula (a15) has at least one fluorinated alkylfluorophosphate anion represented by the general formula (a17). The remaining anionic components may be other anions. Other anions are not particularly limited, and conventionally known anions can be used. Examples include: F ^- , Cr ^- , Br ^- , I ^- and other halogen ions; OH ^- ; ClO ₄ ^- ; FSO ₃ ^- , ClSO ₃ ^- , CH ₃ SO ₃ ^- , C ₆ H ₅ SO ₃ ^- , CF ₃ SO ₃ ^- and other sulfonic acid ions; HSO ₄ ^- , SO ₄ ^2- and other sulfuric acid ions; HCO ₃ ^- , CO ₃ ^2- and other carbonate ions; H ₂ PO ₄ ^- , HPO ₄ ^2- , PO ₄ ^{3 -} and other phosphate ions; PF ₆ ^- , PF ₅ OH ^- and other fluorophosphate ions; BF ₄ ^- , B(C ₆ F ₅ ) ₄ ^- , B(C ₆ H ₄ CF ₃ ) ₄ ^- and other boric acid ions; AlCl ₄ ^- ; and BiF ₆ ^- and the like. In addition, fluoroantimonate ions such as SbF ₆ ^- , SbF ₅ OH ^- , or fluoroarsenic acid ions such as _As F ₆ ^- , A _s F ₅ OH ^- , etc. can also be cited, but these ions contain toxic elements, so they are not good.

In the fluorinated alkyl fluorophosphate anion represented by the general formula (a17), R ^16a represents an alkyl group substituted by a fluorine atom, preferably having 1 to 8 carbon atoms, more preferably 1 to 4 carbon atoms. Specific examples of the alkyl group include linear alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, and octyl; branched alkyl groups such as isopropyl, isobutyl, sec-butyl, and tert-butyl; In addition, cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, etc., the ratio of hydrogen atoms substituted by fluorine atoms in the alkyl group is usually more than 80%, preferably more than 90%, more preferably 100% . When the substitution ratio of fluorine atoms is less than 80%, the acid strength of the fluorinated alkyl fluorophosphate onium salt represented by the general formula (a15) decreases.

R ^16a is particularly preferably a linear or branched perfluoroalkyl group having 1 to 4 carbon atoms and a fluorine atom substitution rate of 100%. Specific examples include: CF ₃ , CF ₃ CF ₂ , (CF ₃ ) ₂ CF, CF ₃ CF ₂ CF ₂ , CF ₃ CF ₂ CF ₂ CF ₂ , (CF ₃ ) ₂ CFCF ₂ , CF ₃ CF ₂ (CF ₃ ) CF, (CF ₃ ) ₃ C. The number t of R ^16a is an integer of 1-5, preferably 2-4, particularly preferably 2 or 3.

Specific examples of preferred fluorinated alkylfluorophosphate anions include [(CF ₃ CF ₂ ) ₂ PF ₄ ] ^- , [(CF ₃ CF ₂ ) ₃ PF ₃ ] ^- , [((CF ₃ ) ₂ CF) ₂ PF ₄ ] ^- , [((CF ₃ ) ₂ CF) ₃ PF ₃ ] ^- , [(CF ₃ CF ₂ CF ₂ ) ₂ PF ₄ ] ^- , [(CF ₃ CF ₂ CF ₂ ) ₃ PF ₃ ] ^- , [((CF ₃ ) ₂ CFCF ₂ ) ₂ PF ₄ ] ^- , [((CF ₃ ) ₂ CFCF ₂ ) ₃ PF ₃ ] ^- , [(CF ₃ CF ₂ CF ₂ CF ₂ ) ₂ PF ₄ ] ^- , or [(CF ₃ CF ₂ CF ₂ ) ₃ PF ₃ ] ^- , among these, [(CF ₃ CF ₂ ) ₃ PF ₃ ] ^- , [(CF ₃ CF ₂ CF ₂ ) ₃ PF ₃ ] ^- , [( (CF ₃ ) ₂ CF) ₃ PF ₃ ] ^- , [((CF ₃ ) ₂ CF) ₂ PF ₄ ] ^- , [((CF ₃ ) ₂ CFCF ₂ ) ₃ PF ₃ ] ^- , or [((CF ₃ ) ₂ CFCF ₂ ) ₂ PF ₄ ] ^- .

Among the fluorinated alkyl fluorophosphate onium salts represented by the general formula (a15), it is particularly preferable to use diphenyl[4-(phenylthio)phenyl]sulfonium trisulfonium represented by the following general formula (a18). Fluorotrifluoroalkylphosphates. the

[chemical 14]

In the formula (a18), u is an integer of 1-8, preferably an integer of 1-4. the

The (A) component acid generator is preferably at least one selected from the general formula (a2) and the general formula (a18). In the general formula (a2), the value of n is preferably 2, and R ^4a is preferably divalent A substituted or unsubstituted alkylene group with a carbon number of 1 to 8, or a substituted or unsubstituted aromatic group. In addition, R ^5a is preferably a substituted or unsubstituted group with a carbon number of 1 to 8 Alkyl, or substituted or unsubstituted aryl.

The above-mentioned (A) components may be used alone or in combination of two or more. the

Moreover, in a positive resist composition, it is preferable that the compounding quantity of (A) component is 0.05-5 mass %. Sufficient sensitivity can be obtained by making the compounding amount of (A) component 0.05 mass % or more, and by making the compounding amount 5 mass % or less, the solubility of this (A) component with respect to a solvent can be improved and a uniform solution to improve storage stability. the

(Resin component (B)) 

The resin component can be a resin comprising at least one of phenolic resin (B1), polyhydroxystyrene resin (B2), and acrylic resin (B3), or it can be a mixed resin or a copolymer. These resin components Solubility with respect to bases is increased by the action of acids. the

[(B1) Phenolic resin] 

As the phenolic resin (B1) whose solubility with respect to alkali increases by the action of an acid, a resin represented by the following general formula (b1) can be used. the

[chemical 15]

In the general formula (b1), R ^1b is an acid dissociative dissolution inhibiting group, R ^2b and R ^3b are each independently a hydrogen atom or an alkyl group with 1 to 6 carbon atoms, and n represents a repeating unit.

In addition, the acid dissociative dissolution inhibiting group represented by R ^1b is preferably a linear, branched or cyclic one having 1 to 6 carbon atoms represented by the following general formula (b2) or (b3): Alkyl, tetrahydropyranyl, tetrafuryl or trialkylsilyl.

[chemical 16]

In the general formula (b2) and general formula (b3), R ^4b and R ^5b are each independently a hydrogen atom or a linear or branched alkyl group with 1 to 6 carbon atoms, and R ^6b is a carbon atom A straight-chain, branched or cyclic alkyl group with a number of 1-10, ^R7b is a straight-chain, branched or cyclic alkyl group with a carbon number of 1-6, and o is 0 or 1 .

In addition, examples of linear or branched alkyl groups having 1 to 6 carbon atoms include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, Isopentyl, neopentyl, and the like, and examples of the cyclic alkyl include cyclopentyl, cyclohexyl, and the like. the

Among them, specifically, the acid dissociative dissolution inhibiting group represented by the general formula (b2) includes methoxyethyl, ethoxyethyl, n-propoxyethyl, isopropoxyethyl , n-butoxyethyl, isobutoxyethyl, tert-butoxyethyl, cyclohexyloxyethyl, methoxypropyl, ethoxypropyl, 1-methoxy-1-methyl -ethyl, 1-ethoxy-1-methylethyl, etc., and examples of the acid-dissociative dissolution-inhibiting group of the formula (b3) include tert-butoxycarbonyl, tert-butoxycarbonylmethyl, and the like. In addition, examples of the trialkylsilyl group include a trialkylsilyl group having 1 to 6 carbon atoms in each alkyl group such as a trimethylsilyl group and a tri-tert-butyldimethylsilyl group. the

[(B2) Polyhydroxystyrene resin] 

As the polyhydroxystyrene resin (B2) whose solubility with respect to alkali increases by the action of an acid, a resin represented by the following general formula (b4) can be used. the

[chemical 17]

In the general formula (b4), R ^8b is a hydrogen atom or an alkyl group having 1 to 6 carbons, R ^9b is an acid dissociative dissolution inhibiting group, and n represents a repeating unit.

In addition, examples of linear or branched alkyl groups having 1 to 6 carbon atoms include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, Isopentyl, neopentyl, and the like, and examples of the cyclic alkyl include cyclopentyl, cyclohexyl, and the like. the

As the acid-dissociative dissolution-inhibiting group represented by R ^9b , the same acid-dissociative dissolution-inhibiting groups as exemplified in the general formulas (b2) and (b3) can be used.

In addition, the polyhydroxystyrene resin (B2) whose solubility with respect to alkali increases by the action of an acid may contain another polymerizable compound as a structural unit in order to control physical and chemical characteristics to an appropriate level. Examples of such polymerizable compounds include well-known radical polymerizable compounds and anion polymerizable compounds. For example, monocarboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid; dicarboxylic acids such as maleic acid, fumaric acid, and methylenesuccinic acid; 2-methacryloyl Oxyethylsuccinic acid, 2-methacryloyloxyethylmaleic acid, 2-methacryloyloxyethylphthalic acid, 2-methacryloyloxyethylhexahydro Methacrylic acid derivatives with carboxyl groups and ester bonds such as phthalic acid; alkyl (meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, and butyl (meth)acrylate Classes; 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate and other hydroxyalkyl (meth)acrylates; phenyl (meth)acrylate, (meth)acrylic acid Aryl (meth)acrylates such as benzyl esters; dicarboxylic acid diesters such as diethyl maleate and dibutyl fumarate; styrene, α-methylstyrene, chlorobenzene Vinyl-containing aromatic compounds such as ethylene, chloromethylstyrene, vinyltoluene, hydroxystyrene, α-methylhydroxystyrene, α-ethylhydroxystyrene; vinyl-containing fats such as vinyl acetate Conjugated dienes such as butadiene and isoprene; polymeric compounds containing nitrile groups such as acrylonitrile and methacrylonitrile; polymeric compounds containing chlorine such as vinyl chloride and vinylidene chloride ; and polymeric compounds containing amide bonds such as acrylamide and methacrylamide. the

[(B3) Acrylic resin] 

As the acrylic resin (B3) whose solubility with respect to alkali increases by the action of an acid, resins represented by the following general formulas (b5) to (b7) can be used. the

[chemical 18]

In the general formulas (b5) to (b7), R ^10b to R ^17b are each independently a hydrogen atom or a linear or branched alkyl group with 1 to 6 carbon atoms, a fluorine atom, or a carbon atom number of A linear or branched fluorinated alkyl group of 1 to 6 (where R ^11b is not a hydrogen atom), and X ^b1 forms a hydrocarbon ring with 5 to 20 carbon atoms together with the carbon atoms bonded to it , X ^b2 is an aliphatic cyclic group or an alkyl group which may have a substituent, n represents a repeating unit, c is 0-4, and d is 0 or 1.

In addition, examples of linear or branched alkyl groups having 1 to 6 carbon atoms include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, Isopentyl, neopentyl, and the like, and examples of the cyclic alkyl include cyclopentyl, cyclohexyl, and the like. In addition, the term "fluorinated alkyl group" means that a part or all of the hydrogen atoms of the alkyl group are replaced by fluorine atoms. the

Regarding the R ^11b , in terms of high contrast, good resolution, depth of focus, and width, the R ^11b is preferably a linear or branched alkyl group with 2 to 4 carbon atoms, and the R ^13b , R ^14b , R ^16b and R ^17b are preferably a hydrogen atom or a methyl group.

The X ^b1 forms an aliphatic cyclic group having 5 to 20 carbon atoms together with the carbon atoms bonded thereto. Specific examples of such aliphatic cyclic groups include groups obtained by removing one or more hydrogen atoms from polycycloalkanes such as monocycloalkanes, bicycloalkanes, tricycloalkanes, and tetracycloalkanes. Specifically, examples include monocyclic alkanes such as cyclopentane, cyclohexane, cycloheptane, and cyclooctane, or adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane. The group obtained after removing more than one hydrogen atom from polycyclic alkanes. Particularly preferred is a group obtained by removing one or more hydrogen atoms from cyclohexane or adamantane (which may further have a substituent).

In addition, when the aliphatic cyclic group of X ^b1 has a substituent on its ring skeleton, examples of the substituent include polar groups such as a hydroxyl group, a carboxyl group, a cyano group, and an oxygen atom (=O). , or a linear or branched lower alkyl group having 1 to 4 carbon atoms. As the polar group, an oxygen atom (=O) is particularly preferred.

Said X ^b2 is an aliphatic cyclic group or an alkyl group, and examples thereof include groups obtained by removing one or more hydrogen atoms from polycycloalkanes such as monocycloalkanes, bicycloalkanes, tricycloalkanes, and tetracycloalkanes. Specifically, examples include monocyclic alkanes such as cyclopentane, cyclohexane, cycloheptane, and cyclooctane, or adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane. Groups that remove more than one hydrogen atom from polycyclic alkanes, etc. Particularly preferred is a group in which one or more hydrogen atoms have been removed from adamantane (it may further have a substituent).

In addition, when the ring skeleton of the aliphatic cyclic group of X ^b2 has a substituent, examples of the substituent include polar groups such as a hydroxyl group, a carboxyl group, a cyano group, and an oxygen atom (=O), or A linear or branched lower alkyl group having 1 to 4 carbon atoms. The polar group is particularly preferably an oxygen atom (=O).

In addition, when X ^b2 is an alkyl group, it is preferably a linear or branched alkyl group having 1 to 20 carbon atoms, preferably 6 to 15 carbon atoms. This alkyl group is particularly preferably an alkoxyalkyl group, and this alkoxyalkyl group can be exemplified: 1-methoxyethyl, 1-ethoxyethyl, 1-n-propoxyethyl, 1-iso Propoxyethyl, 1-n-butoxyethyl, 1-isobutoxyethyl, 1-tert-butoxyethyl, 1-methoxypropyl, 1-ethoxypropyl, 1 -methoxy-1-methyl-ethyl, 1-ethoxy-1-methylethyl and the like.

Preferable specific examples of the acrylic resin represented by the general formula (b5) include acrylic resins represented by the following general formulas (b5-1) to (b5-3). the

[chemical 19]

R ^18b in the general formulas (b5-1) to (b5-3) is a hydrogen atom or a methyl group, and n is a repeating unit.

Preferable specific examples of the acrylic resin represented by the general formula (b6) include acrylic resins represented by the following general formulas (b6-1) to (b6-28). the

[chemical 20]

[chemical 21]

Preferable specific examples of the acrylic resin represented by the general formula (b7) include acrylic resins represented by the following general formulas (b7-1) to (b7-22). the

[chemical 22]

[chemical 23]

[chemical 24]

In addition, the acrylic resin (B3) is preferably a resin containing a copolymer comprising a polymerizable compound further having an ether bond relative to the structural units of the general formulas (b5) to (b7). A structural unit derived from a compound. the

The structural unit is a structural unit derived from a polymerizable compound having an ether bond. Examples of polymerizable compounds having an ether bond include 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, and methoxytriethylene glycol (meth)acrylate , 3-methoxybutyl (meth)acrylate, ethyl carbitol (meth)acrylate, phenoxypolyethylene glycol (meth)acrylate, methoxypolypropylene glycol (meth) Radical polymerizable compounds such as (meth)acrylic acid derivatives having ether bonds and ester bonds such as tetrahydrofurfuryl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, preferably (meth)acrylate-2-methoxyethyl ester, ( 2-Ethoxyethyl Meth)acrylate, Methoxytriethylene Glycol (Meth)acrylate. These compounds can be used alone or in combination of two or more. the

In addition, the acrylic resin (B3) may contain other polymerizable compounds as structural units in order to control physical and chemical properties appropriately. Examples of such polymerizable compounds include well-known radical polymerizable compounds and anion polymerizable compounds. For example, monocarboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid; dicarboxylic acids such as maleic acid, fumaric acid, and methylenesuccinic acid; 2-methacryloyl Oxyethylsuccinic acid, 2-methacryloyloxyethylmaleic acid, 2-methacryloyloxyethylphthalic acid, 2-methacryloyloxyethylhexahydro Methacrylic acid derivatives with carboxyl groups and ester bonds such as phthalic acid; alkyl (meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, and butyl (meth)acrylate Classes; 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate and other hydroxyalkyl (meth)acrylates; phenyl (meth)acrylate, (meth)acrylic acid Aryl (meth)acrylates such as benzyl esters; dicarboxylic acid diesters such as diethyl maleate and dibutyl fumarate; styrene, α-methylstyrene, chlorobenzene Vinyl-containing aromatic compounds such as ethylene, chloromethylstyrene, vinyltoluene, hydroxystyrene, α-methylhydroxystyrene, α-ethylhydroxystyrene; vinyl-containing fats such as vinyl acetate Conjugated dienes such as butadiene and isoprene; polymerizable compounds containing nitrile groups such as acrylonitrile and methacrylonitrile; polymerizable compounds containing chlorine such as vinyl chloride and vinylidene chloride ; and polymeric compounds containing amide bonds such as acrylamide and methacrylamide. the

Furthermore, among the acrylic resin (B3), it is preferable to have a structural unit represented by the general formula (b7), a structural unit derived from a polymerizable compound having an ether bond, a (meth)acrylic acid unit, and A copolymer of structural units composed of alkyl (meth)acrylates. the

Such a copolymer is preferably a copolymer represented by the following general formula (b8). the

[chemical 25]

In the general formula (b8), R ^20b is a hydrogen atom or a methyl group, R ^21b is a linear or branched alkyl or alkoxyalkyl group with 1 to 6 carbon atoms, and R ^22b is a carbon A straight-chain or branched-chain alkyl group having 2 to 4 atoms, and X ^b1 are as defined above.

In addition, in the copolymer represented by the general formula (b8), e, f, and g are expressed in mass ratios, e is 1 to 30% by mass, f is 20 to 70% by mass, and g is 20 to 70% by mass %. the

Moreover, the polystyrene conversion weight average molecular weight of (B) component becomes like this. Preferably it is 10,000-600,000, More preferably, it is 50,000-600,000, More preferably, it is 230,000-550,000. By making the polystyrene-equivalent weight average molecular weight of the component (B) as above, the photoresist film can be kept with sufficient strength without degrading the peelability between the photoresist film and the substrate, and the plating process does not There will be problems with swelling or cracking of the profile. the

Moreover, it is preferable that (B) component is resin whose degree of dispersion is 1.05 or more. Here, the degree of dispersion refers to the value obtained by dividing the weight average molecular weight by the number average molecular weight. By adopting such a degree of dispersion, it is possible to avoid the problem that the photoresist film is stress-resistant to the required plating, or the metal layer obtained by the plating process is easy to expand. the

In the positive photoresist composition, it is preferable that the compounding quantity of such (B) component is 5-60 mass %. the

(Alkali-soluble resin (C)) 

In addition, an alkali-soluble resin can be appropriately compounded in the positive resist composition of this embodiment. Such (C) component is preferably at least one selected from alkali-soluble phenolic resin (C1a), polyhydroxystyrene resin (C1b), acrylic resin (C1c), and vinyl resin (C1d). the

[(C1a) Alkali-soluble phenolic resin]

The alkali-soluble phenolic resin (C1a) preferably has a polystyrene-equivalent weight average molecular weight of 1,000 to 50,000. the

Such a phenolic resin (C1a) can be obtained, for example, by addition-condensing an aromatic compound having a phenolic hydroxyl group (hereinafter simply referred to as "phenols") and aldehydes under an acid catalyst. The phenols used at this time include, for example: phenol, o-cresol, m-cresol, p-cresol, o-ethylphenol, m-ethylphenol, p-ethylphenol, o-butylphenol, m-butylphenol, p-Butylphenol, 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 3,4-xylenol, 3,5-di Cresol, 2,3,5-trimethylphenol, 3,4,5-trimethylphenol, p-phenylphenol, resorcinol, hydroquinone, hydroquinone monomethyl ether, phthalate Trisphenol, phloroglucinol, hydroxybiphenyl, bisphenol A, gallic acid, gallate, α-naphthol, β-naphthol, etc. the

Moreover, examples of aldehydes include formaldehyde, furfural, benzaldehyde, nitrobenzaldehyde, acetaldehyde, and the like. The catalyst during the addition condensation reaction is not particularly limited. For example, if it is an acid catalyst, hydrochloric acid, nitric acid, sulfuric acid, formic acid, oxalic acid, acetic acid, etc. can be used. the

In this embodiment, the flexibility of the resin can be further improved by using ortho-cresol to replace the hydrogen atoms of the hydroxyl groups in the resin with other substituents, or by using bulky aldehydes. the

[(C1b) Alkali-soluble polyhydroxystyrene resin] 

The alkali-soluble polyhydroxystyrene resin (C1b) preferably has a weight average molecular weight of 1,000 to 50,000. the

Examples of the hydroxystyrene compound constituting such a polyhydroxystyrene resin (C1b) include p-hydroxystyrene, α-methylhydroxystyrene, α-ethylhydroxystyrene, and the like. Moreover, the polyhydroxystyrene resin is preferably a copolymer of a hydroxystyrene compound and a styrene resin. The styrene compound constituting this styrene resin can be enumerated: styrene, chlorostyrene, chloromethylstyrene , vinyltoluene, α-methylstyrene, etc. the

[(C1c) Alkali-soluble acrylic resin] 

The alkali-soluble acrylic resin (C1c) preferably has a weight average molecular weight of 50,000 to 800,000. the

The acrylic resin (C1c) preferably contains monomers derived from a polymerizable compound having an ether bond and monomers derived from a polymerizable compound having a carboxyl group. the

Examples of the polymerizable compound having an ether bond include (meth)acrylate-2-methoxyethyl, methoxytriethylene glycol (meth)acrylate, (meth)acrylate-3-methoxy Butyl Ester, Ethyl Carbitol (Meth) Acrylate, Phenoxy Polyethylene Glycol (Meth) Acrylate, Methoxy Polypropylene Glycol (Meth) Acrylate, Tetrahydrofurfuryl (Meth) Acrylate (Meth)acrylic acid derivatives etc. which have an ether bond and an ester bond, 2-methoxyethyl acrylate, and methoxy triethylene glycol acrylate are preferable. These compounds may be used alone or in combination of two or more. the

Examples of the polymerizable compound having a carboxyl group include monocarboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid; dicarboxylic acids such as maleic acid, fumaric acid, and methylenesuccinic acid; Methacryloyloxyethylsuccinic acid, 2-methacryloyloxyethylmaleic acid, 2-methacryloyloxyethylphthalic acid, 2-methacryloyloxy Compounds having a carboxyl group and an ester bond such as ethyl hexahydrophthalic acid, etc., preferably acrylic acid and methacrylic acid. These compounds may be used alone or in combination of two or more. the

[(C1d) Alkali-soluble polyethylene resin] 

The alkali-soluble polyethylene resin (C1d) preferably has a weight average molecular weight of 10,000-200,000, more preferably 50,000-100,000. the

The polyethylene resin (C1d) is poly(ethylene lower alkyl ether), which contains (co) obtained by polymerizing ethylene lower alkyl ether represented by the following general formula (c1) alone or in a mixture of two or more. polymer. the

[chemical 26]

In the general formula (c1), R ^1c is a linear or branched alkyl group having 1 to 6 carbon atoms.

The polyethylene resin (C1d) is a polymer obtained from vinyl compounds. Specifically, such polyethylene resins include: polyvinyl chloride, polystyrene, polyhydroxystyrene, polyvinyl acetate, polyethylene Benzoic acid, polyvinyl methyl ether, polyvinyl ethyl ether, polyvinyl alcohol, polyvinyl pyrrolidone, polyvinyl phenol, and copolymers thereof. Among them, polyvinyl methyl ether is preferable in terms of lowering the glass transition point. the

As for the compounding quantity of such (C) alkali-soluble resin, 5-95 mass parts is preferable with respect to 100 mass parts of said (B) components, More preferably, it is 10-90 mass parts. Crack resistance can be improved by making the blending amount of (C) alkali-soluble resin 5 parts by mass or more, and film reduction during development can be prevented by making the blending amount 95 parts by mass or less. the

(other ingredients)

When used, the positive photoresist composition is preferably used in the form of a solution in which each of the components is dissolved in a solvent. Examples of such solvents include: ketones such as acetone, methyl ethyl ketone, cyclohexanone, methyl isoamyl ketone, and 2-heptanone; ethylene glycol, ethylene glycol monoacetate, diethylene glycol Alcohol, diethylene glycol monoacetate, propylene glycol, propylene glycol monoacetate, dipropylene glycol and dipropylene glycol monoacetate monomethyl ether, monoethyl ether, monopropyl ether, monobutyl ether or monophenyl ether and other polyols and their derivatives; cyclic ethers such as dioxane; ethyl formate, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, methyl acetoacetate, acetyl Ethyl acetate, ethyl pyruvate, ethyl ethoxyacetate, methyl methoxypropionate, ethyl ethoxypropionate, methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, 2- Ethyl hydroxy-2-methylpropionate, methyl 2-hydroxy-3-methylbutyrate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate and other esters; And aromatic hydrocarbons such as toluene and xylene. These solvents may be used alone or in combination of two or more. the

The use amount of these organic solvents is preferably in the range of 30% by mass or more of the solid content concentration in order to make the photoresist layer obtained by using the chemically amplified positive photoresist composition (for example, spin coating method) of this embodiment The film thickness is 1 μm or more. The film thickness of the photoresist layer obtained using the composition of this embodiment is more preferably in the range of 1 μm to 200 μm. the

In the positive chemically amplified photoresist composition, additives with miscibility can be added as needed, for example: addition resins, sensitizers, acid diffusion inhibitors for improving the performance of photoresist films , Adhesive aids, stabilizers, colorants, surfactants and other commonly used additives. the

The organic film 12 in the negative electrode substrate 10 of the present embodiment is preferably an organic film formed of the following positive photoresist composition containing (A2) an alkali-soluble resin and (B2) a quinonediazide group-containing compound, More preferably, the organic film formed from the positive photoresist composition is patterned into a patterned organic film having a predetermined shape by pattern exposure. the

The (A2) component can be listed, for example: in the presence of an acidic catalyst, phenols (phenol, m-cresol, p-cresol, xylenol, trimethylphenol, etc.), and aldehydes (formaldehyde, formaldehyde precursors) , propionaldehyde, 2-hydroxybenzaldehyde, 3-hydroxybenzaldehyde, 4-hydroxybenzaldehyde, etc.) and/or phenolic resins obtained by condensation of ketones (methyl ethyl ketone, acetone, etc.); Hydroxystyrene resins such as polymers, copolymers of hydroxystyrene and other styrene monomers, copolymers of hydroxystyrene and acrylic acid or methacrylic acid or their derivatives; acrylic acid, methacrylic acid, or acrylic acid and methacrylic acid Derivatives of acrylic acid, or acrylic resins such as copolymers of these, etc. the

Especially containing at least two kinds of phenols selected from m-cresol, p-cresol, 3,4-xylenol and 2,3,5-trimethylphenol, and containing at least two kinds of phenols selected from formaldehyde, 2-hydroxybenzene The phenolic resin obtained by condensation reaction of at least one aldehyde among formaldehyde (salicylaldehyde) and propionaldehyde is suitable for preparing a positive photoresist composition with high sensitivity and excellent resolution. (A2) The component can be manufactured according to a normal method. the

The polystyrene-equivalent weight average molecular weight (Mw) of the component (A2) measured by gel permeation chromatography also depends on the type of the component (A2), but it is preferably 2,000 to 100,000, more preferably from the viewpoint of sensitivity and pattern formation. Preferably 3,000 to 30,000. the

In addition, the component (A2) is preferably a phenolic resin (hereinafter, referred to as a classified resin) that is classified into a Mw of 3,000 to 30,000, more preferably 5,000 to 20,000. Using such a graded resin as the component (A2) can obtain a positive-type photoresist composition excellent in heat resistance. The fractionation treatment can be performed, for example, by a fractionation precipitation treatment utilizing molecular weight dependence of polymer solubility. The fractional precipitation treatment is, for example, first dissolving the phenolic resin obtained as a condensation product in a polar solvent, and then adding a poor solvent such as water, heptane, hexane, pentane, or cyclohexane to the solution. At this time, since the low-molecular-weight polymer is always dissolved in the poor solvent, the precipitate can be collected by filtration to obtain a fractionated resin in which the content of the low-molecular-weight polymer is reduced. Examples of polar solvents include alcohols such as methanol and ethanol, ketones such as acetone and methyl ethyl ketone, glycol ether esters such as ethylene glycol monoethyl ether acetate, and cyclic ethers such as tetrahydrofuran. the

The (B2) component is a quinonediazide group-containing compound, especially in terms of high sensitivity, excellent resolution even under low sodium (NA) conditions, and mask linearity or DOF (depth of focus, depth of Focus) is considered, preferably with the following general formula (b2a)

[chemical 27]

[In the general formula (b2a), R ^b1 to R ^b8 independently represent a hydrogen atom, a halogen atom, an alkyl group with 1 to 6 carbon atoms, an alkoxy group with 1 to 6 carbon atoms, or a carbon atom A cycloalkyl group with a number of 3 to 6, R ^b10 and R ^b11 independently represent a hydrogen atom or an alkyl group with a carbon number of 1 to 6, when R ^b9 is a hydrogen atom or an alkyl group with a carbon number of 1 to 6 When, Q ¹ represents a hydrogen atom, an alkyl group with a carbon number of 1 to 6, or the following chemical formula (b2b)

[chemical 28]

[In the general formula (b2b), R ^b12 and R ^b13 independently represent a hydrogen atom, a halogen atom, an alkyl group with 1 to 6 carbon atoms, an alkoxy group with 1 to 6 carbon atoms, or a carbon atom Cycloalkyl group whose number is 3 to 6, c represents an integer of 1 to 3], when Q ¹ and the terminal of R ^b9 are bonded, between Q ¹ and R ^b9 , and between Q ¹ and R ^b9 The carbon atoms together constitute a cycloalkylene chain with a carbon atom chain of 3 to 6, a and b represent an integer of 1 to 3, d represent an integer of 0 to 3, and n represent an integer of 0 to 3] and the compound represented by 1 , The esterification reaction product of 2-naphthoquinonediazidosulfonyl compound (non-benzophenone-based PAC).

Meet the phenolic compound of said general formula (b2a), such as preferred:

[1] Q ¹ is not bonded to the terminal of R ^b9 , R ^b9 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, Q ¹ represents a residue represented by the chemical formula (b2), and n is 0 triphenolic compounds; and

[2] Q ¹ is not bonded to the end of R ^b9 , R ^b9 represents a hydrogen atom or an alkyl group with a carbon number of 1 to 6, Q ¹ represents a hydrogen atom or an alkyl group with a carbon number of 1 to 6, and n is 1 to 6 Integer of 3 linear polyphenol compounds.

More specifically, triphenol-type compounds include tris(4-hydroxyphenyl)methane, bis(4-hydroxy-3-methylphenyl)-2-hydroxyphenylmethane, bis(4-hydroxy-2, 3,5-trimethylphenyl)-2-hydroxyphenylmethane, bis(4-hydroxy-3,5-dimethylphenyl)-4-hydroxyphenylmethane, bis(4-hydroxy-3, 5-Dimethylphenyl)-3-hydroxyphenylmethane, bis(4-hydroxy-3,5-dimethylphenyl)-2-hydroxyphenylmethane, bis(4-hydroxy-2,5- Dimethylphenyl)-4-hydroxyphenylmethane, bis(4-hydroxy-2,5-dimethylphenyl)-3-hydroxyphenylmethane, bis(4-hydroxy-2,5-dimethyl phenyl)-2-hydroxyphenylmethane, bis(4-hydroxy-3,5-dimethylphenyl)-3,4-dihydroxyphenylmethane, bis(4-hydroxy-2,5-di Methylphenyl)-3,4-dihydroxyphenylmethane, bis(4-hydroxy-2,5-dimethylphenyl)-2,4-dihydroxyphenylmethane, bis(4-hydroxyphenyl )-3-methoxy-4-hydroxyphenylmethane, bis(5-cyclohexyl-4-hydroxy-2-methylphenyl)-4-hydroxyphenylmethane, bis(5-cyclohexyl-4- Hydroxy-2-methylphenyl)-3-hydroxyphenylmethane, bis(5-cyclohexyl-4-hydroxy-2-methylphenyl)-2-hydroxyphenylmethane, bis(5-cyclohexyl- 4-hydroxy-2-methylphenyl)-3,4-dihydroxyphenylmethane and the like. the

More specifically, the linear polyphenol compounds include 2,4-bis(3,5-dimethyl-4-hydroxybenzyl)-5-hydroxyphenol, 2,6-bis(2,5-dimethyl Base-4-hydroxybenzyl)-4-methylphenol and other linear trinuclear phenol compounds; 1,1-bis[3-(2-hydroxy-5-methylbenzyl)-4-hydroxy-5-ring Hexylphenyl] isopropane, bis[2,5-dimethyl-3-(4-hydroxy-5-methylbenzyl)-4-hydroxyphenyl]methane, bis[2,5-dimethyl- 3-(4-hydroxybenzyl)-4-hydroxyphenyl]methane, bis[3-(3,5-dimethyl-4-hydroxybenzyl)-4-hydroxy-5-methylphenyl]methane , bis[3-(3,5-dimethyl-4-hydroxybenzyl)-4-hydroxy-5-ethylphenyl]methane, bis[3-(3,5-diethyl-4-hydroxy Benzyl)-4-hydroxy-5-methylphenyl]methane, bis[3-(3,5-diethyl-4-hydroxybenzyl)-4-hydroxy-5-ethylphenyl]methane, Bis[2-hydroxy-3-(3,5-dimethyl-4-hydroxybenzyl)-5-methylphenyl]methane, bis[2-hydroxy-3-(2-hydroxy-5-methyl Benzyl)-5-methylphenyl]methane, bis[4-hydroxy-3-(2-hydroxy-5-methylbenzyl)-5-methylphenyl]methane, bis[2,5-bis Linear tetranuclear phenol compounds such as methyl-3-(2-hydroxy-5-methylbenzyl)-4-hydroxyphenyl]methane; and 2,4-bis[2-hydroxy-3-(4-hydroxy Benzyl)-5-methylbenzyl]-6-cyclohexylphenol, 2,4-bis[4-hydroxy-3-(4-hydroxybenzyl)-5-methylbenzyl]-6-cyclohexyl Linear pentanuclear phenol compounds such as phenol, 2,6-bis[2,5-dimethyl-3-(2-hydroxy-5-methylbenzyl)-4-hydroxybenzyl]-4-methylphenol wait. the

In addition, in addition to triphenol-type compounds and linear polyphenol compounds, phenolic compounds conforming to the general formula (b2a) also include bis(2,3,4-trihydroxyphenyl)methane, bis(2,4-bis Hydroxyphenyl)methane, 2,3,4-trihydroxyphenyl-4'-hydroxyphenylmethane, 2-(2,3,4-trihydroxyphenyl)-2-(2',3',4 '-trihydroxyphenyl) propane, 2-(2,4-dihydroxyphenyl)-2-(2',4'-dihydroxyphenyl)propane, 2-(4-hydroxyphenyl)-2- (4′-hydroxyphenyl)propane, 2-(3-fluoro-4-hydroxyphenyl)-2-(3′-fluoro-4′-hydroxyphenyl)propane, 2-(2,4-dihydroxy Phenyl)-2-(4′-hydroxyphenyl)propane, 2-(2,3,4-trihydroxyphenyl)-2-(4′-hydroxyphenyl)propane, 2-(2,3, 4-trihydroxyphenyl)-2-(4'-hydroxy-3',5'-dimethylphenyl)propane and other bisphenol-type compounds; 1-[1-(4-hydroxyphenyl)isopropyl ]-4-[1,1-bis(4-hydroxyphenyl)ethyl]benzene, 1-[1-(3-methyl-4-hydroxyphenyl)isopropyl]-4-[1,1 -Multinuclear branched compounds such as bis(3-methyl-4-hydroxyphenyl)ethyl]benzene; condensed phenolic compounds such as 1,1-bis(4-hydroxyphenyl)cyclohexane, etc. These phenolic compounds may be used alone or in combination of two or more. the

Among the components (B2), the triphenol-type compound containing bis(5-cyclohexyl-4-hydroxy-2-methylphenyl)-3,4-dihydroxyphenylmethane[ Hereinafter referred to as (B2a)], bis(4-hydroxyl-2,3,5-trimethylphenyl)-2-hydroxyphenylmethane [hereinafter referred to as (B2c)] these three phenolic compounds of naphthoquinone di The photoresist composition of an azide compound is also very excellent in sensitivity and resolution, and thus is preferably used. In addition, if the naphthoquinonediazide esterification of this triphenol type compound is used, the naphthoquinonediazide esterification of other phenolic compounds is used, that is to say, the bisphenol type compound, multinuclear branched type compound and , and naphthoquinone diazide esters of phenolic compounds such as condensed phenolic compounds, a photoresist composition with excellent overall balance of photoresist properties such as resolution, sensitivity, heat resistance, DOF characteristics, and mask linearity can be prepared. , and thus preferred. Bisphenol-type compounds are particularly preferred, and bis(2,4-dihydroxyphenyl)methane [hereinafter abbreviated as (B2b)] is also preferred. In addition, naphthoquinone diazide containing the three phenolic compounds (B2a), (B2c) and (B2b) is preferable because it can form a photoresist pattern with high sensitivity, high resolution, and good shape. A positive type photoresist composition of an ester compound. the

When (B2a) and (B2c) are used, the blending amounts of (B2a) and (B2c) in the (B2) component are preferably 10% by mass or more, more preferably 15% by mass or more, of the total (B2) components. In addition, from the viewpoint of effects, when all of (B2a), (B2b), and (B2c) are used, the compounding amounts of each of the total (B2) components are preferably as follows: the compounding amount of (B2a) is 50 to 90% by mass , preferably 60-80% by mass, the amount of (B2b) is 5-20% by mass, preferably 10-15% by mass, and the amount of (B2c) is 5-20% by mass, preferably 10-15% by mass. the

All or part of the phenolic hydroxyl groups of the compound represented by the general formula (b2a) can be sulfonated with naphthoquinone diazide by a conventional method. For example, the component (B2) can be obtained by condensing naphthoquinonediazidesulfonyl chloride with a compound represented by the general formula (b2a). Specifically, the component (B2) can be prepared, for example, by combining a compound represented by the general formula (b2a) with naphthoquinone-1,2-diazido-4 (or 5 )-sulfonyl chloride is dissolved in an organic solvent such as dioxane, N-methylpyrrolidone, dimethylacetamide, tetrahydrofuran in a predetermined amount, and triethylamine, triethanolamine, pyridine, alkali metal carbonate are added thereto One or more basic catalysts such as alkali metal bicarbonate are reacted, and the obtained product is washed with water and dried. the

As mentioned above, other naphthoquinone diazide esters other than the preferred naphthoquinone diazide esters exemplified above can also be used for component (B2), for example, polyhydroxybenzophenone or gallic acid can also be used. Phenolic compounds such as alkyl esters, esterification reaction products with naphthoquinone diazide sulfonic acid compounds, etc. The usage-amount of these other naphthoquinone diazide ester compounds is preferably 80 mass % or less in (B2) component, Especially preferably, it is 50 mass % or less. the

The amount of component (B2) in the positive resist composition is 20 to 70% by mass, preferably 25 to 60% by mass, based on the total amount of component (A2) and optional component (C2) to be described later. By making the compounding quantity of (B2) component more than the said lower limit, the image faithful to a pattern can be obtained and transferability can be improved. When the compounding quantity of (B2) component is below the said upper limit, the effect that the sensitivity deterioration can be prevented, the homogeneity of the photoresist film formed, and resolution can be improved. the

In the positive photoresist composition, in addition to the components (A2) and (B2), a phenolic hydroxyl group-containing compound having a molecular weight of 1,000 or less as a sensitizer may be further formulated as (C2) Element. This (C2) component is excellent in improving the sensitivity. By using the (C2) component, even under low NA conditions, a material with high sensitivity and high resolution and excellent mask linearity can be obtained. (C2) The molecular weight of a component is 1,000 or less, Preferably it is 700 or less, It is substantially 200 or more, Preferably it is 300 or more. the

The (C2) component is a phenolic hydroxyl-containing compound commonly used in photoresist compositions as a sensitivity improver or a sensitizer. Preferably, there is no particular limitation as long as the molecular weight requirement is met, and one can be selected arbitrarily. or two or more to use. And, wherein preferably with following general formula (c2a)

[chemical 29]

[In the formula, R ^c1 to R ^c8 independently represent a hydrogen atom, a halogen atom, an alkyl group with 1 to 6 carbon atoms, an alkoxy group with 1 to 6 carbon atoms, or an alkoxy group with 3 to 6 carbon atoms. Cycloalkyl, R ^c10 and R ^c11 independently represent a hydrogen atom or an alkyl group with 1 to 6 carbon atoms, when R ^c9 is a hydrogen atom or an alkyl group with 1 to 6 carbon atoms, ^Q2 is a hydrogen atom , an alkyl group having 1 to 6 carbon atoms, or a residue represented by the following chemical formula (c2b)

[chemical 30]

[In the formula, R ^c12 and R ^c13 independently represent a hydrogen atom, a halogen atom, an alkyl group with 1 to 6 carbon atoms, an alkoxy group with 1 to 6 carbon atoms, or an alkoxy group with 3 to 6 carbon atoms. Cycloalkyl, g represents an integer of 0 to 3], when Q ² is bonded to the end of R ^c9 , the carbon atoms between Q ² and R ^c9 and Q ² and R ^c9 together represent a carbon atom chain of 3 to 3 6 cycloalkylene chain, e and f represent an integer of 1 to 3; h represents an integer of 0 to 3; m represents an integer of 0 to 3].

Specifically, as the (C2) component, for example, in addition to the phenolic compound used for the naphthoquinone diazide ester of the phenolic compound exemplified in the (B2) component, bis(3 -Methyl-4-hydroxyphenyl)-4-isopropylphenylmethane, bis(3-methyl-4-hydroxyphenyl)-phenylmethane, bis(2-methyl-4-hydroxyphenyl )-phenylmethane, bis(3-methyl-2-hydroxyphenyl)-phenylmethane, bis(3,5-dimethyl-4-hydroxyphenyl)-phenylmethane, bis(3-ethane Base-4-hydroxyphenyl)-phenylmethane, bis(2-methyl-4-hydroxyphenyl)-phenylmethane, bis(2-tert-butyl-4,5-dihydroxyphenyl)-benzene Triphenyl compounds such as methyl methane. Among them, bis(2-methyl-4-hydroxyphenyl)-phenylmethane, 1-[1-(4-hydroxyphenyl)isopropyl]-4-[1,1-bis(4-hydroxyl) phenyl)ethyl]benzene. the

The compounding quantity of the said (C2) component is the range of 10-70 mass % with respect to the said (A2) component, Preferably it is the range of 20-60 mass %. the

Furthermore, an organic solvent is preferably contained in the positive photoresist composition. The organic solvent is not particularly limited as long as it is a solvent commonly used in photoresist compositions, and one kind or two or more kinds can be selected and used. Specifically, examples of such organic solvents include ketones such as acetone, methyl ethyl ketone, cyclohexanone, methyl isoamyl ketone, and 2-heptanone; ethylene glycol, propylene glycol, diethylene glycol, ethylene glycol, and the like; Glycol monoacetate, propylene glycol monoacetate, diethylene glycol monoacetate, or polyols such as monomethyl ether, monoethyl ether, monopropyl ether, monobutyl ether, or monophenyl ether, and their derivatives substances; cyclic ethers such as dioxane; and methyl acetate, ethyl acetate, butyl acetate, ethyl lactate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate, ethoxypropyl Esters such as ethyl acetate; γ-butyrolactone, etc. the

Among the organic solvents, preferably at least one selected from propylene glycol monomethyl ether, propylene glycol monobutyl ether, propylene glycol monomethyl ether acetate, 2-heptanone, methyl lactate, ethyl lactate and γ-butyrolactone an organic solvent. When using these solvents, it is preferable that these solvents are 50 mass % or less in all organic solvents. the

In addition, the positive photoresist composition may contain compatible additives, such as addition resins, plasticizers, etc. additives, storage stabilizers, surfactants, colorants used to make the developed image more visible, sensitizers or anti-halation dyes used to further improve the sensitization effect, adhesion improvers, etc. of additives. the

Said anti-halation dye can use ultraviolet absorber (such as 2,2',4,4'-tetrahydroxybenzophenone, 4-dimethylamino-2',4'-dihydroxybenzophenone , 5-amino-3-methyl-1-phenyl-4-(4-hydroxyphenylazo)pyrazole, 4-dimethylamino-4′-hydroxyazobenzene, 4-diethylamino -4'-ethoxyazobenzene, 4-diethylaminoazobenzene, curcumin, etc.) and the like. the

The surfactant, for example, can be added to prevent streaks, and for example, Fluorad FC-430, Fluorad FC-431 (trade name, manufactured by Sumitomo 3M Co., Ltd.), and F-Top EF122A, F-Top EF122B, F-Top EF122B, F - Fluorinated surfactants such as Top EF122C and F-Top EF126 (trade name, manufactured by Tohkem Products Co., Ltd.), XR-104, Megafac R-08 (trade name, manufactured by Dainippon Ink Chemical Co., Ltd.), etc. the

[Patterned organic film]

The organic film 12 is formed by coating the positive photoresist composition on the support 11 using a spinner. In addition, the organic film 12 can be formed as a patterned organic film by applying the positive photoresist composition on the support body 11, and then irradiating ultraviolet light, excimer laser (excimer laser) through a mask. ), X-rays, electron beams (electron beam) and other active rays or radiation for image exposure, then heat treatment if necessary, and then perform development treatment using an alkaline developer to dissolve and remove unirradiated parts, and heat as necessary deal with. the

In addition, the aspect ratio of the patterned organic film obtained in this way is preferably 0.1 or more. By making the aspect ratio of the patterned organic film 0.1 or more, the surface area of the negative electrode base material 10 can be increased, and the amount of the metal film formed by the plating treatment described later can be increased, thereby achieving higher output and Higher energy density. the

[Negative Photoresist Composition]

On the other hand, the negative photoresist composition preferably uses an acid generator component (same as component (A)) for generating acid by irradiation with active light or radiation, and a polyfunctional epoxy resin (hereinafter referred to as (D) ) Component) Composition as an essential component. If the component (D) is used in combination with an acid generator, the exposed part becomes alkali-insoluble by cationic polymerization using the acid generated in this part, and only the unexposed part is selectively removed during development, thereby obtaining a light of a predetermined shape. resistance pattern. the

(Multifunctional epoxy resin (D)) 

Although it does not specifically limit about a polyfunctional epoxy resin (D), in order to form a thick pattern, the epoxy resin which has enough epoxy groups in 1 molecule is preferable. This polyfunctional epoxy resin can enumerate: polyfunctional phenol-novolac type epoxy resin, polyfunctional o-cresol novolak type epoxy resin, polyfunctional triphenyl type novolak type epoxy resin, polyfunctional bisphenol A novolak type epoxy resin epoxy resin etc. Among these, polyfunctional bisphenol A novolac epoxy resins are preferably used. The functionality of this polyfunctional bisphenol A novolak type epoxy resin is preferably more than 5 functional, for example, "Epikote 157S70" manufactured by Japan Epoxy Resins (Japan Epoxy Resins) company, "Epiclon" manufactured by Dainippon Ink Chemical Industry Co., Ltd. N-775" is a commercially available product, and it is especially preferably used. the

The polyfunctional bisphenol A novolac epoxy resin is represented by the following general formula (d1). the

[Chemical 31]

The epoxy group of the bisphenol A novolac epoxy resin of formula (d1) may be a polymer polymerized with bisphenol A epoxy resin or bisphenol A novolak epoxy resin. In the formula (d1), R ^1d to r ^6d are H or CH ₃ , and v is a repeating unit.

In the photoresist composition, the content of the multifunctional epoxy resin is preferably 80% by mass to 99.9% by mass, more preferably 92% by mass to 99.4% by mass. Thus, when the photoresist composition is coated on the support 11 , a photoresist film with high sensitivity and appropriate hardness can be obtained. the

(Acid Generator Component (A)) 

As the acid generator component (A), the same acid generator as the acid generator used for the above-mentioned positive resist composition can be used. This acid generator component (A) generates a cationic component by irradiating an active ray or a radiation, and this cationic component functions as a polymerization initiator. the

The said (A) component may be used individually, and may use 2 or more types together. It is preferable that content of the said (A) component is 0.5-20 mass parts with respect to 100 mass parts of said polyfunctional epoxy resins. By making content of (A) component into the said range, sufficient sensitivity can be maintained in a photoresist film, and permanent film characteristic can be maintained. the

(other ingredients)

As with the positive resist composition, conventionally known solvent components can be used for the negative resist composition. In addition, lactone-based solvents such as γ-butyrolactone, β-propiolactone, γ-valerolactone, δ-valerolactone, γ-caprolactone, and ε-caprolactone have the ability to use lactones to form photoresist The heat treatment during patterning opens the ring and reacts with the functional group in the polymer, resulting in the property of being incorporated into the photoresist film, so it is preferably used. Hydroxycarboxylate-based solvents such as alkyl glycolic acid, alkyl lactate, and alkyl 2-hydroxybutyrate have the property of improving coating properties and leveling properties, so they are preferably used conveniently. the

In the negative photoresist composition, an aromatic polycyclic compound having at least two or more substituents capable of crosslinking with the multifunctional epoxy resin can be used as a sensitizer. Utilizing the sensitizing function of the aromatic polycyclic compound, the sensitivity of the photoresist composition can be improved. Specifically, aromatic polycyclic compounds such as naphthalene compounds, binaphthyl compounds, anthracene compounds, and phenanthroline compounds having two or more hydroxyl groups, carboxyl groups, and amino groups are preferably used. Among them, naphthalene compounds are more preferable, and in particular, 1,5-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, and 2,6-dihydroxynaphthalene are preferably used from the viewpoint of improving crosslinking efficiency. the

In addition, in order to improve film-forming properties, the negative photoresist composition may contain a high-molecular linear bifunctional epoxy resin. From the viewpoint of improving the flexibility of the photoresist composition before curing without reducing the physical properties after curing, the negative photoresist composition may contain oxetane derivatives or epoxy resins. derivative. Moreover, the negative photoresist composition may also contain miscible additives as required, such as: addition resins, plasticizers, stabilizers, colorants, surfactants, Conventionally known additives such as coupling agents. the

[Photoresist pattern]

For the positive and negative resist compositions used in this embodiment, for example, a conventional resist pattern forming method using a positive resist composition or a negative resist composition can be applied. Specifically, using a spinner or the like, the photoresist composition prepared in solution is coated on the support body 11 and prebaked to form a photoresist film. Alternatively, a protective film may be used to protect both sides of the photoresist composition to form a dry film, and the dry film may be attached to the support body 11 to form a photoresist film. If it is made into a dry film, the steps of coating and drying on the support body 11 can be omitted, and the photoresist pattern can be formed more simply. the

Next, selectively exposing the photoresist film. Exposure treatment can use g-line, h-line, i-line, KrF excimer laser beam, ArF excimer laser beam, _F2 excimer laser beam, EUV (Extreme ultraviolet), electron beam (EB), soft X-ray , X-rays, etc., can be irradiated through the required mask pattern, or directly written. Preferably a KrF excimer laser beam is used. Next, post-exposure heat treatment (post-exposure bake, hereinafter may also be referred to as PEB (post exposure bake)) is performed. After the PEB treatment, a development treatment is performed using a developer such as an alkaline aqueous solution, and necessary treatments such as washing with water and drying are performed to obtain a resist pattern. The developing solution is not particularly limited, and a conventionally known alkaline aqueous solution or the like can be used.

The heating temperature of prebaking and the heating temperature of post-exposure heating (PEB) are 70-160 degreeC, Preferably it is 100-150 degreeC. The heating time is set in the range of 40 to 180 seconds, preferably in the range of 60 to 90 seconds. In addition, according to circumstances, a post-baking step may be included after the alkali development. the

In addition, the aspect ratio of the photoresist pattern is preferably 0.1 or more. By making the aspect ratio of the photoresist pattern more than 0.1, the surface area of the negative electrode substrate 10 can be increased, and the amount of the metal film formed by the plating process described later can be increased, thus realizing higher output and more high energy density. the

<Metal Film>

The metal film in the negative electrode base material of this embodiment is preferably formed by plating, and is not particularly limited. The plating treatment can be a conventionally known treatment, and is not particularly limited as long as a metal film can be formed on the organic film, composite film, silica-based coating film, or organic film whose surface layer is a metal oxide film. In addition, the metal film may include multiple layers through a multi-stage plating process. The step of forming such a metal film, that is, the plating treatment step is preferably followed by the cleaning step and the catalytic treatment step, followed by an electroless nickel plating or electroless copper plating step, and further includes an electroless tin plating step or an electrolytic tin plating step. the

Hereinafter, the plating process suitable for this embodiment is demonstrated concretely. the

[Cleaning steps]

First, a support having an organic film, a composite film, a silica-based coating film, or an organic film whose surface layer is coated with a metal oxide film is immersed in a phosphoric acid-based solution for cleaning. As the phosphoric acid solution, sodium phosphate or the like is used. The immersion time is preferably 30 to 180 seconds, more preferably 45 to 90 seconds. the

[catalyzed step]

The support that has passed through the cleaning step is immersed in an aqueous solution of tin chloride (SnCl ₂ ) having a predetermined concentration for a predetermined time. The concentration of tin chloride is preferably 0.01 g/dm ³ to 0.10 g/dm ³ , more preferably 0.03 g/dm ³ to 0.07 g/dm ³ . In addition, the immersion time is preferably 15 to 180 seconds, more preferably 30 to 60 seconds.

Next, the support immersed in the tin chloride (SnCl ₂ ) aqueous solution for a predetermined time was immersed in a palladium chloride (PdCl ₂ ) aqueous solution of a predetermined concentration for a predetermined time. The concentration of palladium chloride is preferably 0.01 g/dm ³ to 0.3 g/dm ³ , more preferably 0.03 g/dm ³ to 0.07 g/dm ³ . In addition, the immersion time is preferably 15 to 180 seconds, more preferably 30 to 60 seconds.

[Nickel plating step]

The support body that has passed through the step of catalyzing is dipped in a nickel plating bath and plated with nickel. As the nickel plating bath, conventionally known nickel plating baths can be used. For example, a nickel plating bath containing 0.05M to 0.20M of nickel sulfate, 0.10M to 0.30M of sodium hypophosphite, 0.05ppm to 0.30ppm of lead ions, and 0.05M to 0.30M of a complexing agent can be used. . As the complexing agent, it is preferable to use a carboxylic acid complexing agent. The temperature of the nickel plating bath is preferably 50°C-70°C, and the pH value is preferably 4.0-5.5. Sodium hydroxide, sulfuric acid can be used to adjust the pH value. the

In addition, electroless copper plating may be performed instead of the electroless nickel plating. As the copper plating bath, conventionally known copper plating baths can be used. the

[Non-electrolytic copper plating step] 

Copper plating is carried out by immersing the support body after the catalysis step in a copper plating bath. As the copper plating bath, a conventionally well-known copper plating bath is used. As an example, for example, it can be used containing 0.02M~0.10M copper sulfate, 0.10M~0.40M formalin, 1.0ppm~20.0ppm 2,2'-bipyridyl, 50.0ppm~500ppm surface active Agent (polyethylene glycol, etc.), 0.20M ~ 0.40M complexing agent copper plating bath. As the complexing agent, it is preferable to use a polyethylenepolyamine-based complexing agent. The temperature of the copper plating bath is preferably 50°C-70°C, and the pH value is preferably 11.5-12.5. In addition, stirring is preferably performed by blowing air. Potassium hydroxide, sulfuric acid can be used to adjust the pH. the

[Non-electrolytic tin plating step] 

Immerse the support body that has passed through the steps of electroless nickel plating or electroless copper plating in a tin plating bath to plate tin, so that the organic film, composite film, silicon dioxide-based coating film or surface layer is covered with a metal oxide film A metal film is formed on the covered organic film. As the tin plating bath, conventionally known tin plating baths can be used. For example, reducing agents such as 0.02M to 0.20M tin chloride, 0.02M to 0.08M titanium trichloride, and 0.10M to 0.50M trisodium citrate and ethylenediaminetetraacetic acid can be used. Tin plating bath of disodium (EDTA-2Na), nitrilotriacetic acid (NTA) and other complexing agents. The temperature of the tin plating bath is preferably 45°C-70°C, and the pH value is preferably 6.5-8.5. Sodium carbonate or ammonia and hydrochloric acid can be used to adjust the pH. In addition, it is preferable to perform the tin plating treatment under a nitrogen atmosphere. the

[Electrolytic tin plating step] 

In addition, electrolytic tin plating may be performed instead of the electroless tin plating. In this tin plating step, the support body that has passed through the electroless nickel plating or electroless copper plating step is immersed in a tin plating bath, and electrolytic tin plating is carried out by energizing, thus forming an organic film, a composite film, a carbon dioxide A metal film is formed on a silicon-based coating film or an organic film whose surface layer is coated with a metal oxide film. As the electrolytic tin plating bath, conventionally known electrolytic tin plating baths can be used. By way of example, a plating solution such as the Starter Curumo tin plating bath sold by Leybold Incorporated may be used. The temperature of the tin plating bath is preferably 10°C to 28°C, and the pH value is preferably 1.0 to 1.5. In addition, the applicable current density is preferably 0.5A/dm ² to 6.0A/dm ² .

<Secondary battery>

The negative electrode base material can be suitably used as a negative electrode base material for a secondary battery, especially a negative electrode base material for a lithium secondary battery. Lithium secondary battery is a secondary battery that uses organic solvents and lithium salts as the electrolyte, and realizes charging/discharging through the transfer and reception of charges caused by the movement of lithium ions (Li ⁺ ) between the negative electrode and the positive electrode. It has a high output voltage. , The advantages of high energy density. Conventional lithium secondary batteries have used carbon as the negative electrode and transition metal oxide lithium compounds as the positive electrode. However, in recent years, research has been conducted on negative electrode materials in order to achieve higher output and higher energy density. The negative electrode material is required to be a material capable of forming a thin film and reversibly storing/releasing lithium, and the negative electrode substrate satisfies these requirements and can therefore be suitably used. Here, "occlusion" refers to reversibly encapsulating lithium, forming an alloy, solid solution, etc. with lithium reversibly, or chemically bonding with lithium reversibly.

When utilizing the negative electrode base material as the negative electrode material of the lithium secondary battery, it is necessary to laminate the negative electrode base material on the current collector to form the negative electrode. However, this is not necessary if the support has conductivity, and the support may be used as a current collector. The material and structure of the current collector are not particularly limited as long as it has conductivity. Current collectors used in conventional common lithium secondary batteries can be used. A current collector having good adhesion to the negative electrode substrate is preferred. In addition, a material that does not alloy with lithium is preferable. Specifically, a material containing at least one element selected from the group consisting of copper, nickel, stainless steel, molybdenum, tungsten, titanium, and tantalum is exemplified. In addition, structures such as metal foil, nonwoven fabric, and a metal current collector having a three-dimensional structure are preferable. In particular, metal foil is preferably used, and specifically, copper foil or the like is preferably used. The thickness of the current collector is not particularly limited. the

Generally, a negative electrode formed by laminating a thin-film negative electrode material layer on a current collector can reduce internal resistance compared to a negative electrode formed by laminating a particulate negative electrode material on a current collector together with a binder. . In other words, a lithium secondary battery with high power generation characteristics can be obtained by using a negative electrode formed by laminating the negative electrode base material on a current collector. However, in the negative electrode formed by laminating a thin film-shaped negative electrode material layer on the current collector, the negative electrode material layer has high adhesion to the current collector, so the negative electrode material layer expands/shrinks with charging/discharging, There is a possibility that deformation such as wrinkles may occur in the negative electrode material layer or the current collector. In particular, when a ductile metal foil such as copper foil is used for the current collector, the degree of deformation will further increase. Therefore, simply laminating a thin-film negative electrode material on a current collector may lower the energy density of the battery or deteriorate the charge-discharge cycle characteristics. the

On the other hand, the negative electrode substrate according to this embodiment has a structure in which a metal film is laminated on an organic film, a composite film, a silicon dioxide-based coating film, or an organic film having a metal oxide film on the surface. Stress generated by expansion/contraction due to lithium occlusion/release is relieved solely by the buffering action of the organic film or composite film, silica-based coating film, organic film, and metal oxide film. Therefore, an increase in stress generated during charge/discharge can be suppressed, and as a result, deformation such as wrinkling of the negative electrode base material or the current collector can be suppressed. Furthermore, it is possible to suppress the occurrence of cracks in the negative electrode substrate or peeling off from the current collector. That is, a lithium secondary battery having high output voltage and high energy density and excellent charge-discharge cycle characteristics can be obtained by using the negative electrode formed by laminating the negative electrode base material on the current collector. the

In addition, the configuration other than the negative electrode is not particularly limited, and the same configuration as a conventionally known lithium secondary battery can be employed. Specifically, it mainly includes a positive electrode capable of reversibly storing/releasing lithium, and an electrolyte having lithium conductivity. If necessary, the electrolyte is held by a separator, and lithium is exchanged by bringing the electrolyte held in the separator into contact with the negative electrode and the positive electrode. the

The positive electrode is not particularly limited as long as it can reversibly occlude/release lithium, and a positive electrode generally used in lithium secondary batteries can be used. Specifically, a positive electrode obtained by laminating a positive electrode material layer on a current collector can be used. For example, the positive electrode can be formed by dispersing the positive electrode material, a conductive agent, and a binder in a dispersion solvent to form a slurry, coating the slurry on a current collector, and drying it. The thickness of the current collector and the positive electrode material layer is not particularly limited, and can be set arbitrarily according to the battery design capacity and the like. the

The positive electrode material is also not particularly limited, and conventionally known positive electrode materials such as oxides containing lithium and transition elements can be used. Specifically, LiCoO ₂ , LiNiO ₂ , LiMnO ₂ , LiMn ₂ O ₄ , LiCo _0.5 Ni _0.5 O ₂ and the like can be used. The conductive agent is not particularly limited as long as it is a conductive material, for example, acetylene black, carbon black, graphite powder and the like are used. The binder is not particularly limited as long as it can maintain the shape of the positive electrode material layer after the positive electrode is formed, and a rubber-based binder or a resin-based binder such as a fluororesin can be used.

The material and structure of the separator are not particularly limited as long as it can hold an electrolyte having lithium conductivity and can maintain electrical insulation between the negative electrode and the positive electrode. For example, a porous resin film such as a porous polypropylene film or a porous polyethylene film, or a nonwoven fabric made of a resin containing polyolefin or the like can be used. the

The electrolyte is not particularly limited as long as it has lithium conductivity. For example, a nonaqueous electrolyte solution obtained by dissolving an electrolyte containing lithium in a nonaqueous solvent can be used. As an electrolyte containing lithium, lithium salts such as LiPF ₆ , LiBF ₄ , LiClO ₄ , LiAsF ₆ , and LiCF ₃ SO ₃ are used, for example. Non-aqueous solvents such as propylene carbonate, ethylene carbonate, dimethyl carbonate, ethyl methyl carbonate, diethyl carbonate, γ-butyrolactone, 1,2-dimethoxyethane, 1,2-bis Ethoxyethane, ethoxymethoxyethane, etc. or a mixed solvent of these non-aqueous solvents. The concentration of the non-aqueous electrolyte solution is not particularly limited, and so-called polymer electrolytes, solid electrolytes, and the like can also be used.

A lithium secondary battery using the negative electrode substrate of this embodiment as a negative electrode can be formed in various shapes such as coin-shaped, cylindrical, square, or flat-shaped batteries. In addition, the capacity of the lithium secondary battery is not particularly limited, and it can be applied from small batteries used in precision equipment and the like to large batteries used in hybrid vehicles and the like. the

(Second Embodiment)

<Negative electrode substrate> 

FIG. 2 shows a schematic view of the negative electrode substrate 20 of the present embodiment. As shown in FIG. 2 , the negative electrode substrate 20 of this embodiment includes a support 21 , an organic film 22 whose surface layer is covered with a metal oxide film 23 , and a metal film 24 . More specifically, the negative electrode substrate 20 of the present embodiment is characterized in that the metal film 24 is formed by performing a plating process on the support 21 including the organic film 22 whose surface layer is covered with the metal oxide film 23 . the

<support>

The support body 21 used for the negative electrode base material 20 of this embodiment is the same support body as that of the first embodiment. the

<Organic film>

The organic film 22 in the negative electrode substrate 20 of this embodiment is formed of an organic compound or an organic resin, and is not particularly limited. It is preferably formed of an organic compound having a hydrophilic group or an organic resin having a hydrophilic group. If a hydrophilic group exists on the surface of the organic film 22, the metal oxide film 23 firmly adhered to the organic film 22 can be formed through the interaction of this hydrophilic group with a metal oxide film forming material described later. the

The organic film 22 is preferably an organic film 22 formed of a photoresist composition described later, and more preferably a photoresist pattern patterned into a predetermined shape by pattern exposure. When forming the metal oxide film 23 on the photoresist pattern, if there is a hydrophilic group on the surface of the photoresist pattern, then by the interaction of this hydrophilic group with the metal oxide film forming material described later, the photoresist pattern and the photoresist pattern can be formed. Firmly adhered metal oxide film 23 . That is, a pattern with high density and high mechanical strength can be obtained. the

[Photoresist composition, photoresist pattern] 

When forming the negative electrode substrate 20 of this embodiment, the same photoresist composition and photoresist pattern as those of the first embodiment are used. the

<Metal oxide film>

The metal oxide film 23 covering the surface layer of the organic film 22 is not particularly limited as long as it is formed of a metal oxide. A silica-based coating is preferred. The metal oxide film 23 is formed of a metal oxide film forming material described below. the

[Metal oxide film forming material]

The metal oxide film-forming material of this embodiment is characterized by containing a metal compound capable of generating hydroxyl groups by hydrolysis, and a solvent that dissolves the metal compound and does not have a functional group that reacts with the metal compound. the

[metal compound]

As mentioned above, the metal compound is a compound that can generate a hydroxyl group by hydrolysis. After coating the metal oxide film-forming material containing this metal compound on the organic film 22, or further coating water (preferably deionized water) after coating if necessary, even at a low temperature around room temperature, Metal compounds can also react with moisture in the atmosphere or applied water to generate hydroxyl groups by hydrolysis. Then, the generated hydroxyl groups are dehydrated and condensed to each other, and a plurality of metal compound molecules are bonded to each other, thereby forming a dense metal oxide film 23 with a high film density. In addition, when the organic film 22 has a reactive group such as a carboxyl group or a hydroxyl group, the reactive group of the organic film 22 reacts with the hydroxyl group generated by the metal compound (dehydration condensation, adsorption, etc.), forming metal oxide film 23. the

As the metal compound, for example, a metal compound having a functional group capable of generating a hydroxyl group by hydrolysis, preferably a metal compound in which the functional group is directly bonded to a metal atom is used. The number of functional groups is preferably 2 or more, more preferably 2 to 4, and more preferably 4, per one metal atom. In the case of a metal compound having two or more functional groups per metal atom, the hydroxyl groups generated by hydrolysis are dehydrated and condensed to each other, and a plurality of metal compound molecules are continuously bonded to each other, thereby forming a strong metal oxide film twenty three. the

Examples of functional groups capable of generating hydroxyl groups by hydrolysis include alkoxy groups, isocyanate groups, and carbonyl groups. In addition, since a halogen atom also has the same function, in this embodiment, a halogen group is also included in the said functional group. The alkoxy group can be a straight-chain or branched lower alkoxy group having 1 to 5 carbon atoms. Specifically, methoxy (-O-Me), ethoxy (-O-Et) can be used. , n-propoxy (-O-nPr), isopropoxy (-O-iPr), n-butoxy (-O-nBu), etc. Examples of the halogen atom include a chlorine atom, a fluorine atom, a bromine atom, and an iodine atom, among which a chlorine atom is particularly preferably used. the

When there are reactive groups such as carboxyl groups or hydroxyl groups on the surface of the organic film 22, these reactive groups will undergo condensation reactions with alkoxy groups or isocyanate groups, thereby forming a metal oxide film 23 firmly adhered to the organic film 22, so It is preferred to use. In addition, carbonyl groups or halogen atoms are adsorbed on the organic film 22 by interacting with reactive groups such as carboxyl groups or hydroxyl groups present on the surface of the organic film 22, thereby forming a metal oxide film firmly adhered to the organic film 22. 23, so preferably used. In particular, isocyanate groups and halogen atoms (especially chlorine atoms) are highly reactive and can easily form the metal oxide film 23 without special heat treatment, so they are preferably used, most preferably isocyanate groups. the

Metals constituting the metal compound include boron, silicon, germanium, antimony, selenium, tellurium, and the like, in addition to commonly used metals. Examples of the metal constituting the metal compound include titanium, zirconium, aluminum, niobium, silicon, boron, lanthanum, yttrium, barium, cobalt, iron, zirconium, and tantalum. Among these, titanium and silicon are preferable, and silicon is particularly preferable. In addition, the number of metal atoms in the metal compound may be one, or two or more, but one is preferable. the

The metal compound may have an atom or an organic group other than a functional group capable of generating a hydroxyl group by hydrolysis. For example, hydrogen atoms may be present. The organic group includes, for example, an alkyl group (preferably a lower alkyl group having 1 to 5 carbon atoms), and an ethyl group or a methyl group is preferable. the

Examples of metal compounds having an alkoxy group (hereinafter also referred to as "metal alkoxides") include titanium butoxide (Ti(O-nBu) ₄ ), zirconium propoxide (Zr(O-nPr) ₄ ), butylate Aluminum alkoxide (Al(O-nBu) ₃ ), niobium butoxide (Nb(O-nBu) ₅ ), silicon tetramethoxide (Si(O-Me) ₄ ), boron ethoxide (B(O-Et) ₃ ), etc. Metal alkoxide compounds other than rare earth metals; metal alkoxide compounds of rare earth metals such as lanthanum isopropoxide (Ln(O-iPr) ₃ ) and yttrium isopropoxide (Y(O-iPr) ₃ ); barium titanium alkoxide ( Bisalkoxide compounds such as BaTi(OR ⁶⁰ ) _x ) (in addition, wherein "R ⁶⁰ " is a lower alkyl group with 1 to 5 carbons, and X is an integer of 2 to 4); methyltrimethoxysilane (MESi( O-Me) ₃ ), diethyldiethoxysilane (Et ₂ Si(O-Et) ₂ ) and other metal alkoxide compounds having two or more alkoxy groups and organic groups other than alkoxy groups; A metal alkoxide compound having a ligand such as an acetylacetonate group and having two or more alkoxy groups, etc.

In addition, fine particles of alkoxide sol or alkoxide gel obtained by adding a small amount of water to the metal alkoxides to partially hydrolyze and condense the metal alkoxides may also be used. Further, titanium butoxide tetramer (C ₄ H ₉ O[Ti(OC ₄ H ₉ ) ₂ O] ₄ C ₄ H ₉ ) and other dinuclear or cluster alkoxide compounds with multiple or more metal elements , or polymers based on metal alkoxide compounds that are one-dimensionally crosslinked via oxygen atoms, etc. are also included in the metal alkoxides.

Examples of metal compounds having isocyanate groups include compounds having two or more isocyanate groups represented by the general formula [M(NCO) _x ] (M is a metal atom, and X is an integer of 2 to 4). Specifically, silane tetraisocyanate (Si(NCO) ₄ ), titanium tetraisocyanate (Ti(NCO) ₄ ), zirconium tetraisocyanate (Zr(NCO) ₄ ), triisocyanate Aluminum (Al(NCO) ₃ ), etc.

Metal compounds with halogen atoms can be listed: with the general formula [M(X ₁ ) _n ] (M is a metal atom, X ₁ is selected from a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and n is 2 ∼4) is a metal halide having 2 or more (preferably 2 to 4) halogen atoms. Specifically, titanium tetrachloride (TiCl ₄ ), tetrachlorosilane (SiCl ₄ ), and the like are mentioned. In addition, the metal compound having a halogen atom may be a metal complex, and cobalt chloride (COCl ₂ ) or the like may be used.

Metal compounds having a carbonyl group include metal carbonyl compounds such as titanium oxoacetoacetate (TiO(CH ₃ COCH ₂ COO) ₂ ), iron pentacarbonyl (Fe(CO) ₅ ), and multinuclear clusters of these metal carbonyl compounds.

From the viewpoint of high activity and the fact that the metal oxide film 13 can be easily formed without heat treatment, among the above-mentioned various metal compounds, it is particularly preferable to use a metal compound having 2 or more (preferably 2 to 4) isocyanate groups and/or Or a silicon compound of a halogen atom. The number of silicon in one molecule of the silicon compound may be one or two or more, but one is preferred. Particularly preferred is a compound represented by the general formula [SiWa] (a represents an integer of 2 to 4, W represents an isocyanate group or a halogen atom, and a plurality of W may be the same or different from each other). The a is more preferably 4, and the halogen atom is more preferably a chlorine atom as described above. Among these, silicon compounds having an isocyanate group are particularly preferable. the

In addition, the metal compounds described above may be used alone or in combination of two or more kinds. the

[solvent]

The metal oxide film-forming material of this embodiment is obtained by dissolving the above-mentioned metal compound in a solvent (S). The solvent (S) may be any solvent (S1) as long as it does not have a functional group reactive with the metal compound and can dissolve the metal compound to be used, and conventionally known organic solvents can be used. Examples of the functional group reactive with the metal compound include a group having a carbon-carbon double bond such as a vinyl group, a hydroxyl group, a carboxyl group, a halogen group, and the like. Therefore, as long as the solvent does not have these functional groups, the metal compound can stably exist in the solvent. the

Specifically, the solvent (S1) is preferably an aliphatic compound. Among them, "aliphatic" in this specification is a relative concept to aromatic, and is defined as a group, compound, etc. that do not have aromaticity. That is, "aliphatic compound" refers to a compound that does not have aromaticity. The aliphatic compound may be a chain compound having no ring in its structure, or a cyclic compound having a ring in its structure, preferably a cyclic compound. The cyclic compound is preferably a hydrocarbon compound, more preferably a saturated hydrocarbon compound. Examples of such cyclic compounds include polycycloalkanes such as monocycloalkanes, bicycloalkanes, tricycloalkanes, and tetracycloalkanes, compounds in which substituents such as alkyl groups are bonded to these rings, and the like. the

In addition, the solvent (S1) is preferably a solvent that has less impact on the environment, for example, a solvent whose starting material is a natural substance is preferably used. Solvents whose starting materials are natural substances include terpene-based solvents obtained from essential oil components of plants (for example, monocyclic monoterpenes such as p-menthane, o-menthane, and m-menthane, or pinane and other bicyclic monoterpenes, etc.). the

In addition, it is preferable to use a solvent that does not dissolve the organic film 22 as the solvent (S1). Such a solvent is less likely to damage the shape of the resist pattern especially when the metal oxide film 23 is formed on the surface of the resist pattern. the

It is particularly preferable to use a compound represented by the following general formula (1) as the solvent (s-1) from the viewpoints of no reaction with metal compounds, less impact on the environment, and no dissolution of photoresist patterns. the

[Chemical 32]

[In formula (1), R ²¹ to R ²³ are each independently a hydrogen atom, or a linear or branched alkyl group, and at least two of R ²¹ to R ²³ are alkyl groups, and the alkyl group can be combined with the ring A carbon atom other than the carbon atom bonded to the alkyl group in the hexane ring is bonded to form a ring]

In formula (1), at least two of R ²¹ to R ²³ are linear or branched alkyl groups. That is, two of R ²¹ to R ²³ may be linear or branched alkyl groups, and the other may be a hydrogen atom, or all of R ²¹ to R ²³ may be linear or branched. shaped alkyl. Two of R ²¹ to R ²³ are preferably linear or branched alkyl groups.

The linear or branched alkyl group for R ²¹ to R ²³ is preferably a lower alkyl group having 1 to 5 carbon atoms, more preferably a lower alkyl group having 1 to 3 carbon atoms. Specifically, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, pentyl group, isopentyl group, neopentyl group, etc. are mentioned. Among these, methyl or isopropyl is particularly preferred.

At least two alkyl groups in R ²¹ to R ²³ may be the same or different. Preferably at least one of R ²¹ to R ²³ is a branched alkyl group, more preferably at least one is an isopropyl group. The solvent (s-1) particularly preferably has both isopropyl and methyl groups.

The alkyl groups of R ²¹ to R ²³ may be bonded to carbon atoms other than the carbon atoms bonded to the alkyl groups in the cyclohexane ring to form a ring. Among them, "to form a ring by bonding to a carbon atom other than the carbon atom bonded to the alkyl group in the cyclohexane ring" refers to a group (alkylene) that removes one hydrogen atom from the alkyl group, and A crosslink is formed between a carbon atom bonded to the alkyl group on the cyclohexane ring and a carbon atom other than the carbon atom.

There is no particular limitation on the bonding positions of R ²¹ to R ^23. Preferably, at least two alkyl groups are respectively bonded to the 1-position and 4-position (para-position), or the 1-position and 3-position (meta-position) of the cyclohexane ring. )superior.

Specifically, the compound represented by the above-mentioned formula (1) includes p-menthane (boiling point: about 170°C), m-menthane (boiling point: about 170°C), and o-menthane (boiling point: about 170°C). , pinane (boiling point is about 169 ° C), etc. The structures of these compounds are shown below. Among these, p-menthane is particularly preferred. the

[Chemical 33]

p-menthane m-menthane o-menthane pinane

The solvent (S1) may be used alone or in combination of two or more. In the solvent (S), the ratio of the solvent (S1) is preferably in the range of 50 to 100% by mass, more preferably 80 to 100% by mass, and still more preferably 100% by mass. the

The solvent (S) may contain a solvent (S2) other than the solvent (S1) within the range not impairing the effect of the present invention. As a solvent (S2), methanol, ethanol, propanol, n-hexane, n-heptane, toluene, benzene, cumene, etc. are mentioned, for example. Among them, n-heptane (boiling point: about 98°C) and cumene (boiling point: about 152°C) are preferable because a dense film can be formed. The solvent (S2) may be used alone or in combination of two or more. the

The content of the solvent (S) is not particularly limited, but the molar concentration (the total concentration of the metal compound and the following organic compound used as needed) in the composition for forming a metal oxide film is preferably about 1 to 200 mM, It is preferably used in the range of 50 to 150 mM, more preferably in the range of 50 to 100 mM. If the molar concentration is within this range, a more uniform metal oxide film can be formed, which is preferable. the

[arbitrary ingredients]

The metal oxide film forming material may contain optional components other than the metal compound and the solvent (S). Examples of optional components include organic compounds. By using a metal oxide film-forming material containing an organic compound, a composite film of a metal oxide and an organic compound can be formed. The organic compound is not particularly limited as long as it can be dissolved in the solvent (S). The dissolution mentioned here is not limited to the case where the organic compound can be dissolved alone, but also includes the case where it is dissolved in a solvent such as chloroform by complexing with a metal alkoxide like 4-phenylazobenzoic acid. Also, the molecular weight of the organic compound is not particularly limited. the

From the viewpoint of film strength or the viewpoint of making the adhesion between the metal oxide film and the organic film 22 more firm, the organic compound preferably has a plurality of reactive groups (preferably hydroxyl or carboxyl), and at room temperature (25 ℃) is a solid state. Such organic compounds are preferably used, for example: polymer compounds having hydroxyl or carboxyl groups such as polyacrylic acid, polyvinyl alcohol, polyvinylphenol, polymethacrylic acid, and polyglutamic acid; polysaccharides such as starch, glycogen, and polysialic acid; disaccharides and monosaccharides such as glucose and mannose; and porphyrin compounds or dendrimers with hydroxyl or carboxyl groups at the end, etc. the

In addition, cationic polymer compounds can also be preferably used as the organic compound. Since the metal alkoxides or metal oxides interact as anions with the cations of the cationic polymer compound, strong bonding can be achieved. Specific examples of the cationic polymer compound include: PDDA (polydimethyldiallyl ammonium chloride), polyethyleneimine, polylysine, chitosan, dendrites having amino groups at the end polymer etc. the

These organic compounds function as structural components for forming a thin film with high mechanical strength. In addition, these organic compounds may also function as functional parts for imparting functions to the obtained thin film, or may function as a component that removes molecules of the organic compound after film formation to form in the thin film. Pores corresponding to their molecular shape. An organic compound may be used alone or in combination of two or more. The content of the organic compound is preferably 0.1 to 50 parts by mass, particularly preferably 1 to 20 parts by mass, relative to 100 parts by mass of the metal compound. the

[Formation of metal oxide film]

Using the metal oxide film forming material, a metal oxide film 23 is formed on the organic film 22 . Specifically, after the metal oxide film forming material is coated on the surface of the organic film 22, the surface is washed with an organic solvent and then dried. That is, after the metal oxide film forming material is applied, washing is performed to remove excess metal compounds (for example, metal compounds adhering to the support body 21 ). Then, until the drying is completed, the metal compound is slowly hydrolyzed by moisture in the air to generate hydroxyl groups, and the hydroxyl groups are dehydrated and condensed to form the metal oxide film 23 on the surface of the organic film 22 . When the metal oxide film forming material contains an organic substance, the metal oxide film 23 composed of a composite thin film of the organic substance and the metal oxide is formed. the

Among them, the conventional silicon dioxide-based coating film requires high-temperature treatment such as spin-on-glass (SOG, spin-on-glass) method, so when a photoresist pattern is used as the organic film 22, for example, , the photoresist pattern can become overheated due to high temperature processing. On the other hand, the metal oxide film forming material of this embodiment can form the metal oxide film 23 at a low temperature, so the shape of the photoresist pattern covered by it will not be damaged. In addition, from the viewpoint of controlling the reactivity, it is preferable to perform the operation of forming the metal oxide film 23 under an inert gas atmosphere. At this time, the treatment was performed without utilizing moisture in the air. the

As the coating method of the metal oxide film forming material, a conventionally well-known method can be used, and it is not particularly limited. For example, the method of immersing the support 21 provided with the organic film 22 in the metal oxide film material (dip coating method); or coating the organic film 22 with the metal oxide film forming material by spin coating. Alternatively, the metal oxide film 23 may be formed by a method such as an alternating adsorption method. the

The temperature at which the metal oxide film-forming material is applied to the organic film 22 (coating temperature) varies depending on the activity of the metal compound used, and cannot be uniformly determined, but is usually in the range of 0 to 100°C. In addition, the time from applying the metal oxide film-forming material on the organic film 22 to drying (including coating, washing, and if necessary, adsorption, etc.) is the time between the metal oxide film-forming material and the organic film before hydrolysis. The contact time of the film 12 and the temperature (contact temperature) during this period vary according to the activity of the metal compound used, and cannot be determined uniformly. It is usually several seconds to several hours, and the temperature is at the same temperature as the coating temperature. within range. the

As the organic solvent used for cleaning, the same solvents as those exemplified as the solvent (S) of the metal oxide film forming material can be preferably used. Cleaning can preferably be performed by a method in which an organic solvent is supplied to the surface of the coating film formed of the metal oxide film forming material by a spray method, etc., and then the excess organic solvent is sucked under reduced pressure to clean; Or a method of cleaning by dipping in an organic solvent; a method of cleaning by spraying; a method of cleaning by steam, and the like. The temperature conditions at the time of cleaning are the same as those at the time of coating the metal oxide film forming material. the

After coating the metal oxide film forming material on the surface of the organic film 22, washing is performed to remove excess metal compound on the support 21, thereby forming the metal oxide film 23 with excellent uniformity of film thickness. That is to say, by cleaning, only the metal compound adsorbed on the support body 21 mainly by weak physical adsorption is removed, and only the chemically adsorbed metal compound remains on the surface of the organic film 22 uniformly, so it can be performed with extremely good accuracy and repeatability. It can form nano-scale uniform thin film with high reproducibility. Therefore, the cleaning operation is particularly effective when chemical adsorption occurs between the organic film 22 and the metal compound. the

Wherein, "chemisorption" in this description refers to the formation of chemical bonds (covalent bonds, hydrogen bonds, coordination bonds, etc.) Electrostatic bonding (ionic bonding, etc.), whereby a metal compound or its metal ion is bonded to the surface of the organic film 22 . In addition, "physical adsorption" refers to a state in which a metal compound or its metal ions are bonded to the surface of the organic film 22 by weak intermolecular forces such as van der Waals force. the

The method of drying after washing is not particularly limited, and conventionally known methods can be used. For example, drying gases such as nitrogen can be used, and if the metal oxide film forming material is coated with a spinner, it can be spin-dried directly using a spinner. the

After the metal oxide film-forming material is applied until drying, treatment such as standing may be performed as necessary to promote chemical adsorption and/or chemical adsorption of the organic film 22 and the metal compound in the coating film formed of the metal oxide film-forming material. or physical adsorption. the

After the coating film formed of the metal oxide film-forming material is washed and dried, it may be treated with water, and the coating film may be brought into contact with water to hydrolyze the metal compound on the surface to generate hydroxyl groups. Thereby, the metal oxide film 23 on which a multilayer coating film is laminated can be easily formed, and the thickness of the metal oxide film 23 can be adjusted. That is to say, the hydroxyl group generated on the surface of the coating film formed by the metal oxide film forming material reacts with the metal compound in the coating film formed by further coating the metal oxide film forming material on the coating film to form a strong bond. The metal oxide film 23 on which the multilayer coating film was laminated was obtained. As the method of adding water, a conventionally well-known method can be used, and it is not particularly limited. For example, the most common method is a sol-gel method in which a coating film is brought into contact with water. More specifically, there may be mentioned a method of applying water to the surface of the coating film, or a method of immersing the coating film in an organic solvent containing a small amount of water. In addition, when a metal compound having high reactivity with water is included, it can be hydrolyzed by reacting with water vapor in the air when it is left in the air, so the water addition treatment does not need to be performed. It is preferable to use deionized water in order to prevent mixing of impurities and the like and generate high-purity metal oxides. In addition, by using a catalyst such as an acid or an alkali in the water treatment, the treatment time can be significantly shortened. the

The film thickness of the metal oxide film 23 is not particularly limited. Preferably it is 0.1 nm or more, More preferably, it is 0.5-50 nm, More preferably, it is 1-30 nm. The film thickness of the metal oxide film 23 can be adjusted by repeating application, washing, and water treatment of the metal oxide film forming material. That is to say, it is possible to form a uniform film having a desired thickness by repeating a series of operations of applying a metal oxide film-forming material to form a coating film, washing it, leaving it to stand if necessary, and then performing a hydrolysis treatment. Metal oxide film 23 composed of a thin film. For example, the metal oxide film 23 can be formed with a thickness of several nm to several tens of nm, and a film thickness of several hundred nm depending on conditions, with high precision. the

When a metal oxide film-forming material containing a metal alkoxide containing one metal atom, such as silicon tetraisocyanate or titanium butoxide, is used as the metal compound, several angstroms in thickness can be successively laminated depending on the contact conditions. film. In this case, the increased film thickness per one cycle corresponds to the number of layers of the metal oxide film forming material. On the other hand, if fine particles of alkoxide gel or the like are used as the metal compound, a thin film having a thickness of about 60 nm may be laminated per cycle. In addition, when a coating film formed of a metal oxide film forming material is formed by a spin coating method, the film thickness can be arbitrarily controlled to several nm by changing the concentration of the solvent or metal compound used, the rotation speed, etc. ~200nm or so. Also at this time, by changing the type of the metal compound used for each cycle, the metal oxide film 23 in which thin films made of different types of metal oxides are laminated is obtained. the

In addition, the total film thickness of the organic film 22 and the metal oxide film 23 is not particularly limited, but is preferably 1 μm or less, more preferably 0.7 μm or less, and more preferably 0.5 μm or less. The total lower limit is not particularly limited, but is preferably 0.01 μm or more, more preferably 0.05 μm or more. the

The plating treatment of the negative electrode substrate and the lithium ion secondary battery of the present embodiment are the same as those of the plating treatment and the lithium ion secondary battery of the first embodiment. the

[Third Embodiment]

<Negative electrode substrate> 

FIG. 3 shows a schematic view of the negative electrode substrate 30 of this embodiment. As shown in FIG. 3 , the negative electrode base material 30 of this embodiment includes: a support body 31 , a composite film 32 and a metal film 33 . More specifically, the negative electrode substrate 30 of the present embodiment is characterized in that the metal film 33 is formed on the support body 30 including the composite film 32 . the

<support>

The support body 31 used in the negative electrode base material 30 of this embodiment is the same support body as that of the first embodiment. the

<Composite film>

The composite film 32 in the negative electrode base material 30 of the present embodiment is formed by a composite film forming material containing organic components such as organic compounds or organic resins, and inorganic components such as inorganic compounds or inorganic resins. There is no particular requirement for the composite film forming materials. As a limitation, the composite film 32 is preferably a composite film formed of a composite film forming material described below, and more preferably a patterned composite film patterned into a predetermined shape by pattern exposure. the

[Composite film forming material]

The composite film-forming material used to form the negative electrode substrate 30 of this embodiment is not particularly limited as long as it contains organic components such as organic compounds and organic resins and inorganic components such as inorganic compounds and inorganic resins. the

The inorganic component is not particularly limited as long as it satisfies required transparency with respect to the exposure light at the time of pattern exposure, and examples thereof include glass, ceramics (cordierite, etc.), metals, and the like. More specifically, PbO-SiO ₂ system, PbO-B ₂ O ₃ -SiO ₂ system, ZnO-SiO ₂ system, ZnO-B ₂ O ₃ -SiO ₂ system, BiO-SiO ₂ system, BiO- Glass powders such as lead borosilicate glass, zinc borosilicate glass, and bismuth borosilicate glass of B ₂ O ₃ -SiO ₂ system; cobalt oxide, iron oxide, chromium oxide, nickel oxide, copper oxide, manganese oxide, oxide Neodymium, vanadium oxide, cerium oxide titanium yellow, cadmium oxide, ruthenium oxide, silicon dioxide, magnesium oxide, spinel and other oxides of Na, K, Mg, Ca, Ba, Ti, Zr, Al, etc.; ZnO: Zn, Zn ₃ (PO ₄ ) ₂ : Mn, Y ₂ SiO ₅ : Ce, CaWO ₄ : Pb, BaMgAl ₁₄ O ₂₃ : Eu, ZnS: (Ag, Cd), Y ₂ O ₃ : Eu, Y ₂ SiO ₅ :Eu, Y ₃ Al ₅ O ₁₂ :Eu, YBO ₃ :Eu, (Y,Gd)BO ₃ :Eu,GdBO ₃ :Eu,ScBO ₃ :Eu,LuBO ₃ :Eu,Zn ₂ SiO ₄ :Mn,BaAl ₁₂ O ₁₉ : Mn, SrAl ₁₃ O ₁₉ : Mn, CaAl ₁₂ O ₁₉ : Mn, YBO ₃ : Tb, BaMgAl ₁₄ O ₂₃ : Mn, LuBO ₃ : Tb, GdBO: Tb, ScBO ₃ : Tb, Sr ₆ Si ₃ Phosphors such as O ₃ Cl ₄ :Eu, ZnS:(Cu, Al), ZnS:Ag, Y ₂ O ₂ S:Eu, ZnS:Zn, (Y, Cd)BO ₃ :Eu, BaMgAl ₁₂ O ₂₃ :Eu Powder; metal powder of iron, nickel, palladium, tungsten, copper, aluminum, silver, gold, platinum, etc. Glass, ceramics, etc. are excellent in transparency and are preferable. Among them, when glass powder (glass paste) is used, the most remarkable effect is exhibited, so it is particularly preferable.

The particle size of the inorganic component varies depending on the pattern shape of the composite film at the time of patterning, but the average particle size is preferably 0.5 to 10 μm, preferably 1 to 8 μm. When the average particle diameter is within the above range, surface irregularities will not be generated when forming a high-precision pattern, and exposure light at the time of patterning will not be diffused so that it is difficult for the light to reach the bottom. Examples of the shape of the inorganic component include a spherical shape, a massive shape, a flake shape, a dendritic crystal shape, and the like. These inorganic components may be used alone or in combination of two or more. the

In addition, the inorganic component may be a mixture of fine particles having different physical property values. In particular, shrinkage during firing can be suppressed by using glass powder or ceramic powder having different thermal softening points. Moreover, since the average particle diameter of the inorganic component is 0.5 to 10 μm, in order to prevent its secondary aggregation and improve dispersibility, it is also possible to use organic acids, inorganic Acids, silane coupling agents, titanate-based coupling agents, aluminum-based coupling agents, and surfactants are surface-treated in advance. The surface treatment method is preferably a method of dissolving a treatment agent in an organic solvent or water, adding and stirring an inorganic component, distilling off the solvent, and performing heat treatment at about 50°C to 200°C for 2 hours or more. Moreover, you may add a processing agent when gelatinizing a composite membrane forming material. the

The organic component preferably contains (A3) a water-soluble cellulose derivative, (B3) a photopolymerizable monomer, and (C3) a photopolymerization initiator, and more preferably contains (D3) an acrylic resin having a hydroxyl group. the

[(A3) Water-soluble cellulose derivatives]

The (A3) water-soluble cellulose derivatives are not particularly limited, and specific examples include: carboxymethyl cellulose, hydroxyethyl cellulose, hydroxyethyl methyl cellulose, hydroxypropyl cellulose, ethyl Hydroxyethyl cellulose, carboxymethyl ethyl cellulose, hydroxypropyl methyl cellulose and the like. These water-soluble cellulose derivatives may be used alone or in combination of two or more. The composite film-forming material containing such a water-soluble cellulose derivative as a binder resin has a high transmittance to active rays or radiation such as ultraviolet rays, excimer lasers, X-rays, and electron beams, so it has excellent development resistance. High-precision patterned composite films can be formed. the

[(B3) Photopolymerizable monomer]

The (B3) photopolymerizable monomer is not particularly limited, and specific examples include: ethylene glycol diacrylate, ethylene glycol dimethacrylate, triethylene glycol diacrylate, triethylene glycol diacrylate Methacrylate, Trimethylolpropane Triacrylate, Trimethylolpropane Trimethacrylate, Trimethylolethane Triacrylate, Trimethylolethane Trimethacrylate, Pentaerythritol Diacrylate ester, pentaerythritol dimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, dipentaerythritol tetraacrylate, dipentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate Acrylate, dipentaerythritol pentamethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, glycerol acrylate, glycerol methacrylate, phenolphthalein epoxy diacrylate, will In these exemplary compounds, (meth)acrylate is replaced by fumarate, methylene succinate is replaced by methylene succinate, and maleate is replaced by esters of maleic acid esters, etc. the

[(C3) Photopolymerization Initiator] 

The (C3) photopolymerization initiator is not particularly limited, for example, benzophenones, benzoins, benzoin alkyl ethers, acetophenones, aminoacetophenones, benzils, Benzoin alkyl ethers, benzil alkyl ketals, anthraquinones, ketals, thioxanthones, etc. More specifically, 2,4-bis-trichloromethyl-6-(3-bromo-4-methoxy)phenyl-s-triazine, 2,4-bis-trichloromethyl- 6-(2-bromo-4-methoxy)phenyl-s-triazine, 2,4-bis-trichloromethyl-6-(3-bromo-4-methoxy)styrylphenyl- s-triazine, 2,4-bis-trichloromethyl-6-(2-bromo-4-methoxy)styrylphenyl-s-triazine, 2,4,6-trimethylbenzoyl Diphenylphosphine oxide, 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 2,4-diethylthioxanthone , 2,4-dimethylthioxanthone, 2-chlorothioxanthone, 1-chloro-4-propoxythioxanthone, 3,3-dimethyl-4-methoxybenzophenone, Benzophenone, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 1-(4-dodecylphenyl)-2-hydroxy-2- Methylpropan-1-one, 4-benzoyl-4′-methyldimethylsulfide, 4-dimethylaminobenzoic acid, methyl 4-dimethylaminobenzoate, 4-dimethylaminobenzoate Ethyl aminobenzoate, butyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2-isoamyl 4-dimethylaminobenzoate, 2, 2-diethoxyacetophenone, benzil dimethyl ketal, benzyl-β-methoxyethyl acetal, 1-phenyl-1,2-propanedione-2-(o-ethyl Oxycarbonyl) oxime, methyl phthaloylbenzoate, bis(4-dimethylaminophenyl)ketone, 4,4'-bis(diethylamino)benzophenone, benzil, benzoin , benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin n-butyl ether, benzoin isobutyl ether, p-dimethylaminoacetophenone, p-tert-butyl trichloroacetophenone, p-tert-butyl dichloroacetophenone Ketone, thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, dibenzocycloheptanone, α,α-dichloro-4-phenoxyacetophenone, amyl-4 -Dimethylaminobenzoate, 2-(o-chlorophenyl)-4,5-diphenylimidazolyl dimer, etc. These photopolymerization initiators may be used alone or in combination of two or more kinds. the

The preferred content of the (C3) photopolymerization initiator is 0.1 to 10 parts by mass, more preferably 0.2 to 5 parts by mass. When the photopolymerization initiator is within the above-mentioned range, it is possible to suppress poor bottom curing due to light absorption by the photopolymerization initiator without reducing curability. the

[(D3) Acrylic resin having a hydroxyl group]

(D3) The acrylic resin which has a hydroxyl group can be mix|blended with the said organic component as needed. Examples of such acrylic resins having hydroxyl groups include copolymers obtained by polymerizing monomers having hydroxyl groups as main copolymerizable monomers and other monomers that can be copolymerized with these monomers having hydroxyl groups. . the

The monomer having a hydroxyl group is suitably a monoester compound of acrylic acid or methacrylic acid and a monoalcohol having 1 to 20 carbon atoms. Specifically, hydroxymethyl acrylate, hydroxymethyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxymethacrylate -Hydroxypropyl acrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 2-hydroxybutyl acrylate, 2-hydroxybutyl methacrylate, 3-hydroxybutyl acrylate, methyl 3-hydroxybutyl acrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, etc. In addition, monoesters of acrylic acid or methacrylic acid and a diol having 1 to 10 carbon atoms, or glycerol acrylate, glycerol methacrylate, dipentaerythritol monoacrylate, dipentaerythritol monomethyl Epoxy ester compounds such as acrylate, ε-caprolactone modified hydroxyethyl acrylate, ε-caprolactone modified hydroxyethyl methacrylate, 2-hydroxy-3-phenoxypropyl acrylate. the

Examples of other monomers that can be copolymerized with the monomer having a hydroxyl group include: acrylic acid, methacrylic acid, methylene succinic acid, citraconic acid, methylene succinic acid, maleic acid, trans α, β-unsaturated carboxylic acids such as butenedioic acid, and anhydrides or half-esterified products of these α, β-unsaturated carboxylic acids; methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, acrylic acid n-butyl acrylate, isobutyl acrylate, sec-butyl acrylate, cyclohexyl acrylate, 2-ethylhexyl acrylate, octadecyl acrylate, methyl methacrylate, ethyl methacrylate, methacrylic acid N-propyl, isopropyl methacrylate, sec-propylmethacrylate, n-butyl methacrylate, isobutyl methacrylate, sec-butyl methacrylate, methyl Cyclohexyl acrylate, 2-ethylhexyl methacrylate, octadecyl methacrylate, 2,2,2-trifluoromethyl acrylate, 2,2,2-trifluoromethacrylate α,β-unsaturated carboxylic acid esters such as methyl esters; and styrenes such as styrene, α-methylstyrene, p-vinyltoluene, etc. In addition, acrylonitrile, methacrylonitrile, acrylamide, methacrylamide, vinyl acetate, glycidyl acrylate, glycidyl methacrylate, etc. can also be used. These monomers may be used alone or in combination of two or more kinds. the

The (D3) acrylic resin having a hydroxyl group preferably has a molecular weight of 20,000 or less. More preferably, it is 15,000-5,000, More preferably, it is 12,000-8,000. If the molecular weight exceeds 20,000, the (D3) acrylic resin having a hydroxyl group is preferably 50 parts by mass or less relative to 100 parts by mass of the total of the (A3) water-soluble cellulose derivative and (D3) acrylic resin having a hydroxyl group. the

In addition, the content of (D3) acrylic resin having a hydroxyl group is preferably 50 to 90 parts by mass, more preferably 60 to 80 parts by mass, and most preferably 65 to 75 parts by mass relative to 100 parts by mass of the total resin components in the composite film forming material. share. By making the compounding quantity of (D) component into the said range, all performance, such as the formation precision of a pattern, development resistance, development performance, and development residue generation, can be made favorable, and it is preferable. the

[other]

In addition, in addition to the components (A3) to (D3), the following additives may be appropriately added to the organic component as needed: ultraviolet absorbers, sensitizers, sensitization assistants, polymerization inhibitors, plasticizers, Thickener, organic solvent, dispersant, defoamer, organic or inorganic anti-sedimentation agent, etc. the

A sensitizer is added to increase sensitivity. Specifically, 2,4-diethylthioxanthone, isopropylthioxanthone, 2,3-bis(4-diethylaminobenzylidene)cyclopentanone, 2,6-bis (4-Dimethylaminobenzylidene) cyclohexanone, 2,6-bis(4-dimethylaminobenzylidene)-4-methylcyclohexanone, Michler's ketone, 4,4-bis(diethylamino)-benzophenone, 4,4-bis(dimethylamino)chalcone, 4,4-bis(diethylamino)chalcone, p-dimethyl Aminocinnamylideneindanone, p-Dimethylaminobenzylideneindanone, 2-(p-Dimethylaminophenylvinylidene)-isonaphthothiazole, 1,3-bis(4-dimethyl Aminobenzylidene) acetone, 1,3-carbonyl-bis(4-diethylaminobenzylidene)acetone, 3,3-carbonyl-bis(7-diethylaminocoumarin), N-phenyl -N-ethylethanolamine, N-phenylethanolamine, N-tolyldiethanolamine, N-phenylethanolamine, isoamyl dimethylaminobenzoate, isoamyl diethylaminobenzoate, 3-phenyl -5-benzoylthiotetrazole, 1-phenyl-5-ethoxycarbonylthiotetrazole and the like. These sensitizers may be used alone or in combination of two or more. the

The polymerization inhibitor is added to improve thermal stability during storage. Specifically, hydroquinone, monoesters of hydroquinone, N-nitrosodiphenylamine, phenothiazine, p-tert-butylcatechol, N-phenylnaphthylamine, 2 , 6-di-tert-butyl-p-cresol, tetrachlorobenzoquinone, pyrogallol, etc. the

The purpose of adding plasticizers is to improve the followability of the composite film to the substrate, and phthalates and the like can be used as plasticizers. More specifically, dibutyl phthalate (DBP), dioctyl phthalate (DOP), dicyclohexyl phthalate, polyethylene glycol, glycerol, ditartrate Butyl ester etc. the

The defoaming agent is added to reduce the air bubbles in the composite film forming material or the composite film, and to reduce the porosity after firing. Specifically, alkanediol-based antifoaming agents such as polyethylene glycol (molecular weight: 400 to 800), silicone-based, and higher alcohol-based antifoaming agents may be mentioned. the

The composite film-forming material can be prepared by dissolving or dispersing it in a solvent. The solvent is preferably a solvent that has a high affinity with inorganic components and has good solubility in organic components. In addition, there are no particular limitations on the solvent as long as it can impart moderate viscosity to the composite film forming material and can be easily evaporated and removed by drying. Specifically, ketones such as diethyl ketone, methyl butyl ketone, dipropyl ketone, and cyclohexanone; n-pentanol, 4-methyl-2-pentanol, cyclohexanol, and diacetone Alcohols such as alcohol; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, Ether alcohols such as ethylene glycol dimethyl ether and diethylene glycol diethyl ether; saturated aliphatic monocarboxylic acid alkyl esters such as n-butyl acetate and amyl acetate; lactic acid esters such as ethyl lactate and n-butyl lactate Class; methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethyl-3-ethoxypropionate, acetic acid-2 -Methoxybutyl, 3-methoxybutyl acetate, 4-methoxybutyl acetate, 2-methyl-3-methoxybutyl acetate, 3-methyl-3 -Methoxybutyl, 3-ethyl-3-methoxybutyl acetate, 2-ethoxybutyl acetate, 4-ethoxybutyl acetate, 4-propoxybutyl acetate esters, ether-based esters such as 2-methoxypentyl acetate, etc. These solvents may be used alone or in combination of two or more kinds. the

In order to maintain the viscosity of the composite film-forming material in an appropriate range, the content of the solvent is preferably 300 parts by mass or less with respect to 100 parts by mass of the total of the organic component and the inorganic component. More preferably, it is 10-70 mass parts, More preferably, it is 25-35 mass parts. the

In the composite film-forming material used to form the negative electrode substrate 30 of the present embodiment, the ratio of the organic component to the inorganic powder is preferably 5 to 35 parts by mass relative to the total of 100 parts by mass of the composite film-forming material. parts, and the inorganic component is 95 to 65 parts by mass. More preferably, the organic component is 10-30 mass parts, and the inorganic component is 90-70 mass parts, More preferably, the organic component is 15-25 mass parts, and the inorganic component is 85-75 mass parts. the

[Patterned Composite Film]

For the composite film forming material, methods such as coating it on the support body 31 or screen printing on the support body 31 can be applied. When it is necessary to form a higher-precision pattern, it is preferable to attach and transfer a dry film formed by applying and drying the composite film-forming material to the support body 31 . For coating, an applicator, bar coater, wire bar coater, roll coater, curtain coater, etc. can be used. In particular, a roll coater is preferable because it is excellent in film thickness uniformity and can form a thick film efficiently. the

The composite film formed on the support body 31 by coating or transfer as described above is irradiated with active rays or radiation such as ultraviolet rays, excimer lasers, X-rays, and electron beams through a mask to perform image exposure. Next, a development treatment is performed using an alkaline developer or water to dissolve and remove the unirradiated portion, and if necessary, bake the patterned composite film formed on the support 31 . Alternatively, the entire composite film is exposed without using a mask, a patterned composite film is formed without performing a development treatment, and baking is performed as necessary. To form a higher-precision pattern, the dry film is transferred onto the support body 31, image exposure is performed, and then a development treatment is performed to form a patterned composite film. Alternatively, the entire composite film may be exposed without image exposure, and then a cured coating film may be formed without performing a development treatment, and then baked if necessary. The firing temperature may be any temperature that can burn off the organic components in the composite film forming material, and for example, firing at 400 to 600° C. for 10 to 90 minutes can be selected. That is, the "composite film" and "patterned composite film" of this embodiment also include the film which burnt the organic component. In addition, when transferring the dry film, thermocompression bonding can be performed using a heat roll laminator or the like. As a radiation irradiation device used for exposure, an ultraviolet irradiation device generally used in photolithography, an exposure device used in the manufacture of semiconductors and liquid crystal display devices, and the like can be used. the

The alkaline components of the alkaline developing solution used in the development process include: hydroxides of alkali metals such as lithium, sodium, and potassium; carbonates, bicarbonates, phosphates, and pyrophosphates; primary compounds such as benzylamine and butylamine Amines; secondary amines such as dimethylamine, dibenzylamine, diethanolamine; tertiary amines such as trimethylamine, triethylamine, triethanolamine; cyclic amines such as morpholine, piperazine, pyridine; ethylenediamine, hexamethylenediamine, etc. Amines; ammonium hydroxides such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, trimethylbenzyl ammonium hydroxide, trimethylphenylbenzyl ammonium hydroxide; trimethylsulfonium hydroxide; Sulfonium hydroxides such as trimethylsulfonium hydroxide, diethylmethylsulfonium hydroxide, and dimethylbenzylsulfonium hydroxide; choline, silicate-containing buffers, and the like. In addition, during the development treatment, according to the characteristics of the composite film forming material, the type, composition, concentration, development time, development temperature, and development method (such as dipping method, shaking method, spraying method, spraying method, etc.) of the developing solution are appropriately selected. Stirring method), developing device, etc. the

In addition, the aspect ratio of the patterned composite film obtained in this way is preferably 0.1 or more. By making the aspect ratio of the patterned composite film 0.1 or more, the surface area of the negative electrode substrate 30 can be increased, and the amount of the metal film formed by the plating treatment described later can be increased, thereby realizing higher output and higher output. energy density. the

The plating treatment of the negative electrode substrate and the lithium ion secondary battery of the present embodiment are the same as those of the plating treatment and the lithium ion secondary battery of the first embodiment. the

(Fourth Embodiment)

<Negative electrode substrate> 

FIG. 4 shows a schematic view of a negative electrode substrate 40 of the present embodiment. As shown in FIG. 4 , the negative electrode substrate 40 of the present embodiment includes a support 41 , a silica-based coating film 42 , and a metal film 43 . More specifically, the negative electrode substrate 40 of the present embodiment further includes a metal film 43 on the surface of the support body 41 having the patterned silica-based coating film 42 . the

The negative electrode substrate 40 of this embodiment can be obtained as follows. First, a photoresist pattern is formed on the support body 41 . On the formed resist pattern, a coating liquid for forming a silica-based coating film is applied to form a silica-based coating film. Next, unnecessary photoresist patterns are removed to obtain a patterned silica-based coating film 42 on the support body 41 . Finally, a metal film 43 is formed on the support body 41 having the patterned silica-based coating film 42 . the

<support>

The support body 41 used in the negative electrode substrate 40 of this embodiment is not particularly limited as long as a photoresist pattern or a silica-based coating film 42 can be formed on the surface thereof. For example, conventionally well-known supports such as substrates for electronic components can be used. Specifically, a silicon wafer, a silicon wafer provided with an organic or inorganic antireflection film, a silicon wafer formed with a magnetic film, a substrate made of metal such as copper, chromium, iron, or aluminum, or a glass substrate, etc. may be mentioned. In addition, these supports can also serve as current collectors such as materials containing at least one element selected from copper, nickel, stainless steel, molybdenum, tungsten, titanium, and tantalum, metal foils, non-woven fabrics, and metal collectors with three-dimensional structures. , can also be formed on these current collectors. the

[Photoresist composition, photoresist pattern] 

The photoresist composition and photoresist pattern used to form the negative electrode substrate 40 of this embodiment are the same photoresist composition and photoresist pattern as those of the first embodiment. the

<Silica based coating>

The silica-based coating film 42 in the negative electrode base material 40 of this embodiment is formed of a coating liquid for forming a silica-based coating film. Specifically, after the coating solution for forming a silica-based coating film is applied to the photoresist pattern formed on the negative electrode substrate 40, the silicon dioxide remaining on the support body 41 when the photoresist pattern is removed. A coating film 42 is attached. The coating liquid for forming a silica-based coating film includes a composition for forming a silica-based coating film containing a siloxane polymer and a solvent. the

[Siloxane polymer]

As the siloxane polymer, it is preferable to use a reaction product obtained by subjecting at least one selected from silane compounds represented by the following general formula (I) to a hydrolysis reaction. the

[Chemical 34]

R _4-n Si(OR') _n (I)

In the general formula (I), R represents a hydrogen atom, an alkyl group or a phenyl group, R' represents an alkyl group or a phenyl group, and n represents an integer of 2-4. When multiple R's are bonded to Si, the multiple R's may be the same or different. A plurality of (OR') groups bonded to Si may be the same or different. The alkyl group for R is preferably a linear or branched alkyl group having 1 to 20 carbon atoms, and more preferably a linear or branched alkyl group having 1 to 4 carbon atoms. The alkyl group for R' is preferably a linear or branched alkyl group having 1 to 5 carbon atoms. In particular, the alkyl group as R' preferably has 1 or 2 carbon atoms in view of the hydrolysis rate. the

When n in the general formula (I) is 4, the silane compound (i) is represented by the following general formula (II). the

[Chemical 35]

Si(OR ¹ ) _a (OR ² ) _b (OR ³ ) _c (OR ⁴ ) _d (II)

In the general formula (II), R ¹ , R ² , R ³ and R ⁴ each independently represent the same alkyl group or phenyl group as R'. a, b, c, and d are integers satisfying the conditions of 0≤a≤4, 0≤b≤4, 0≤c≤4, 0≤d≤4, and a+b+c+d=4.

When n in the general formula (I) is 3, the silane compound (ii) is represented by the following general formula (III). the

[Chemical 36]

R ⁵ Si(OR ⁶ ) _e (OR ⁷ ) _f (OR ⁸ ) _g (III)

In the general formula (III), R ⁵ represents a hydrogen atom, the same alkyl group as R, or a phenyl group. R ⁶ , R ⁷ and R ⁸ each independently represent the same alkyl group or phenyl group as R'. e, f, and g are integers satisfying the conditions of 0≤e≤3, 0≤f≤3, 0≤g≤3, and e+f+g=3.

When n in the general formula (I) is 2, the silane compound (iii) is represented by the following general formula (IV). the

[Chemical 37]

R ⁹ R ¹⁰ Si(OR ¹¹ ) _b (OR ¹² ) _i (IV)

In the general formula (IV), R ⁹ and R ¹⁰ represent a hydrogen atom, the same alkyl group or phenyl group as R above. R ¹¹ and R ¹² each independently represent the same alkyl group or phenyl group as R'. h and i are integers satisfying the conditions of 0≤h≤2, 0≤i≤2, and h+i=2.

Specific examples of the silane compound (i) can include: tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, tetrapentoxysilane, tetraphenoxysilane, trimethoxysilane Oxymonoethoxysilane, Dimethoxydiethoxysilane, Triethoxymonomethoxysilane, Trimethoxymonopropoxysilane, Monomethoxytributoxysilane, Monomethoxy Tripentyloxysilane, Monomethoxytriphenoxysilane, Dimethoxydipropoxysilane, Tripropoxymonomethoxysilane, Trimethoxymonobutoxysilane, Dimethoxy Dibutoxysilane, Triethoxymonopropoxysilane, Diethoxydipropoxysilane, Tributoxymonopropoxysilane, Dimethoxymonoethoxymonobutoxysilane, Diethoxymonomethoxymonobutoxysilane, Diethoxymonopropoxymonobutoxysilane, Dipropoxymonomethoxymonoethoxysilane, Dipropoxymonomethoxy Monobutoxysilane, Dipropoxymonoethoxymonobutoxysilane, Dibutoxymonomethoxymonoethoxysilane, Dibutoxymonoethoxymonopropoxysilane, Monomethoxysilane Among tetraalkoxysilanes such as oxymonoethoxymonopropoxymonobutoxysilane, tetramethoxysilane and tetraethoxysilane are preferable. the

Specific examples of the silane compound (ii) include: trimethoxysilane, triethoxysilane, trippropoxysilane, tripentoxysilane, triphenoxysilane, dimethoxymonoethoxy Silane, diethoxymonomethoxysilane, dipentoxymonomethoxysilane, dipentoxymonoethoxysilane, dipentoxymonomethoxysilane, dipentoxymonoethoxysilane Silane, Dipentoxymonopropoxysilane, Diphenoxymonomethoxysilane, Diphenoxymonoethoxysilane, Diphenoxymonopropoxysilane, Methoxyethoxypropoxy Monopropoxydimethoxysilane, Monopropoxydiethoxysilane, Monopropoxydiethoxysilane, Monobutoxydimethoxysilane, Monopentoxydiethoxysilane, Monophenoxydiethoxysilane silane, methyltrimethoxysilane, methyltriethoxysilane, methyltrippropoxysilane, methyltripentoxysilane, ethyltrimethoxysilane, ethyltripropoxysilane, ethyl propyl tripentoxysilane, ethyltriphenoxysilane, propyltrimethoxysilane, propyltriethoxysilane, propyltripentoxysilane, propyltriphenoxysilane, butyltrimethoxysilane butylsilane, butyltriethoxysilane, butyltripropoxysilane, butyltripentoxysilane, butyltriphenoxysilane, methyl monomethoxydiethoxysilane, ethylmono Methoxydiethoxysilane, Propyl Monomethoxydiethoxysilane, Butyl Monomethoxydiethoxysilane, Methyl Monomethoxy Dipropoxysilane, Methyl Monomethoxy Dipentyloxysilane, methyl monomethoxydiphenoxysilane, ethyl monomethoxydipropoxysilane, ethyl monomethoxydipentoxysilane, ethyl monomethoxydipropoxysilane Phenoxysilane, Propyl Monomethoxydipropoxysilane, Propyl Monomethoxydipentoxysilane, Propyl Monomethoxydiphenoxysilane, Butyl Monomethoxydipropoxysilane butyl silane, butyl monomethoxy dipentoxy silane, butyl mono methoxy diphenoxy silane, methyl methoxy ethoxy propoxy silane, propyl methoxy ethoxy propoxy butyl silane, butyl methoxy ethoxy propoxy silane, methyl monomethoxy monoethoxy monobutoxy silane, ethyl mono methoxy monoethoxy monobutoxy silane, propyl monomethyl Oxymonoethoxymonobutoxysilane, butylmonomethoxymonoethoxymonobutoxysilane, etc., among them, trimethoxysilane, triethoxysilane, and methyltrimethoxysilane are preferable. the

Specific examples of the silane compound (iii) include: dimethoxysilane, diethoxysilane, dipropoxysilane, dipentoxysilane, diphenoxysilane, methoxyethoxysilane , Methoxypropoxysilane, Methoxypentoxysilane, Methoxyphenoxysilane, Ethoxypropoxysilane, Ethoxypentoxysilane, Ethoxyphenoxysilane, Methyl Dimethoxysilane, Methylmethoxyethoxysilane, Methyldiethoxysilane, Methylmethoxypropoxysilane, Methylmethoxypentyloxysilane, Methylmethoxy Phenoxysilane, ethyldipropoxysilane, ethylmethoxypropoxysilane, ethyldipentoxysilane, ethyldiphenoxysilane, propyldimethoxysilane, propylmethoxysilane Oxyethoxysilane, Propylethoxypropoxysilane, Propyldiethoxysilane, Propyldipentoxysilane, Propyldiphenoxysilane, Butyldimethoxysilane, Butylmethoxysilane Oxyethoxysilane, Butyldiethoxysilane, Butylethoxypropoxysilane, Butyldipropoxysilane, Butylmethyldipentoxysilane, Butylmethyldiphenoxysilane, Methyldimethoxysilane, Dimethylmethoxyethoxysilane, Dimethyldiethoxysilane, Dimethyldipentoxysilane, Dimethyldiphenoxysilane, Dimethylethyl Oxypropoxysilane, Dimethyldipropoxysilane, Diethyldimethoxysilane, Diethylmethoxypropoxysilane, Diethyldiethoxysilane, Diethylethoxysilane Propyloxysilane, Dipropyldimethoxysilane, Dipropyldiethoxysilane, Dipropyldipentoxysilane, Dipropyldiphenoxysilane, Dibutyldimethoxysilane , Dibutyldiethoxysilane, dibutyldipropoxysilane, dibutylmethoxypentyloxysilane, dibutylmethoxyphenoxysilane, methylethyldimethoxysilane, methyl ethyl Diethoxysilane, methylethyldipropoxysilane, methylethyldipentoxysilane, methylethyldiphenoxysilane, methylpropyldimethoxysilane, methylpropyl Diethoxysilane, methylbutyldimethoxysilane, methylbutyldiethoxysilane, methylbutyldipropoxysilane, methylethylethoxypropoxysilane, ethyl Propyldimethoxysilane, Ethylpropylmethoxyethoxysilane, Dipropyldimethoxysilane, Dipropylmethoxyethoxysilane, Propylbutyldimethoxysilane , propylbutyldiethoxysilane, dibutylmethoxyethoxysilane, dibutylmethoxypropoxysilane, dibutylethoxypropoxysilane, etc., among them, dimethoxysilane, Diethoxysilane, Methyldimethoxysilane, Methyldiethoxysilane. the

Among these silane compounds, a combination of methyltrialkoxysilane and tetraalkoxysilane is preferable. The molar ratio of methyltrialkoxysilane to tetraalkoxysilane is preferably 30:70 to 90:10. the

In addition, the siloxane polymer preferably has a weight average molecular weight within a range of 1,000 to 10,000. This is mainly because it is easy to secure film-forming properties and flatness of the film, and it is also excellent in etching rate resistance. In particular, if the molecular weight is too low, the siloxane polymer will volatilize, and there is a possibility that the film cannot be formed. the

[solvent]

Said solvent can be enumerated: monohydric alcohols such as methanol, ethanol, propanol, butanol; Polyhydric alcohols such as ethylene glycol, diethylene glycol, propylene glycol, glycerol, trimethylolpropane, hexanetriol; Ethylene glycol Monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol Alcohol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether and other polyol monoethers; methyl acetate, ethyl acetate, butyl acetate and other esters; acetone, methyl Ethyl ketone, cycloalkyl ketone, methyl isoamyl ketone and other ketones; ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dipropyl ether, ethylene glycol dibutyl ether, propylene glycol dimethyl ether (PGDM), Propylene Glycol Diethyl Ether, Propylene Glycol Dibutyl Ether, Diethylene Glycol Dimethyl Ether, Diethylene Glycol Methyl Ether, Diethylene Glycol Diethyl Ether, etc. Polyol ethers in which all hydroxyl groups of polyols are alkyl-etherified class etc. Among these, cycloalkyl ketones or alkanediol dialkyl ethers are more preferred. In addition, the alkanediol dimethyl ether is preferably PGDM (propylene glycol dimethyl ether). These organic solvents may be used alone or in combination of two or more. It is preferable that the compounding quantity of the said solvent is the range of 70-99 mass % in the composition for silica-type coating film formation. the

[other]

The composition for forming a silica-based coating film may contain other components than the siloxane polymer and solvent. For example, a cyclic basic compound may also be contained. The cyclic basic compound is preferably a cyclic amine, and more specifically, DBU (1,8-diazabicyclo (5.4.0) undec-7-ene, 1,8-diazabicyclo (5.4 .0) undec-7-ene). the

The added amount of the cyclic basic compound is preferably 10 ppm to 1% relative to the solid content of the siloxane polymer. If the added amount of the cyclic basic compound is within this range, the polymerization of the siloxane polymer can be promoted and the moisture content in the coating film can be reduced. Furthermore, the solution stability of the composition for forming a silica-based coating film improves, and the applicability becomes favorable. the

In addition, the composition for forming a silica-based coating film may contain a pore former. The pore-forming agent refers to a material that decomposes when the coating film formed from the composition for forming a silica-based coating film is fired to form pores in the finally-formed silica-based coating film 42 . Examples of the pore forming agent include polyalkylene glycols and terminal alkylated products of polyalkylene glycols. the

The number of carbon atoms in the alkylene of the polyalkylene glycol is preferably 1-5, more preferably 1-3. Specific examples of polyalkylene glycols include lower alkylene glycols such as polyethylene glycol and polypropylene glycol. the

The terminal alkylate of the polyalkylene glycol refers to the alkoxylation of a single terminal or two terminal hydroxyl groups of the polyalkylene glycol with an alkyl group. The alkyl group used to alkoxylate the terminal may be a linear or branched alkyl group, and the number of carbon atoms in the alkyl group is preferably 1-5, more preferably 1-3. Straight-chain alkyl groups such as methyl, ethyl, and propyl are particularly preferred. the

The weight average molecular weight (Mw) of this polyalkylene glycol is preferably 100 to 10,000, more preferably 200 to 5,000, more preferably 400 to 4,000. When the weight-average molecular weight is not more than the upper limit of the range, good applicability can be obtained without impairing the compatibility of the polyalkylene glycol in the coating solution, and the silica-based coating film 42 The film thickness uniformity is good. By making the weight average molecular weight more than the lower limit of the above-mentioned range, the silica-based coating film 42 can be made porous, thereby achieving a greater buffering effect, which is preferable. the

The amount of the pore forming agent used is preferably 25 to 100% by mass, more preferably 30 to 70% by mass, based on the solid content (mass in terms of SiO ₂ ) of the composition for forming a silica-based coating film. By making the usage amount of the solvent component more than the lower limit value of the above-mentioned range, the silica-based coating film 42 can be made porous, and by making the usage amount thereof not more than the upper limit value of the above-mentioned range, strength can be obtained. Sufficient silica-based coating film 42 .

The silica-based coating film 42 is obtained by applying a coating liquid for forming a silica-based coating film on a support 41 on which a photoresist pattern has been formed, followed by heating, drying, and firing. , remove the photoresist pattern. The coating method of the coating liquid for forming a silica-based coating film is not particularly limited, and any coating method such as a spray method, a spin coating method, a dip coating method, or a roll coating method may be used. the

The heat drying is preferably carried out at 80 to 300° C. for 1 to 6 minutes, and it is more preferable to raise the temperature stepwise in three or more stages. For example, in the air or in an inert gas environment such as nitrogen, dry at 70 to 120°C for 30 seconds to 2 minutes as the first drying treatment, and then dry at 130 to 220°C for 30 seconds to 2 minutes as the second drying treatment. The second drying process is followed by drying at 150 to 300° C. for 30 seconds to 2 minutes as the third drying process. In this way, the surface of the coating film can be made uniform by performing stepwise drying treatment in three or more stages, preferably in about three to six stages. the

In addition, it is preferable to bake at a temperature of about 300 to 400° C. in a nitrogen atmosphere. the

The silicon dioxide-based coating film formed on the upper part of the photoresist pattern can be removed by performing etching treatment (etch-back) or the like on the entire surface of the support as appropriate. In addition, the etching treatment at this time can be performed using a well-known etching method. the

The stripping liquid used for removing the resist pattern is not particularly limited, and conventionally known stripping liquids for resists can be used. For example, any of an organic stripping solution, an aqueous stripping solution, and O ₂ ashing treatment may be used.

The plating treatment of the negative electrode substrate and the lithium ion secondary battery of the present embodiment are the same as those of the plating treatment and the lithium ion secondary battery of the first embodiment. the

[Example]

Hereinafter, the present invention will be described in more detail using examples. However, the present invention is not limited to the following examples. the

<pattern formation>

[Example 1]

100 parts by mass of polyfunctional bisphenol A novolac epoxy resin "Epikote 157S70 (trade name, manufactured by Japan Epoxy Resin Co., Ltd.)", 5 parts by mass of diphenyl[4-(phenylthio)phenyl]sulfonium A mixture of hexafluorophosphate and thiobis-p-phenylene-bis(diphenylsulfonium)-bis(hexafluorophosphate) "UVI-6992 (trade name, manufactured by Dow Chemical Company)", 5 parts by mass Negative photoresist composition 1 was prepared by mixing 1,5-dihydroxynaphthalene and 43 parts by mass of γ-butyrolactone. the

[Example 1a]

After coating this negative resist composition 1 on a silicon wafer using a spin coater, it was dried to obtain a photosensitive resin composition layer having a film thickness of 20 μm. Using a hot plate, the negative photoresist composition layer 1 was prebaked at 60° C. for 5 minutes and at 90° C. for 5 minutes. Then, pattern exposure (soft touch, GHI line) was performed using PLA-501F (contact aligner, manufactured by Canon Inc.), post-exposure heating (PEB) was performed at 90° C. for 5 minutes on a hot plate, and PGMEA was used. method for 4 minutes of development. Next, post-baking the developed resin pattern together with the substrate at 200° C. for 1 hour using an oven, thereby obtaining a columnar photoresist pattern 1 a with a width of 10 μm (a pitch of 20 μm) on the silicon wafer. the

[Example 1b]

In addition, 1 mass part of the compound represented by the following structural formula (z1) (K-1S (trade name), manufactured by San-Apro Corporation), 40 mass parts of the compound represented by the following structural formula (z2) relative to the base Resin whose solubility is increased by the action of an acid, 60 parts by mass of a phenolic resin obtained by addition condensation of m-cresol and p-cresol in the presence of formaldehyde and an acid catalyst, and 1 part by mass of 1,5 -Dihydroxynaphthalene, uniformly dissolved in propylene glycol monomethyl ether acetate, filtered through a filter membrane with a pore size of 1 μm, to prepare a positive photoresist composition with a solid content mass concentration of 40% by mass, using the same The same method was used to form the pattern of the negative photoresist composition, and a columnar photoresist pattern 1b with a width of 10 μm (a pitch of 20 μm) was obtained on the silicon wafer. the

[Chemical 38]

[Example 1c]

Mixed phenols using m-cresol/p-cresol/2,3,5-trimethylphenol=40/35/25 (molar ratio) as component (A), and salicylaldehyde/formaldehyde=1/ 13 g of a phenolic resin with Mw = 5,200 synthesized by a conventional method using a mixture of aldehydes of 5 (molar ratio), and 1 mole of bis(5-cyclohexyl-4-hydroxy-2-methylphenyl) as component (B) )-3,4-dihydroxyphenylmethane (B1) and 2 moles of 1,2-naphthoquinonediazido-5-sulfonyl chloride [hereinafter referred to as (5-NQD)] esterification reaction product, The esterification reaction product of 1 mole of bis(2,4-dihydroxyphenyl)methane (B2) and 2 moles of 5-NQD, and 1 mole of bis(4-hydroxy-2,3,5-trimethyl Phenyl)-2-hydroxyphenylmethane (B3) and 7.5g (mass mixing ratio=B1:B2:B3=4:1:1) of the mixture of the esterification reaction product of 2 moles of 5-NQD, as (C ) component of bis(2-methyl-4-hydroxyphenyl)-phenylmethane 5.5 g and propylene glycol monomethyl ether acetate solvent 74 g were mixed to prepare a positive photoresist composition. the

This positive photoresist composition was coated on a silicon wafer and prebaked to form an organic film with a film thickness of 1.48 μm. This organic film was selectively exposed using an i-line exposure device (product name "NSR-2005i10D", manufactured by Tokyo Ohka Industry Co., Ltd.), and then, using a concentration of 2.38% by mass of tetramethylammonium hydroxide aqueous solution (product name "NMD-3", manufactured by Tokyo Ohka Industry Co., Ltd.) was developed for 60 seconds, rinsed with pure water for 30 seconds, and then dried to form a columnar patterned organic pattern with a width of 5 μm (a pitch of 20 μm). Membrane 1c. the

[Example 2a]

A photoresist pattern was formed in the same manner as in Example 1a except that no metal oxide film was formed. On the other hand, silane tetraisocyanate (Si(NCO) ₄ ) was dissolved in p-menthane so as to be 100 mM to prepare a metal oxide film-forming material. By spin coating (coating with 100rpm for 10 seconds), after this metal oxide film forming material is coated on the photoresist pattern uniformly, wash (wash with 500rpm for 10 seconds) with p-menthane, and then Drying was performed at 2000 rpm for 10 seconds, and at 3000 rpm for 10 seconds. As a result, a photoresist pattern 2 a in which a uniform covering layer (silicon oxide film (SiO ₂ )) was formed on the surface of the photoresist pattern was obtained. This coating layer is an ultra-thin film with a film thickness of about 1 nm.

[Example 2b]

The photoresist pattern 2b was formed by the same method as Example 2a except having used the photoresist pattern 1b. the

[Example 3]

Using a stirrer, 5 parts by mass of hydroxypropyl cellulose as a water-soluble cellulose derivative, styrene/hydroxyethyl methacrylate=60/40 (mass %) copolymer (Mw =30000) 5 parts by mass, 15 parts by mass of acrylate-2-hydroxyl-3-phenoxypropyl ester (trade name M-600A, manufactured by Kyoeisha Chemical Co., Ltd.) as a photopolymerizable monomer, as a photopolymerizable 1.0 parts by mass of 2,2-dimethoxy-2-phenylacetophenone (trade name IR-651, manufactured by Ciba-Geigy Company) of initiator, dicyclohexyl phthalate as plasticizer 12 parts by mass, and 100 parts by mass of ethyl acetate as a solvent were mixed for 3 hours to prepare an organic component solution. Next, 35 parts by mass of this organic component solution (solid content: 50% by mass) and 82.5 parts by mass of glass paste as an inorganic component were kneaded to prepare a composite film forming material. the

Next, the composite film-forming material prepared above was coated on polyethylene terephthalate, and the coated film was dried at 100° C. for 6 minutes to completely remove the solvent to form a composite film with a thickness of 27 μm. the

Next, the composite film produced above was laminated at 105° C. on a silicon wafer previously heated to 80° C. using a hot roll laminator. The air pressure was 3 kg/cm ² , and the lamination speed was 1.0 m/min. Next, the polyethylene terephthalate as the support film was peeled off, and ultraviolet exposure was performed at an irradiation dose of 500 mJ/cm ² through a pattern mask using an ultra-high pressure mercury lamp. Using water with a liquid temperature of 30°C and a spray pressure of 3 kg/cm ² , spray development was performed five times the size of the development point to form a columnar patterned composite film 3 with a width of 10 μm (a pitch of 20 μm). Here, the term "developing point" refers to the time until the unexposed portion completely disappears when the exposure process is performed.

[Example 4]

A positive-type photoresist composition was obtained in the same manner as in Example 2b, except that the solid content mass concentration was 20% by mass. the

This positive photoresist composition was coated on a silicon wafer with a spin coater, and then dried to obtain a photosensitive resin composition layer having a film thickness of 2 μm. The positive photoresist composition layer was prebaked at 130° C. for 1 minute using a hot plate. Then, pattern exposure (soft touch, GHI line) was performed using PLA-501F (contact aligner, manufactured by Canon Corporation), and post-exposure heating (PEB) was performed at 75° C. for 5 minutes using a hot plate, using 3% by mass of Tetramethylammonium hydroxide was used to develop for 2 minutes by dipping. A hole-shaped photoresist pattern with a diameter of 1 μm (a pitch of 2 μm) was thus obtained on the silicon wafer. the

On the other hand, 220.0 g of methyltrimethoxysilane, 246.0 g of tetramethoxysilane, and 301.0 g of propylene glycol monopropyl ether were mixed and stirred. To this mixture were added 204.0 g of water, 52 μL of 60% nitric acid, and stirred for an additional 3 hours. Then, it reacted at 26 degreeC for 2 days. 8.0 g of the reactant, 11.8 g of propylene glycol monopropyl ether, and 0.2 g of a DBU of 0.1% propylene glycol monopropyl ether solution were mixed to obtain a silica-based coating film-forming composition. the

The obtained composition for forming a silica-based coating film was coated on the silicon wafer on which the photoresist pattern was formed by spin coating, and each of the hot plates at 80°C, 150°C, and 200°C Heat for 1 minute. Next, dipping treatment was performed at 70°C for 20 minutes using Peeler 104 (manufactured by Tokyo Ohka Kogyo Co., Ltd.), and then baked at 400°C for 30 minutes in a nitrogen atmosphere to form a silicon dioxide-based coating with a film thickness of about 2 μm. film4. the

<Preparation of negative electrode substrate>

The silicon wafer on which the silicon oxide film is formed on the photoresist patterns 1a and 1b, or the photoresist patterns 2a and 2b are formed, the composite film 3 is patterned, and the silicon dioxide-based coating film 4 on the pattern is patterned. The silicon wafer of the organic membrane 5 was dipped in a sodium phosphate solution for 60 seconds to perform cleaning treatment. Next, the silicon wafer that has passed through the cleaning step is immersed in a 0.05 g/dm ³ tin chloride (SnCl ₂ ) aqueous solution for 60 seconds, and then immersed in a 0.05 g/dm ³ palladium chloride (PdCl ₂ ) aqueous solution. 60 seconds, with which the catalysis step was carried out.

Next, immerse the silicon wafer through the catalysis step in a nickel plating bath containing 0.20M nickel sulfate, 0.30M sodium hypophosphite, 0.30ppm lead ions, and 0.30M carboxylic acid complexing agent. Nickel treatment. In addition, the temperature of the nickel plating bath at this time was 70 degreeC, and pH value was adjusted to 5.5. the

Then, immerse the silicon wafer through the electroless nickel plating step in a tin plating bath containing 0.20M tin chloride, 0.08M titanium trichloride and other reducing agents, 0.50M trisodium citrate deal with. In addition, the temperature of the tin plating bath at this time was 70 degreeC, and pH value was adjusted to 8.5. the

Production: use the non-aqueous electrolyte secondary battery (hereinafter referred to as battery embodiment 1a) with the negative electrode substrate having the photoresist pattern 1a obtained in the above-mentioned embodiment 1, use the negative electrode substrate with the photoresist pattern 1b A nonaqueous electrolyte secondary battery (hereinafter referred to as battery embodiment 1b), a nonaqueous electrolyte secondary battery using a negative electrode substrate having a photoresist pattern 2a (hereinafter referred to as battery embodiment 2a), a nonaqueous electrolyte secondary battery using The nonaqueous electrolyte secondary battery (hereinafter referred to as battery embodiment 2b) of the negative electrode substrate of the photoresist pattern 2b, the nonaqueous electrolyte secondary battery (hereinafter referred to as battery embodiment 2b) using the negative electrode substrate with the patterned composite film 3 Battery Example 3), a non-aqueous electrolyte secondary battery (hereinafter referred to as Battery Example 4) using a negative electrode substrate having a silicon dioxide-based coating film 4 on a pattern, using a patterned organic film 5 A non-aqueous electrolyte secondary battery (hereinafter referred to as Battery Example 5) based on a negative electrode substrate. The discharge capacity of these batteries after 1 to 3 cycles was measured by the following method. The results are shown in Table 1 below. the

The nonaqueous electrolyte secondary battery is produced in the following manner. Each of the negative electrode substrates obtained in Examples was used as a working electrode, LiCoO ₂ was used as a counter electrode (positive electrode), and the two electrodes faced each other through a separator. A mixture of LiPF ₆ /ethylene carbonate and dimethyl carbonate (with a capacity ratio of 1:1) was used as a non-aqueous electrolyte, and a non-aqueous electrolyte secondary battery was produced by a conventional method. In this non-aqueous electrolyte secondary battery, the capacitance ratio of the positive electrode and the negative electrode is 1:1.

The discharge capacity (mAh/cm ² ) per unit volume after 1 to 3 cycles was measured and used as the discharge capacity of each non-aqueous electrolyte secondary battery. The discharge capacitance per unit volume is based on the volume of the negative electrode. However, the expansion of the negative electrode during charging is not considered.

[Table 1]

Among the negative electrode base materials, the surface area of the tin-plated negative electrode base material in Examples was about 190% of that of the case where the tin-plating treatment was performed in a planar shape. The negative electrode substrate with only the patterned organic film 5 is about 115%. the

[Industrial availability] 

Utilizing the negative electrode base material of the present invention, a battery having high output voltage and high energy density and excellent charge-discharge cycle characteristics can be realized, and it can be applied to small batteries used in portable devices, etc., to hybrid vehicles, etc. Various uses of any capacitor of a large battery. the

Claims (17)

1. a base material of cathode is included in the organic membrane on the supporter, and the top layer of described organic membrane is covered by metal oxide film, it is characterized in that: metal film is formed on the described metal oxide film.

2. base material of cathode according to claim 1 is characterized in that: described metal oxide film is silica-based by overlay film.

3. base material of cathode according to claim 2, it is characterized in that: described metal oxide film is formed by silica-based lining film formation material, this silica-based lining film formation material contains: can generate the metallic compound of hydroxyl by hydrolysis, and dissolve this metallic compound and do not have the functional group's of metallic compound reaction solvent therewith.

4. base material of cathode according to claim 1 is characterized in that: described organic membrane is the photoresistance film.

5. base material of cathode according to claim 1 is characterized in that: described organic membrane is the photoresistance pattern that is patterned to the regulation shape by pattern exposure.

6. base material of cathode according to claim 5 is characterized in that: the aspect ratio of described photoresistance pattern is more than 0.1.

7. base material of cathode according to claim 4 is characterized in that: described photoresistance film is formed by the eurymeric photoresistance composition of the resinous principle that contains by irradiation active ray or radioactive ray acidic acid producing agent composition and increase with respect to the effect by acid of the dissolubility of alkali.

8. base material of cathode according to claim 4 is characterized in that: described photoresistance film is formed by the minus photoresistance composition that contains radical polymerization initiator and polyfunctional epoxy resin.

9. base material of cathode according to claim 4 is characterized in that: described photoresistance film by contain (A2) alkali soluble resins, and the eurymeric photoresistance composition that (B2) contains the compound of quinone diazido formed.

10. base material of cathode according to claim 9 is characterized in that: described (A2) composition be selected from phenolic resins, hydroxy styrenes be resin, and acrylic resin at least a.

11. base material of cathode according to claim 9 is characterized in that:

Described (B2) composition is with following general formula (b2a)

[changing 1]

[in the described general formula (b2a), R ^B1～R ^B8Independent respectively expression hydrogen atom, halogen atom, carbon number are that 1～6 alkyl, carbon number are that 1～6 alkoxyl or carbon number are 3～6 cycloalkyl, R ^B10And R ^B11Independent respectively expression hydrogen atom or carbon number are 1～6 alkyl, work as R ^B9When being 1～6 alkyl for hydrogen atom or carbon number, Q ¹Expression hydrogen atom, carbon number are 1～6 alkyl or with following chemical formula (b2b)

[changing 2]

[in the described general formula (b2b), R ^B12And R ^B13Independent respectively expression hydrogen atom, halogen atom, carbon number are that 1～6 alkyl, carbon number are that 1～6 alkoxyl or carbon number are 3～6 cycloalkyl, and c represents 1～3 integer]

Represented residue is worked as Q ¹With R ^B9Terminal bonding the time, Q ¹With R ^B9, and Q ¹With R ^B9Between carbon atom to constitute carbon atom chain together be 3～6 ring alkylene chain, a and b represent 1～3 integer, d represents 0～3 integer, n represents 0～3 integer]

Represented compound, with 1, the esterification reaction product of 2-naphthoquinones diazido sulfonyl compound.

12. base material of cathode according to claim 1 is characterized in that: described metal film is to handle by plating to form.

13. base material of cathode according to claim 12 is characterized in that: described plating handle be selected from that electroless plating copper is handled, electroless plating nickel is handled, electroless plating tin is handled, and at least a plating handled in the group that is formed of electrolytic tinning handle.

14. base material of cathode according to claim 12, it is characterized in that it is that the multistage plating is handled that described plating is handled, comprise: at least a plating during at least a plating processing during the processing of electroless plating copper is handled with electroless plating nickel and the processing of electroless plating tin and electrolytic tinning are handled is handled.

15. base material of cathode according to claim 1 is characterized in that: described base material of cathode is the secondary battery cathode base material.

16. a secondary cell is characterized in that comprising: base material of cathode according to claim 1, electrolyte solution and can occlusion and discharge the anodal base material of this electrolyte solution.

17. the manufacture method of a base material of cathode is used to make base material of cathode, it is characterized in that comprising:

(i) step of formation organic membrane on supporter;

(ii) on described organic membrane, form the step of metal oxide film; And

(iii) handle, on described metal oxide film, form the plating treatment step of metal film by plating.

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