TW201436344A - Interdigitated electrode, method for producing same, and rechargeable battery - Google Patents

Abstract

Provided are: an interdigitated electrode provided to a high-voltage and/or high-capacity rechargeable battery a method for producing the interdigitated electrode and a rechargeable battery containing the interdigitated electrode. This interdigitated electrode forms a comb-shaped positive electrode and negative electrode. A plurality of electrode units positioned facing each other exists in such a manner that the comb-shaped teeth of the positive electrode and negative electrode alternately mesh, and the electrode units are connected in series and/or in parallel. This method for producing the interdigitated electrode comprises: a current collector forming step in which a pair of comb-shaped current collectors (2a, 2b) are formed on the surface of a substrate (4) a resist coating step in which a resist layer (6) is formed on the surface of the substrate (4) and a guide hole forming step in which guide holes (7a, 7b) for forming the positive electrode (1a) or the negative electrode (1b) are formed. A specific resist composition is used as a resist composition for forming the resist layer (6). This rechargeable battery contains the interdigitated electrode.

Description

Comb electrode, method of manufacturing the same, and secondary battery

The present invention relates to a comb-shaped electrode, a method for producing the same, and a secondary battery. More specifically, the positive electrode and the negative electrode are respectively formed in a comb shape, and a plurality of combs for combing the positive electrode and the negative electrode are present. A comb-shaped electrode in which the tooth portions are arranged in a staggered manner in combination with each other, and the comb-shaped electrode connected in parallel and/or in series, a method of manufacturing the comb-shaped electrode, and a secondary battery having the comb-shaped electrode.

In recent years, microdevices that are smaller than smaller devices such as mobile phones have been developed, and as a power source for such micro devices, micron-sized secondary batteries are required. Such a secondary battery must efficiently drive the battery in a limited space inside the micro device, so the design of the battery becomes important. As for the design of the battery, it is known that the positive electrode and the negative electrode are formed into a fine comb shape by photolithography, and the comb teeth portions of the comb shape are arranged to face each other. For example, a battery having a comb-type electrode obtained by the production method described in Patent Document 1 can be cited. In the case of the battery of such a structure, by bringing the positive electrode and the negative electrode into close proximity to each other through a small space, the area in which the positive electrode and the negative electrode are brought into contact can be increased by the minute space which becomes the spacer material, and it is expected Take out the increase in current.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2011-238589

However, the voltage and battery capacity of a secondary battery having a comb-shaped electrode hitherto known are limited by the characteristics or amount of the positive electrode active material and the negative electrode active material, and it is difficult to obtain a high voltage and/or a high capacitance using a comb-shaped electrode. Secondary battery.

The present invention has been made in view of such circumstances, and an object thereof is to provide a comb-shaped electrode for a secondary battery that imparts high voltage and/or high capacitance, a method of manufacturing the comb-shaped electrode, and a secondary battery having the comb-shaped electrode .

The inventors of the present invention have repeatedly conducted active research to solve the above problems. As a result, it has been found that the positive electrode and the negative electrode are respectively formed in a comb shape, and the plurality of electrode units arranged in opposite directions are connected in parallel and/or in series by interlocking the positive and negative electrodes in a comb-shaped comb-tooth portion. The above problems can be solved, and thus the present invention has been completed. Specifically, the present invention provides the following.

The first aspect of the present invention is a comb-shaped electrode in which a positive electrode and a negative electrode are respectively formed in a comb shape, and a plurality of opposite positive and negative electrodes are alternately arranged in a comb-shaped portion of the comb shape. The electrode units are connected in parallel and/or in series.

A second aspect of the present invention is a method for manufacturing a comb-shaped electrode, wherein the positive electrode and the negative electrode of the comb-shaped electrode are respectively formed in a comb shape, and a plurality of comb-shaped portions of the positive electrode and the negative electrode in a comb shape are alternately staggered. A comb-type electrode in which the electrode units are arranged in opposite directions and the parallel connection and/or series connection are performed. The manufacturing method is characterized in that the conductive layer is formed on the surface of the substrate to be formed in a plan view. a current collector forming step of patterning the conductive layer to form a current collector in the same shape as the comb-shaped electrode, and coating the surface of the substrate on the current collector portion formed in the current collector forming step a resist composition, a resist coating step of forming a resist layer, and development of light by irradiating a surface of the resist layer through a mask to form a positive electrode or a negative electrode over the current collector a conductive hole forming step of the via hole, wherein the resist composition is any one of the resist compositions of the following (1) to (4), and (1) a cationic polymerization resist composition containing an epoxy Basic And a cationic polymerization initiator, (2) a novolac-based resist composition containing a novolac resin and a sensitizer, and (3) a chemically amplified resist composition comprising a dissociative group having acid dissociation, and The leaving group is desorbed by the action of an acid generated by the photoacid generator by exposure, thereby increasing the alkali-soluble resin and photoacid generation. (4) a radical polymerization-based resist composition containing a monomer having an ethylenically unsaturated bond and/or a resin, and a radical polymerization initiator, when a monomer having an ethylenically unsaturated bond is contained The number of ethylenically unsaturated bonds contained in one molecule of the monomer is three or less.

A third aspect of the invention is a secondary battery having the comb-shaped electrode described above.

According to the present invention, a comb-shaped electrode for applying a secondary battery having a high voltage and/or a high capacitance, a method of manufacturing the comb-shaped electrode, and a secondary battery having the comb-shaped electrode can be provided.

1a, 1b, 1c-1, 1c-2‧‧‧ electrodes

2‧‧‧ Conductive layer

2a, 2b, 2c‧‧‧ collector

3a, 3b, 3c-1, 3c-2‧‧‧ active material layer

4‧‧‧Substrate

5‧‧‧Resistant layer for collector formation

5a, 5b‧‧‧ resin pattern

6‧‧‧Resist layer

7a, 7b‧‧‧ Guide hole

11a, 11b‧‧‧ electrodes

13a, 13b‧‧‧ active material layer

20‧‧‧Electrode units

100, 100A‧‧‧ comb electrode

Fig. 1 is a plan view schematically showing a comb-shaped electrode according to a first embodiment of the present invention.

Fig. 2 is a perspective view schematically showing one of a plurality of electrode units in the comb-type electrode according to the first embodiment of the present invention.

3 (a) to (i) are perspective views showing the steps of a method of manufacturing a comb-shaped electrode according to a first embodiment of the present invention in order.

Fig. 4 is a view schematically showing a comb-shaped electrode according to a second embodiment of the present invention. (a) is a plan view, and (b) is a longitudinal cross-sectional view of the cut surface when the comb-shaped electrode shown by (a) is cut along the A-A line.

Fig. 5 is a plan view schematically showing a comb-type electrode (positive electrode active material layer 13a: negative electrode active material layer 13b = 2: 1) according to a third embodiment of the present invention.

Fig. 6 is a plan view schematically showing a comb-type electrode (positive electrode active material layer 13a: negative electrode active material layer 13b = 4:1) according to a third embodiment of the present invention.

Fig. 7 is a plan view schematically showing a comb-shaped electrode according to a third embodiment of the present invention.

Hereinafter, the comb-shaped electrode according to the first embodiment of the present invention will be described with reference to the drawings. Fig. 1 is a plan view schematically showing a comb-shaped electrode according to a first embodiment of the present invention. Fig. 2 is a perspective view schematically showing one of a plurality of electrode units in the comb-type electrode according to the first embodiment of the present invention. 3(a) to 3(i) are perspective views showing the steps of a method of manufacturing a comb-shaped electrode according to a first embodiment of the present invention. Further, Fig. 3(h) considers the visibility of the drawing, and omits the current collector 2a existing at the bottom of the via hole 7a.

First, the comb-type electrode 100 according to the first embodiment of the present invention will be briefly described with reference to Figs. 1 and 2 . The comb-shaped electrode 100 has two electrode units 20, and the electrode units 20 are connected in parallel. In the electrode unit 20, the electrodes 1a and 1b are each formed in a comb shape, and the comb-shaped comb-shaped portions are arranged in a direction opposite to each other. Here, the electrode 1a is a positive electrode, and the electrode 1b is a negative electrode. By making the electrode 1a and According to this configuration, 1b, the distance between the electrodes is shortened, the electrolyte resistance is made constant, and lithium ion exchange is performed efficiently, and the battery capacity can be increased. Further, since the comb-shaped electrode 100 is connected in parallel with two electrode units 20, the battery capacitance can be further increased.

A spacer (not shown) for separating or isolating between the electrode 1a and the electrode 1b is provided to electrically separate the two. The electrodes 1a and 1b are formed on the surface of the substrate 4 whose surface is non-conductor. The substrate 4 is exemplified as a tantalum substrate having an oxide film on its surface.

As shown in Fig. 2, the electrode 1a of the positive electrode has a current collector 2a for taking out electric current, and a positive electrode active material layer 3a formed on the surface of the current collector 2a. The current collector 2a is formed into a comb shape in plan view. Further, the positive electrode active material layer 3a is formed on the surface of the comb-shaped current collector 2a, and is formed into a comb shape in plan view similarly to the current collector 2a.

The current collector 2a is made of a metal for imparting conductivity, and is preferably made of gold. Further, in order to secure the adhesion between the current collector 2a and the substrate 4, an adhesion providing layer (not shown) is formed between the current collector 2a and the substrate 4 as necessary. The adhesion providing layer is appropriately determined in consideration of the material of the current collector 2a and the material of the substrate 4. As an example, when the current collector 2a is made of gold and the substrate 4 is made of tantalum, it is preferable to use a film of titanium as the adhesion providing layer. The thickness of the current collector 2a and the thickness of the adhesion providing layer are not particularly limited and can be arbitrarily determined. As an example, the thickness of the current collector 2a is 100 nm, and the thickness of the adhesion providing layer is 50 nm, but is not limited.

The electrode 1b of the negative electrode has a current collector 2b for taking out a current, and a negative electrode active material layer 3b formed on the surface of the current collector 2b. electrode The other matters other than 1b are the same as those of the above-described electrode 1a of the positive electrode, and thus the description thereof is omitted.

An electrolyte (not shown) is provided between the electrode 1a of the positive electrode and the electrode 1b of the negative electrode. Thereby, the electrode 1a and the electrode 1b can respectively cause an electrode reaction, and current is taken out from the current collector 2a and the current collector 2b.

The material constituting the positive electrode active material layer 3a and the negative electrode active material layer 3b and the type of the electrolyte are appropriately determined depending on which battery is formed. In the case of a lithium ion secondary battery, the material of the positive electrode active material layer 3a is a transition metal oxide such as lithium cobalt oxide, and the material of the negative electrode active material layer 3b is exemplified by carbon, graphite, lithium titanate or the like. The electrolyte is exemplified by an electrolyte solution containing a salt such as lithium hexafluorophosphate or an organic solvent such as diethyl carbonate in which the salt is dissolved.

Next, a method of manufacturing the comb-shaped electrode 100 of the present embodiment will be described. The method for producing the comb-shaped electrode 100 of the present embodiment includes at least a current collector forming step, a resist coating step, and a via forming step, and further includes an active material layer forming step. Hereinafter, each step will be described with reference to FIG. 3. Further, in FIG. 3, in the comb-type electrode 100, in particular, each step of a method of forming a portion corresponding to the electrode unit 20 is shown, but in the current collector forming step and the via hole forming step, the corresponding electrode body 100 is formed. Instead of forming a pattern corresponding to the electrode unit 20, the comb-shaped electrode 100 can be manufactured in the same manner as the method shown in FIG.

[Collector forming step]

The current collector forming step is followed by the steps shown in Figs. 3(a) to (f).

This step first forms a thin film conductive layer 2 on the surface of the substrate 4 (Figs. 3(a) to (b)). The substrate 4 is a conductor or a semiconductor which is a non-conductor or a layer forming a non-conductor at least on the surface, and is exemplified by, for example, a crucible substrate having an oxide film on its surface. The conductive layer 2 is a conductor, preferably a thin film of metal. When the conductive layer 2 is formed on the surface of the substrate 4, various conventional methods such as a vapor deposition method using a PVD method or a CVD method, a sputtering method, a plating method, and a metal foil bonding method can be used. The thickness of the conductive layer 2 may be appropriately determined in consideration of the performance required for the electrodes 1a and 1b.

For example, the substrate 4 is a tantalum substrate having an oxide film on its surface, and when the conductive layer 2 is formed of a gold thin film, a film (not shown) in which titanium is first formed on the surface of the tantalum substrate 4 by sputtering, followed by sputtering A method of forming a gold thin film of the conductive layer 2 on the surface of the titanium film by plating. In this case, the film of titanium is provided to improve the adhesion of the conductive layer 2 to the ruthenium substrate 4. The thickness of the titanium thin film and the conductive layer 2 is 50 nm and 100 nm, respectively, but it may be appropriately determined in consideration of necessary performance.

After the conductive layer 2 is formed, as shown in FIG. 3(c), a current collector forming resist is applied to the surface of the conductive layer 2 to form a current collector forming resist layer 5. The current collector forming resist layer 5 is provided for patterning the conductive layer 2 to form comb-shaped current collectors 2a and 2b.

As the resist for forming a current collector, various conventional resist compositions can be used. Moreover, the term "component for forming a current collector" is used to distinguish it from a resist used to form the via holes 7a and 7b which will be described later. The current collector forming resist may be the same as or different from the resist used in the via forming step described later.

There is no particular limitation on the method of applying the resist for forming a current collector. List the conventional methods. These methods are exemplified by a spin coating method, a dipping method, a brush coating method, and the like.

The formed resist layer 5 for forming a current collector is selectively exposed and developed through a mask pattern of a comb shape to form resin patterns 5a and 5b for forming a current collector. Thereby, as shown in FIG. 3(d), resin patterns 5a and 5b for forming a current collector are formed on the surface of the conductive layer 2. In the comb-shaped resin patterns 5a and 5b, the number of comb teeth, the thickness of the comb teeth, the gap between the pattern and the pattern (space gap), and the like may be appropriately set in consideration of necessary performance. The number of comb teeth is, for example, 5 to 500 pairs, the thickness of the comb teeth is, for example, 1 to 50 μm, and the space gap is, for example, 1 to 50 μm. As an example, the number of comb teeth is 100 pairs (the number of comb teeth in the resin pattern of one side is 100), the thickness of the comb teeth is 20 μm, and the space gap is 10 to 20 μm, but it is not limited.

Next, the regions of the conductive layer 2 that are not covered by the patterns 5a and 5b are removed. When the conductive layer 2 is removed, a conventional method can be used without particular limitation. The method is exemplified by an etching method, an ion milling method, and the like. The comb-shaped current collectors 2a and 2b are formed by removing portions of the conductive layer 2 that are not covered by the patterns 5a and 5b (Fig. 3(e)). Subsequently, the patterns 5a and 5b are removed, and as shown in Fig. 3(f), the comb-shaped current collectors 2a and 2b are exposed on the surface of the substrate 4.

[Resistant coating step]

Next, the resist coating step will be described. The resist coating step is a step performed after the above-described current collector forming step, as shown in FIG. 3(g) The steps.

In this step, a resist composition is formed on the surface of the substrate 4 including a portion of the current collectors 2a and 2b formed in the above-described current collector forming step to form a resist layer 6.

A method of applying a resist composition to the surface of the substrate 4 and forming the resist layer 6 can be carried out without any particular limitation. On the resist layer 6, as will be described later, via holes 7a and 7b for forming the positive electrode active material layer 3a and the negative electrode active material layer 3b are formed. Since the via holes 7a and 7b are formed as a mold for forming the positive electrode active material layer 3a and the negative electrode active material layer 3b, they must be formed to have a sufficient depth for forming the positive electrode active material layer 3a and the negative electrode active material layer 3b. Since the thickness of the resist layer 6 is the depth of the future via holes 7a and 7b, it is appropriately determined in consideration of the depths of the necessary via holes 7a and 7b. The thickness of the resist layer 6 is exemplified as 10 to 100 μm, but is not particularly limited.

As a resist composition for forming the resist layer 6, (1) a cationic polymerization resist composition containing a compound having an epoxy group and a cationic polymerization initiator, (2) a novolak resin and a photosensitive resin are used. a novolac-based resist composition, (3) containing an acid-dissociable leaving group, and the leaving group is detached by an action of an acid generated by a photo-acid generator by exposure, thereby increasing alkali solubility a chemically amplified resist composition of the resin and the photoacid generator, or (4) a monomer and/or a resin having an ethylenically unsaturated bond, and a radical polymerization initiator, and having an ethylenic property In the case of a monomer having an unsaturated bond, the ethylenically unsaturated bond contained in one molecule of the monomer is any one of three or less radical polymerization inhibitor compositions. . Hereinafter, each resist composition will be described.

First, the cationic polymerization inhibitor composition of the above (1) will be described. The cationic polymerization-based resist composition is a compound containing at least an epoxy group and a cationic polymerization initiator, and a cationic polymerization initiator is generated by irradiation of an active energy ray such as ultraviolet rays, and the cation has an epoxy group. A composition in which a compound is polymerized to be polymerized and hardened.

The compound having an epoxy group is not particularly limited as long as it has an epoxy group in the molecule, but has a complex number in the molecule based on the viewpoint of imparting solvent resistance or plating solution resistance to a pattern formed of the resist composition. The epoxy group-containing compound is preferred. The compound is exemplified as a polyfunctional epoxy resin.

The polyfunctional epoxy resin may be any epoxy resin as long as it is an epoxy resin containing a sufficient amount of epoxy groups to cure the component layer 6 formed of the resist composition in one molecule. The polyfunctional epoxy resin is preferably exemplified as a phenol novolak type epoxy resin, an o-cresol novolak type epoxy resin, a triphenyl type novolac type epoxy resin, a bisphenol A novolac type epoxy resin. Resin.

The number of functional groups of the epoxy group contained in one molecule of the polyfunctional epoxy resin is preferably 3 or more, more preferably 4 to 12. By setting the functionality of the polyfunctional epoxy resin to three or more, it is preferable to form a resin pattern having high aspect ratio and resolution, and the functionality of the polyfunctional epoxy resin is 12 or less. It is preferable to control the synthesis of the resin easily, and it is possible to suppress an excessive increase in the internal stress of the resin pattern.

The mass average molecular weight of the multifunctional epoxy resin is preferably 700~5000, more preferably 1000~4000. By making the mass average molecular weight of the polyfunctional epoxy resin 700 or more, it is possible to suppress the heat-flowing property of the curable resin composition by irradiation of the active energy ray before curing, by making the multifunctional epoxy resin The mass average molecular weight is 5,000 or less, which is preferable in terms of obtaining an appropriate dissolution rate at the time of development.

As such a polyfunctional epoxy resin, an 8-functional bisphenol A novolac type epoxy resin (product name jER157S70 manufactured by Nippon Epoxy Resin Co., Ltd.) or an average 6.4-functional bisphenol A novolac type epoxy resin is preferable. Resin (product name EPICLON N-885 manufactured by DIC Corporation), average 5.6-functional bisphenol A novolac type epoxy resin (product name EPICLON N-865 manufactured by DIC Corporation), and the like.

The above polyfunctional bisphenol A novolac type epoxy resin is represented, for example, by the following general formula (1).

(In the above formula (1), R ¹ to R ⁶ are a hydrogen atom or a methyl group, and x is 0 or a positive integer, preferably an integer of 1 to 10, more preferably an integer of 1 to 5, and The epoxy group in the above formula (1) can be reacted and bonded with other bisphenol A type epoxy resin or bisphenol A novolak type epoxy resin).

The content of the polyfunctional epoxy resin in the cationic polymerization resist composition is preferably from 70 to 95% by mass, more preferably from 75 to 93% by mass, based on the solid content of the resist composition. When the concentration of the polyfunctional epoxy resin in the cationic polymerization resist composition is 70% by mass or more based on the solid content, it is preferable to impart sufficient strength to the cured product obtained by curing. In addition, when the concentration of the polyfunctional epoxy resin in the cationic polymerization inhibitor composition is 95% by mass or less based on the solid content, it is preferable to obtain a sufficient sensitivity when the cationic polymerization resist composition is photocured. In the present specification, the term "solid content" means a component remaining after removing a solvent component from the composition.

Next, the cationic polymerization initiator will be described. The cationic polymerization initiator used in the present invention is irradiated with an active energy ray such as ultraviolet light, far ultraviolet ray, KrF or ArF, or an active energy ray such as an X-ray or an electron beam to generate a cation, and the cation thereof can be used as a polymerization initiator. Compound.

The cationic polymerization initiator is represented, for example, by the following formula (2).

(In the above formula (2), R ⁷ and R ⁸ each independently represent a hydrogen atom, a halogen atom, a hydrocarbon group which may contain an oxygen atom or a halogen atom, or an alkoxy group which may have a substituent bonded thereto, and R ⁹ represents a hydrogen atom thereof. One or more atoms of the atom may be substituted with a halogen atom or an alkyl group, and R ¹⁰ represents a hydrogen atom, a hydrocarbon group which may have an oxygen atom or a halogen atom, a benzoyl group which may have a substituent, Polyphenyl having a substituent, A ^- represents a relative ion of a cerium ion).

In the above formula (2), A ^{- is} specifically exemplified as SbF ₆ ^- , PF ₆ ^- , AsF ₆ ^- , BF ₄ ^- , SbCl ₆ ^- , ClO ₄ ^- , CF ₃ SO ₃ ^- , CH ₃ SO ₃ ^- , FSO ₃ ^- , F ₂ PO ₂ ^- , p-toluenesulfonate, nonafluorobutanesulfonate, adamantane carboxylate, tetraarylborate, fluorinated alkylfluorophosphate anion represented by the following formula (3), etc. .

[(3) [(Rf) _b PF _6-b ] ^- (3)

(In the above formula (3), Rf represents an alkyl group in which 80% or more of a hydrogen atom is substituted by a fluorine atom, b represents a number thereof, and is an integer of 1 to 5, and b Rf's may be the same or different).

Such cationic initiators are exemplified by 4-(2-chloro-4-benzylidenephenylthio)phenyldiphenylphosphonium hexafluoroantimonate, 4-(2-chloro-4-benzhydryl) Phenylthio)phenylbis(4-fluorophenyl)phosphonium hexafluoroantimonate, 4-(2-chloro-4-benzylidenephenylthio)phenylbis(4-chlorophenyl)phosphonium Fluoride, 4-(2-chloro-4-benzylidenephenylthio)phenylbis(4-methylphenyl)phosphonium hexafluoroantimonate, 4-(2-chloro-4-benzene Methylmercaptophenylthio)phenylbis(4-(β-hydroxyethoxy)phenyl)phosphonium hexafluoroantimonate, 4-(2-methyl-4-benzylidenephenylthio)benzene Bis(4-fluorophenyl)phosphonium hexafluoroantimonate, 4-(3-methyl-4-benzylidenephenylthio)phenylbis(4-fluorophenyl)phosphonium hexafluoroantimonate 4-(2-Fluoro-4-benzylidenephenylthio)phenylbis(4-fluorophenyl)phosphonium hexafluoroantimonate, 4-(2-methyl-4-benzylidenebenzene) Thio) Phenyl bis(4-fluorophenyl)phosphonium hexafluoroantimonate, 4-(2,3,5,6-tetramethyl-4-benzylidenephenylthio)phenylbis(4-fluorobenzene) Hexafluoroantimonate, 4-(2,6-dichloro-4-benzylidenephenylthio)phenylbis(4-fluorophenyl)phosphonium hexafluoroantimonate, 4-(2 ,6-dimethyl-4-benzhydrylphenylthio)phenylbis(4-fluorophenyl)phosphonium hexafluoroantimonate, 4-(2,3-dimethyl-4-benzamide Phenylthio)phenylbis(4-fluorophenyl)phosphonium hexafluoroantimonate, 4-(2-methyl-4-benzylidenephenylthio)phenylbis(4-chlorophenyl) Hexafluoroantimonate, 4-(3-methyl-4-benzylidenephenylthio)phenylbis(4-chlorophenyl)phosphonium hexafluoroantimonate, 4-(2-fluoro-4 -benzimidylphenylthio)phenylbis(4-chlorophenyl)phosphonium hexafluoroantimonate, 4-(2-methyl-4-benzylidenephenylthio)phenyl bis(4- Chlorophenyl)phosphonium hexafluoroantimonate, 4-(2,3,5,6-tetramethyl-4-benzylidenephenylthio)phenylbis(4-chlorophenyl)phosphonium hexafluoroantimony Acid salt, 4-(2,6-dichloro-4-benzylidenephenylthio)phenylbis(4-chlorophenyl)phosphonium hexafluoroantimonate, 4-(2,6-dimethyl 4-Benzylmercaptophenylthio)phenylbis(4-chlorophenyl)phosphonium hexafluoroantimonate, 4-(2,3-dimethyl-4-benzomethylphenylthio)benzene Base double (4- Phenyl) hexafluoroantimonate, 4-(2-chloro-4-ethenylphenylthio)phenyldiphenylphosphonium hexafluoroantimonate, 4-(2-chloro-4-(4- Methyl benzhydryl)phenylthio)phenyldiphenylphosphonium hexafluoroantimonate, 4-(2-chloro-4-(4-fluorobenzylidene)phenylthio)phenyldiphenyl Hexafluoroantimonate, 4-(2-chloro-4-(4-methoxybenzylidene)phenylthio)phenyldiphenylphosphonium hexafluoroantimonate, 4-(2-chloro- 4-dodecylmercaptophenylthio)phenyldiphenylphosphonium hexafluoroantimonate, 4-(2-chloro-4-ethinylphenylthio)phenylbis(4-fluorophenyl)fluorene Hexafluoroantimonate, 4-(2-chloro-4-(4-methylbenzylidene)phenylthio)phenylbis(4-fluorophenyl)phosphonium hexafluoroantimonate, 4-(2 -chloro-4-(4-fluorobenzylidene)phenylthio)phenylbis(4-fluorophenyl)phosphonium hexafluoroantimonate, 4-(2-chloro-4-(4-methoxy) Benzhydryl)phenylthio)phenyl bis (4- Fluorophenyl) hexafluoroantimonate, 4-(2-chloro-4-dodecylphenylthio)phenylbis(4-fluorophenyl)phosphonium hexafluoroantimonate, 4-(2 -chloro-4-ethinylphenylthio)phenylbis(4-chlorophenyl)phosphonium hexafluoroantimonate, 4-(2-chloro-4-(4-methylbenzylidene)phenylsulfonate Phenyl bis(4-chlorophenyl)phosphonium hexafluoroantimonate, 4-(2-chloro-4-(4-fluorobenzylidene)phenylthio)phenyl bis(4-chlorophenyl) ) hexafluoroantimonate, 4-(2-chloro-4-(4-methoxybenzylidene)phenylthio)phenylbis(4-chlorophenyl)phosphonium hexafluoroantimonate, 4 -(2-chloro-4-dodecylsulfonylphenyl)phenylbis(4-chlorophenyl)phosphonium hexafluoroantimonate, 4-(2-chloro-4-benzylidenephenylthio) Phenyldiphenylphosphonium hexafluorophosphate, 4-(2-chloro-4-benzylidenephenylthio)phenyldiphenylphosphonium tetrafluoroborate, 4-(2-chloro-4-benzene Methylmercaptophenylthio)phenyldiphenylphosphonium perchlorate, 4-(2-chloro-4-benzylidenephenylthio)phenyldiphenylphosphonium trifluoromethane, 4-( 2-Chloro-4-benzylidene phenylthio)phenyl bis(4-fluorophenyl)phosphonium hexafluorophosphate, 4-(2-chloro-4-benzomethylphenylthio)phenyl double (4-fluorophenyl)phosphonium tetrafluoroborate, 4-(2-chloro-4-benzylidenephenylthio)phenyl bis(4-fluorobenzene鋶Perchlorate, 4-(2-chloro-4-benzylidene phenylthio)phenyl bis(4-fluorophenyl)phosphonium trifluoromethanesulfonate, 4-(2-chloro-4) -benzylidene phenylthio)phenylbis(4-fluorophenyl)indole p-toluenesulfonate, 4-(2-chloro-4-benzylidenephenylthio)phenyl bis(4- Fluorophenyl) camphorsulfonate, 4-(2-chloro-4-benzylidenephenylthio)phenylbis(4-fluorophenyl)phosphonium hexafluorobutanesulfonate, 4-(2 -chloro-4-benzylidene phenylthio)phenylbis(4-chlorophenyl)phosphonium hexafluorophosphate, 4-(2-chloro-4-benzylidenephenylthio)phenyl bis ( 4-chlorophenyl)indole tetrafluoroborate, 4-(2-chloro-4-benzylidenephenylthio)phenylbis(4-chlorophenyl)phosphonium perchlorate, 4-(2- Chloro-4-benzylidene phenylthio)phenyl bis(4-chlorophenyl)phosphonium trifluoromethanesulfonate, diphenyl[4-(phenylthio)phenyl]phosphonium trifluoride (five Fluoroethyl)phosphoric acid Salt, diphenyl [4-(p-triphenylthio)phenyl]phosphonium hexafluoroantimonate, diphenyl[4-(p-triphenylthio)phenyl]phosphonium trifluoride Reference (pentafluoroethyl) phosphate. Among these compounds, 4-(2-chloro-4-benzylidenephenylthio)phenylbis(4-fluorophenyl)phosphonium tetrahexafluoroantimonate (made by ADEKA Co., Ltd., ADEKAOPTOMER-SP-172), diphenyl[4-(phenylthio)phenyl]phosphonium trifluoromethane (pentafluoroethyl) phosphate (manufactured by SAN-APRO Co., Ltd., CPI-210S), diphenyl [4-(p-(triphenylthio)phenyl)phosphonium hexafluoroantimonate, diphenyl[4-(p-triphenylthio)phenyl]indole trifluoromethane (pentafluoroethylene) Phosphate (HS-APRO, manufactured by SAN-APRO Co., Ltd.).

The content of the cationic polymerization initiator in the cationic polymerization-based resist composition is preferably from 0.1 to 10% by mass, more preferably from 0.5 to 5% by mass, based on the solid content of the resist composition. When the content of the cationic polymerization initiator in the cationic polymerization-based resist composition is 0.1% by mass or more based on the solid content, the curing time of the cationic polymerization resist composition by the active energy ray exposure is appropriate. Preferably. In addition, when the content of the cationic polymerization initiator in the cationic polymerization inhibitor is 10% by mass or less based on the solid content, it is preferred that the developability after exposure with an active energy ray is good.

The cationic polymerization-based resist composition may be added with a sensitizer, a decane coupling agent, a solvent or the like according to the required properties.

The sensitizer is exemplified by a naphthol type sensitizer. When the sensitivity of the cationic polymerization-based resist composition is high, when there is a gap between the photomask and the resist layer 6, as a result of the exposure, the size of the obtained resin pattern (hardened material) may be compared with that of the photomask. The case where the size becomes thicker, but the thicker one The phenomenon can be suppressed without lowering the sensitivity by the naphthol-containing sensitizer. Accordingly, when a naphthol type sensitizer is added, it is preferable to suppress the size of the resin pattern from the error in the size of the mask.

The naphthol type sensitizer is preferably exemplified by 1-naphthol, β-naphthol, α-naphthol methyl ether, and α-naphthol ethyl ether, and the effect of suppressing the coarsening of the resin pattern without lowering the sensitivity is considered. More preferably, it is exemplified as 1-naphthol.

The decane coupling agent is used to improve the adhesion between the resin pattern formed by the resist layer 6 and the substrate 4. The decane coupling agent can be used without any particular limitation, but the adhesion between the resin pattern and the substrate 4 is made stronger by allowing the molecules of the decane coupling agent to enter the molecules of the resin pattern. From the viewpoint of the above, a decane coupling agent having an epoxy group is preferably used. The decane coupling agent is exemplified by 3-glycidoxypropyltrimethoxydecane, 3-glycidoxypropyltriethoxydecane, and the like. The amount of the decane coupling agent added is exemplified as 1 to 10% by mass based on the solid content of the cationic polymerization inhibitor composition.

The solvent is used to increase the sensitivity of the cationic polymerization-based resist composition, and the viscosity of the cationic polymerization-based resist composition is suitable for application to the surface of the substrate 4. The solvent is exemplified by propylene glycol monomethyl ether acetate (PGMEA), methyl isobutyl ketone (MIBK), butyl acetate, methyl amyl ketone (2-heptanone), ethyl acetate, methyl ethyl ketone. (MEK) and so on. The amount of the solvent to be added in the cationic polymerization-based resist composition may be appropriately determined in consideration of the coatability of the cationic polymerization-based resist composition.

Hereinafter, the composition of the novolac-based resist of the above (2) will be described. The phenolic varnish-based resist composition contains a novolak-type resin and a feeling A photo-agent which is a composition which increases the solubility in an alkaline aqueous solution of a developing solution by irradiation with an active energy ray such as ultraviolet rays.

The novolac type resin is alkali soluble. The alkali-soluble novolac type resin is not particularly limited, and an alkali-soluble novolac type resin conventionally used in a conventional positive-type resist composition can be used. For example, phenol, cresol or xylenol can be used in the presence of an acidic catalyst. The aromatic hydroxy compound is condensed with an aldehyde such as formaldehyde.

The sensitizer uses a compound containing a quinonediazide group. Examples of the quinonediazide group-containing compound include polyhydroxybenzophenone such as 2,3,4-trihydroxybenzophenone and 2,3,4,4'-tetrahydroxybenzophenone, and 1 -[1-(4-hydroxyphenyl)isopropyl]-4-[1,1-bis(4-hydroxyphenyl)ethyl]benzene, 1,4-bis(4-hydroxyphenyl isopropylidene) Benzene, ginseng (4-hydroxyphenyl)methane, bis(4-hydroxy-3,5-dimethylphenyl)-4-hydroxyphenylmethane, bis(4-hydroxy-2,5-dimethyl Phenyl)-4-hydroxyphenylmethane, bis(4-hydroxy-3,5-dimethylphenyl)-2-hydroxyphenylmethane, bis(4-hydroxy-2,5-dimethylbenzene A hydroxyphenyl)methane or a methyl substituted product thereof as described in JP-A-4-29242, and the like, and naphthoquinone-1,2-diazide- A fully esterified or partially esterified product of 5-sulfonic acid or naphthoquinone-1,2-diazide-4-sulfonic acid. In particular, 1-[1-(4-hydroxyphenyl)isopropyl]-4-[1,1-bis(4-hydroxyphenyl)ethyl]benzene, 1,4-bis(4-hydroxyl) can be used. Phenylisopropylidene)benzene, the above-mentioned ginseng (hydroxyphenyl)methane or its methyl substituent, and naphthoquinone-1,2-diazide-5-sulfonic acid or naphthoquinone-1,2- A fully esterified or partially esterified product of the diazide-4-sulfonic acid can be preferably used as a sensitizer for excimer laser or far ultraviolet light. In addition, other compounds containing quinonediazide groups such as o-benzoquinone may also be used. Diazide, o-naphthoquinonediazide, o-quinonediazide, or o-naphthoquinonediazide sulfonate or such nuclear-substituted derivatives, o-quinonediazide-sulfonium chloride, etc. a hydroxy or amine group compound such as phenol, p-methoxyphenol, dimethyl phenol, hydroquinone, bisphenol A, naphthol, pyrocatechol, pyrogallol, pyrogallol monomethyl ether, The reaction product of pyrogallol-1,3-dimethyl ether, gallic acid, a part of hydroxyl group esterified or etherified gallic acid, aniline, p-aminodiphenylamine or the like is used as a sensitizer. These sensitizers may be used alone or in combination of two or more.

The above-mentioned sensitizer is preferably 5 to 200 parts by mass, more preferably 10 to 60 parts by mass per 10 parts by mass of the above-mentioned novolak-type resin. When the amount of the novolac type resin used falls within the above range, the reproducibility of the novolac-based resist composition can be improved.

In the novolac-based resist composition, a plasticizer, a solvent, or the like can be added depending on the desired characteristics. The plasticizer can be a conventional plasticizer without any particular limitation. The plasticizer is exemplified by polymethyl vinyl ether or the like. Further, the solvent can be used in the same manner as described above for the cationic polymerization inhibitor composition.

When a compound having two or more naphthoquinonediazide groups in one molecule is used as a sensitizer, the hydroxyl group contained in the novolac type resin can be made sensitized by post-hardening by irradiating the formed resin pattern with ultraviolet rays. It is preferred to crosslink the naphthoquinonediazide group contained therein to improve the solvent resistance of the resin pattern.

Next, the chemical amplification resist composition of the above (3) will be described. The chemical amplification resist composition contains at least an acid dissociable leaving group, and the leaving group is produced from a photoacid generator by exposure. The acid is removed and the alkali-soluble resin and the photoacid generator are increased. That is, the resin contained in the chemical amplification resist composition is small in alkali solubility after being exposed to the alkali-soluble substituent by the protective group before exposure, but is formed by the photoacid generator after exposure. The action of the acid causes the above-mentioned protective group to be detached to exhibit a substituent which imparts alkali solubility, and the alkali solubility becomes large. By this action, the chemically amplified resist composition is developed and removed by a region selected to be exposed through the mask to form a resin pattern.

The photoacid generator is not particularly limited as long as it is an acid which is irradiated with an active energy ray such as ultraviolet rays, and a conventional compound which is conventionally used as an acid generator in a chemically amplified resist composition can be used. The photoacid generator may, for example, be [2-(propylsulfonyloxyimino)-2,3-dihydrothiophene-3-ylidene] (o-tolyl)acetonitrile (IRGACURE PAG103 (trade name) ), Ciba Specialty Chemicals Co., Ltd.), bis(p-toluenesulfonyl)diazomethane, methylsulfonyl-p-toluenesulfonyldiazomethane, 1-cyclohexylsulfonyl-1- (1,1-dimethylethylsulfonyl)diazomethane, bis(1,1-dimethylethylsulfonyl)diazomethane, bis(1-methylethylsulfonyl) Nitrogen methane, bis(cyclohexylsulfonyl)diazomethane, bis(2,4-dimethylphenylsulfonyl)diazomethane, bis(4-ethylphenylsulfonyl)diazomethane, Bis(3-methylphenylsulfonyl)diazomethane, bis(4-methoxyphenylsulfonyl)diazomethane, bis(4-fluorophenylsulfonyl)diazomethane, bis( 4-chlorophenylsulfonyl)diazomethane, bis(4-tert-butylphenylsulfonyl)diazomethane, etc.; dimethylsulfonyldiazomethane; 2-methyl-2-(p- Toluenesulfonyl)propiophenone, 2-(cyclohexylcarbonyl)-2-(p-toluenesulfonyl)propane, 2-methanesulfonyl-2- a sulfonylcarbonyl alkane such as methyl-(p-methylthio)propiophenone or 2,4-dimethyl-2-(p-toluenesulfonyl)pentan-3-one; 1-p-toluene Sulfomethyl-1-cyclohexylcarbonyldiazomethane, 1-diazo-1-methylsulfonyl-4-phenyl-2-butanone, 1-cyclohexylsulfonyl-1-cyclohexylcarbonyl Nitrogen methane, 1-diazo-1-cyclohexylsulfonyl-3,3-dimethyl-2-butanone, 1-diazo-1-(1,1-dimethylethylsulfonyl) -3,3-dimethyl-2-butanone, 1-ethenyl-1-(1-methylethylsulfonyl)diazomethane, 1-diazo-1-(p-toluenesulfonate) -3,3-dimethyl-2-butanone, 1-diazo-1-phenylsulfonyl-3,3-dimethyl-2-butanone, 1-diazo-1-(pair -toluenesulfonyl)-3-methyl-2-butanone, 2-diazo-2-(p-toluenesulfonyl)acetic acid cyclohexyl ester, 2-diazo-2-phenylsulfonyl acetic acid Tributyl ester, 2-diazo-2-methanesulfonyl isopropyl acetate, 2-diazo-2-benzenesulfonyl acetic acid cyclohexyl ester, 2-diazo-2-(p-toluenesulfonyl) ) sulfonylcarbonyl diazomethane such as acetic acid-t-butyl ester; 2-nitrobenzyl p-toluenesulfonate, 2,6-dinitrobenzyl p-toluenesulfonate, p-trifluoromethane Nitrobenzyl group such as toluene-2,4-dinitrobenzyl sulfonate Biological; methanesulfonate of pyrogallol, besylate of pyrogallol, p-toluenesulfonate of pyrogallol, p-methoxybenzenesulfonate of pyrogallol, Mesitylene trisyl sulfonate, benzyl sulfonate of pyrogallol, methanesulfonate of alkyl gallate, benzenesulfonate of alkyl gallate, gallic acid P-toluenesulfonate of alkyl ester, p-methoxybenzenesulfonate of alkyl gallate, mesitylene sulfonate of alkyl gallate, benzyl of alkyl gallate An ester of a polyhydroxy compound such as a sulfonate ester and an aliphatic or aromatic sulfonic acid. The alkyl group in the above alkyl catenate is preferably an alkyl group having 1 to 15 carbon atoms, preferably an octyl group and a lauryl group. Among the above photoacid generators, preferred are disulfonyldiazomethanes, of which di(cyclohexane) is preferably used. Sulfosyl) diazomethane and bis(2,4-dimethylphenylsulfonyl)diazomethane. These photoacid generators may be used singly or in combination of two or more.

The resin used in the chemical amplification resist composition is an alkali-soluble one by the action of an acid generated from a photo-acid generator, and the conventional resin used in the chemical-amplified resist composition can be used. Know synthetic resin. The resin may, for example, be a polyacrylic acid which protects a part of a carboxyl group with a protecting group, or a polyhydroxystyrene which protects a part of a hydroxyl group with a protecting group. The protecting group is shown, for example, as a third butoxycarbonyl group, a third butyl group, a third pentyloxycarbonyl group, an alkoxyalkyl group, a tetrahydropyranyl group, a tetrahydrofuranyl group, a 1-ethylcyclohexane-1- Base.

The amount of the photoacid generator to be used in the chemically amplified resist composition may be appropriately set in accordance with the combination with the above resin, but is preferably 0.1 to 20 parts by mass per 100 parts by mass of the resin.

A sensitivity adjusting agent, a solvent, and the like may be added to the chemical amplification resist composition as needed. The sensitivity adjuster is added to capture a part of the acid generated from the photoacid generator, and is used to improve the sensitivity or resolution of the resist composition. Such a sensitivity adjuster (quenching agent) is exemplified by an aliphatic amine, particularly a secondary aliphatic amine or a tertiary aliphatic amine, and specific examples thereof are n-hexylamine, n-heptylamine, n-octylamine, n-decylamine, and positive a monoalkylamine such as guanamine; a dialkylamine such as diethylamine, di-n-propylamine, di-n-heptylamine, di-n-octylamine or dicyclohexylamine; trimethylamine, triethylamine, tri-n-propylamine, and tri-n-butyl a trialkylamine such as an amine, tri-n-pentylamine, tri-n-hexylamine, tri-n-heptylamine, tri-n-octylamine, tri-n-decylamine, tri-n-decylamine or tri-n-dodecylamine; diethanolamine, triethanolamine, Diisopropanolamine, triisopropanolamine, di-n-octanolamine, tri-n-octanolamine, etc. Alkanolamine. The solvent can be the same as those described in the above cationic polymerization inhibitor composition.

Next, the radical polymerization resist composition of the above (4) will be described. The radical polymerization-based resist composition contains at least a monomer and/or a resin having an ethylenically unsaturated bond, and a radical polymerization initiator, which is produced by irradiation of an active energy ray such as ultraviolet rays to cause a radical polymerization initiator A composition in which a radical and a monomer and/or a resin having an ethylenically unsaturated group are polymerized to be polymerized and hardened by a radical.

As the monomer or resin having an ethylenically unsaturated bond, those conventionally used for the radical polymerizable resist composition can be used. However, when a monomer having an ethylenically unsaturated bond is used, the number of ethylenically unsaturated bonds contained in one molecule of the monomer must be three or less. When the number of the ethylenically unsaturated bonds contained in the monomer is four or more, the monomer molecule volume becomes large, and residue occurs after development, and the reproducibility of the pattern is slightly lowered. For normal use, there is almost no problem of reproducibility with the occurrence of this residue. However, in the comb-shaped electrode produced by the present invention, when the fine structure is close to the pattern and the pattern, when the residue is generated, it is difficult to extract patterns such as the shapes of the current collectors 2a and 2b, which will be described later. The shapes of the pilot holes 7a and 7b are smaller than those of the current collectors 2a and 2b in plan view. In this case, a sufficient amount of the positive electrode active material layer 3a and the negative electrode active material layer 3b cannot be formed on the surfaces of the current collectors 2a and 2b, and the battery capacity may not be sufficiently obtained. Therefore, when a monomer having an ethylenically unsaturated bond is used in the present invention, a monomer having three or less ethylenically unsaturated bonds in one molecule of the monomer is used. According to this, sufficient pattern reproducibility can be obtained when manufacturing a comb-shaped electrode of a fine structure.

The resin having an ethylenically unsaturated bond is exemplified by, for example, a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a phenol novolak type epoxy resin, and a terminal glycidyl ether of a propylene oxide adduct of bisphenol A. An epoxy group (meth) acrylate of a reaction product of an epoxy resin such as an epoxy resin with (meth)acrylic acid; a reactant of a polyol and an organic isocyanate and a hydroxyl group-containing ethylenically unsaturated compound; Amino methacrylate (meth) acrylate; a polyester (meth) acrylate of a polyhydric alcohol and a (meth) acrylate esterified product. These may be used alone or in combination of two or more. Further, the resin having an ethylenically unsaturated bond may have four or more ethylenically unsaturated bonds in one molecule, unlike the monomer having an ethylenically unsaturated bond.

The monomer having an ethylenically unsaturated bond has three or less ethylenically unsaturated bonds contained in one molecule of the monomer. Such monomers are exemplified by, for example, (meth) acrylamide, hydroxymethyl (meth) acrylamide, methoxymethyl (meth) acrylamide, ethoxymethyl (meth) propylene oxime. Amine, propoxymethyl (meth) acrylamide, butoxy methoxymethyl (meth) acrylamide, acrylic acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, lemon Kang acid, citraconic anhydride, crotonic acid, 2-propenylamine-2-methylpropane sulfonic acid, t-butyl acrylamide sulfonic acid, methyl (meth) acrylate, ethyl (meth) acrylate, Butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxyl (meth)acrylate Butyl ester, 2-phenoxy-2-hydroxypropyl (meth)acrylate, 2-(methyl)propenyloxy-2-hydroxypropyl phthalate, glycerol mono(methyl Acrylate, tetrahydrofurfuryl (meth)acrylate, dimethylamino (methyl) Acrylate, glycidyl (meth)acrylate, 2,2,2-trifluoroethyl (meth)acrylate, 2,2,3,3-tetrafluoropropyl (meth)acrylate, o-phenylene a half (meth) acrylate of a formic acid derivative, N-methylol (meth) acrylamide, two bisphenol A compounds, a bisphenol F type compound or a bisphenol S type compound (methyl group) 2,2-bis[4-{(methyl)propenyloxytriethoxy}phenyl]propane, 2,2-bis[4-{(methyl)propene oxime Pentaethoxy}phenyl]propane, 2,2-bis[4-{(methyl)propenyloxydecaethoxy}phenyl]propane, 2,2-bis[4-{(methyl) Acryloxytripropenyl}phenyl]propane, 2,2-bis[4-{(methyl)propenyloxypentapropoxy}phenyl]propane, and 2,2-bis[4] Bisphenol (A, F or S) such as -{(methyl)propenyloxydapoxy}phenyl]propane (A, F or S) modified diacrylate, diethylene glycol di(meth)acrylate, tetraethylene Alcohol di(meth)acrylate, butanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, trishydroxyl Propane tri(meth)acrylate, glycerol di(a) Acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, 2,2-bis(4-(methyl)propenyloxydiethoxyphenyl)propane, 2, 2-bis(4-(methyl)propenyloxypolyethoxyphenyl)propane, 2-hydroxy-3-(methyl)propenyloxypropyl (meth) acrylate, ethylene glycol II Glycidyl ether di(meth)acrylate, diethylene glycol diglycidyl ether di(meth)acrylate, diglycidyl di(meth)acrylate, glycerol triacrylate, Methylene bis(meth) acrylamide, (meth) acrylamide methyl ether, formaldehyde triacrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, Polyethylene polypropylene glycol di(meth)acrylate, ethylene glycol di(meth)acrylate , propylene glycol di(meth)acrylate, polyethylene polytrimethylolpropane di(meth)acrylate, 2-(meth)acryloxy-2-hydroxypropyl phthalate, 2 -(Methyl)acryloxyethyl 2-hydroxyethyl phthalate, a compound obtained by reacting a glycidyl group-containing compound with an α,β-unsaturated carboxylic acid, a urethane Monomer, γ-chloro-β-hydroxypropyl-β'-(meth)propenyloxyethyl-o-phthalate, β-hydroxyethyl-β'-(methyl)propene oxime Oxyethyl-o-phthalate, β-hydroxypropyl-β'-(meth)acryloxyethyl-o-phthalate, and the like. These may be used alone or in combination of two or more.

The compound obtained by reacting the glycidyl group-containing compound with an α,β-unsaturated carboxylic acid may, for example, be triglycerol di(meth)acrylate, but is not limited thereto.

The above urethane monomer is exemplified by, for example, a (meth)acrylic monomer having an OH group at the β-position with isophorone diisocyanate, 2,6-toluene diisocyanate, 2,4-toluene diisocyanate, Addition reactant such as 6-hexamethylene diisocyanate, EO modified urethane di(meth)acrylate, EO, PO modified urethane di(meth)acrylic acid Ester and the like.

As the radical polymerization initiator, a conventional one used in the conventional radical polymerization inhibitor composition can be used. Examples of such a radical polymerization initiator include thioxene such as 2,4-diethylthioxanthone, isopropylthioxanthone, 2-chlorothioxanthone, and 2,4-dimethylthioxanthone. Ketone derivatives; benzophenone, N,N'-tetramethyl-4,4'-diaminobenzophenone, N,N'-tetraethyl-4,4'-diaminodiphenyl Methyl ketone, 4-methoxy-4'-dimethylaminobenzophenone, 2-benzyl-2-dimethyl Aromatic 1-(4-morpholinylphenyl)-butanone-1, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinyl-acetone-1 Ketone; 2-ethyl fluorene, phenanthrenequinone, 2-tert-butyl fluorene, octamethyl hydrazine, 1,2-benzopyrene, 2,3-benzopyrene, 2-phenyl Bismuth, 2,3-diphenylanthracene, 1-chloroindole, 2-methylindole, 1,4-naphthoquinone, 9,10-phenanthrenequinone, 2-methyl-1,4-naphthalene Anthraquinones such as hydrazine and 2,3-dimethylhydrazine; benzoin ether compounds such as benzoin methyl ether, benzoin ethyl ether, and benzoin phenyl ether; benzoin and methyl benzene a benzoin compound such as a benzyl benzoin; a benzyl derivative such as a benzyl dimethyl ketal; a 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer, 2- (o-chlorophenyl)-4,5-bis(methoxyphenyl)imidazole dimer, 2-(o-fluorophenyl)-4,5-diphenylimidazole dimer, 2-( o-Methoxyphenyl)-4,5-diphenylimidazole dimer, 2-(p-methoxyphenyl)-4,5-diphenylimidazole dimer, 2,4,5 a 2,4,5-triarylimidazole dimer such as a triaryl imidazole dimer; an acridine such as 9-phenyl acridine or 1,7-bis(9,9'-acridinyl)heptane; Derivative; ethyl ketone, 1-[9-ethyl-6-(2- Benzoyl-yl group) -9H- carbazol-3-yl] -, 1- (O- acetyl oxime), etc. Oxime esters; N-phenyl glycine; and coumarin compounds. The radical polymerization initiators may be used singly or in combination of two or more.

The amount of the radical polymerization initiator to be used is preferably from 1 to 10 parts by mass, more preferably from 1 to 5 parts by mass, per 100 parts by mass of the monomer and/or resin having an ethylenically unsaturated group. When the amount of the radical polymerization initiator to be used is in the above range, it is possible to impart good curability to the radical polymerization-based resist composition, and it is possible to suppress an increase in cost due to excessive addition of the radical polymerization initiator.

Free radical polymerization inhibitor composition can also be added as needed A resin component having no ethylenically unsaturated bond, a decane coupling agent, a polymerization inhibitor, a solvent, or the like. The resin component which does not have an ethylenic unsaturated bond is added for the improvement of developability, and an example of this is a (meth)acrylic resin which the carboxyl group of a side chain can be esterified by alcohol.

The decane coupling agent is used to impart adhesion between the resin pattern formed by the resist layer 6 and the substrate 4. The decane coupling agent can be used without any particular limitation, but based on the viewpoint that the adhesion between the resin pattern and the substrate 4 is stronger by the molecule in which the decane coupling agent is incorporated in the molecule of the resin pattern, It is preferred to use a decane coupling agent having an ethylenically unsaturated bond. Such a decane coupling agent is exemplified by 3-methacryloxypropyltrimethoxydecane, 3-methylpropenyloxypropylmethyldimethoxydecane, 3-methylpropenyloxypropyl Methyl diethoxy decane, 3-methacryloxypropyl triethoxy decane, p-styryl trimethoxy decane, and the like. The amount of the decane coupling agent to be added is, for example, 1 to 10% by mass based on the solid content ratio of the radical polymerization-based resist composition.

The polymerization inhibitor is added to suppress halation during exposure. The polymerization inhibitor can be used without any particular limitation. The polymerization inhibitor is exemplified by 1,5-dihydroxynaphthalene, 1,4-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 1,3-dihydroxynaphthalene, 1,8- Dihydroxynaphthalene and the like. The amount of the polymerization inhibitor added is, for example, 0.1 to 5% by mass based on the solid content ratio of the radical polymerization-based resist composition. As the solvent, the same ones as those described above for the radical polymerization-based resist composition can be used.

[Guiding hole forming step]

Next, the via hole forming step will be described. The via hole forming step is a step performed after the above-described resist coating step, and is a step shown in FIG. 3(h). Further, in FIG. 3(h), the current collector 2a existing at the bottom of the via hole 7a is omitted in consideration of the ease of viewing of the drawing.

In this embodiment, in the resist layer 6 formed in the resist application step, the via holes 7a and 7b having the same shape as the comb-shaped current collectors 2a and 2b in plan view are formed. The via holes 7a and 7b are formed as through holes penetrating the resist layer 6 up to the surfaces of the current collectors 2a and 2b. In the active material layer forming step described later, the via holes 7a and 7b are used as a mold for depositing a positive electrode or a negative electrode active material.

In the present embodiment, in this step, first, the resist layer 6 formed by the resist application step is selectively exposed by a mask having the same shape as the current collectors 2a and 2b in plan view. According to this, when the resist layer 6 is formed of a negative-type resist, the portion which will not become the via holes 7a and 7b will be hardened in the future and become insoluble in the developing solution, and the developing layer will be a portion of the via holes 7a and 7b in the future. Become soluble. Further, when the resist layer 6 is formed of a positive resist, portions which become the via holes 7a and 7b in the future are made soluble in the developing solution, and the portions which are not to be the via holes 7a and 7b in the future are insoluble to the developing solution.

The selectively exposed resist layer 6 is developed. Development can be carried out by a known method using a conventional developer. Such a developing solution is exemplified by, for example, an alkaline aqueous solution. Further, the developing method is exemplified by a dipping method, a spraying method, and the like.

The developed resist layer 6 has the same shape as the comb-shaped current collectors 2a and 2b in plan view and penetrates to the current collectors 2a and 2b. Guide holes 7a and 7b on the surface. The resist layer 6 on which the via holes 7a and 7b are formed may be subjected to post-baking by irradiation with an active energy ray such as ultraviolet rays, or may be post-baked by additional heat treatment. The resist layer 6 is further cured by post-hardening or post-baking to further improve the solvent resistance or plating solution resistance necessary for the active material layer forming step described later.

[Active material layer forming step]

Next, the active material layer forming step will be described. The active material layer forming step is a step performed after the above-described via forming step, and is a step shown in FIG. 3(i).

In this step, the via holes 7a and 7b formed in the above-described via hole forming step are used as a mold, and the positive electrode active material layer 3a is formed on the surface of the current collector 2a, respectively, and the negative electrode active material layer 3b is formed on the surface of the current collector 2b. Thereby, the electrodes 1a and 1b are completed.

The method of forming the active material layers 3a and 3b on the surfaces of the current collectors 2a and 2b using the via holes 7a and 7b as a mold is exemplified by an electrophoresis method or a plating method. The methods are described below.

In the electrophoresis method, the substrate 4 on which the via holes 7a and 7b have been formed is immersed in a polar solvent in which the positive electrode or the negative electrode active material particles are dispersed, and a voltage is applied to either of the current collectors 2a or 2b to disperse in the solvent. The method of selectively depositing particles of the positive electrode or the negative electrode active material on the surface of the current collector to which the voltage has been applied. Thereby, the via hole 7a or 7b can be used as a mold, and the active material layer 3a or 3b can be deposited on either of the current collectors 2a or 2b.

The active material dispersed in the solvent is exemplified by positive electrode active material particles such as LiCoO ₂ , LiFePO ₄ , and LiMn ₂ O ₄ having a particle diameter of 100 to 10000 nm, preferably 100 to 1000 nm, or graphite, Li ₄ Ti ₅ O ₁₂ , and Sn alloy. A negative electrode active material particle such as a Si-based compound. Further, the amount of the active material dispersed in the solvent is exemplified as 1 to 50 g/L, and the solvent to be used is exemplified by acetonitrile, N-methylpyrrolidone, acetone, ethanol, water or the like. Further, a conductive auxiliary agent such as carbon black, polyvinylidene fluoride or iodine or an adhesive may be added to the solvent. The amount of the conductive auxiliary agent or the adhesive in the solvent is exemplified as 0.1 to 1 g/L, respectively.

Further, when performing electrophoresis, a substrate such as nickel or gold may be used as a counter electrode for electrophoresis about 1 cm above the current collector 2a or 2b. The voltage at this time is exemplified as 1 to 1000V. The electric field density is 1 to 1000 V/cm between the current collectors 2a and 2b, or between the current collectors 2a or 2b and the electrodes opposed to the current collectors 2a or 2b.

The plating method is a method of forming the active material layer 3a or 3b on the surface of the current collector 2a or 2b using a water-soluble plating solution. The plating solution is exemplified by SnCl ₂ . 2H ₂ O 0.01~0.3M aqueous solution, SnCl ₂ . 2H ₂ O and NiCl ₂ . 6H ₂ O mixed 0.01~0.3M aqueous solution, SnCl ₂ . Mixing 2H ₂ O with SbCl ₃ 0.01~0.3M aqueous solution, SnCl ₂ . Mixing 2H ₂ O with CoCl ₂ 0.01~0.3M aqueous solution, SnCl ₂ . A mixture of 2H ₂ O and CuSO ₄ is mixed in an aqueous solution of 0.01 to 0.3 M. Further, in the plating solution, for example, glycine acid, K ₄ P ₂ O ₇ , NH ₄ OH aqueous solution or the like may be added as an additive at a concentration of 0.01 to 0.5 M.

Although the active material layer 3a or 3b is selectively formed on the current collector 2a or 2b by the above electrophoresis method, the active material layer 3a or 3b is not formed by the above plating method. Another episode The electric body 2b or 2a selectively forms the active material layer 3b or 3a. According to this, the positive electrode active material layer 3a can be selectively formed on the surface of the current collector 2a, and the negative electrode active material layer 3b can be selectively formed on the surface of the current collector 2b.

Further, when the active material layer 3a or 3b is formed on the surface of the current collector 2a or 2b, in addition to the above electrophoresis method or plating method, the cathode active material particles or the anode active material particles may be dispersed in the solvent by a capillary. The injection solution is injected into the pilot holes 7a or 7b.

As described above, the active material layers 3a and 3b are formed by electrophoresis or plating using the via holes 7a and 7b formed on the resist layer 6 as a mold. Therefore, the resist layer 6 in the active material layer forming step preferably has resistance to a plating solution used in an electrophoresis method or a plating solution used in a plating method. In the point that the respective resist compositions listed in the above (1) to (4) are based on the resistance to the plating solution, the cationic polymerization inhibitor composition of (1), (2) A novolac-based resist composition or (3) a chemically amplified resist composition is preferred. Further, the resist composition of the above (1) to (3) is more preferably a cationic polymerization inhibitor composition of (1) from the viewpoint of imparting resistance to a solvent used in the above electrophoresis method.

After the active material layers 3a and 3b are formed on the surfaces of the current collectors 2a and 2b, respectively, the resist layer 6 on which the via holes 7a and 7b are formed is removed. Thereby, the electrodes 1a and 1b shown in Fig. 2 are formed. The method of removing the resist layer 6 is exemplified by an ashing method or an etching method in which the resist layer 6 is decomposed by heating at a high temperature.

Next, a comb type electric motor according to a second embodiment of the present invention The pole is described with reference to the drawings. Fig. 4 is a view schematically showing a comb-shaped electrode according to a second embodiment of the present invention. (a) is a plan view, and (b) is a longitudinal cross-sectional view showing the cut surface when the comb-shaped electrode shown in (a) is cut along the line A-A. In the description of the present embodiment, the same components as those in the first embodiment are denoted by the same reference numerals, and their description will be omitted.

The comb-type electrode 100A according to the second embodiment of the present invention includes two electrode units 20, and the electrode units 20 are connected in series. In the electrode unit 20, the electrodes 1a and 1c-1, or the electrodes 1c-2 and 1b are formed in a comb shape, respectively, and are arranged in a facing arrangement in such a manner that the comb-shaped comb portions are alternately shifted and combined. Here, the electrodes 1a and 1c-2 are positive electrodes, and the electrodes 1c-1 and 1b are negative electrodes. By using the electrodes 1a and 1c-1, or the electrodes 1c-2 and 1b, the distance between the electrodes is shortened, the electrolyte resistance is made constant, and lithium ion exchange is efficiently performed, and the battery capacity can be increased. Further, since the comb-shaped electrode 100A is connected in series to two electrode units 20, the voltage of the obtained secondary battery can be increased.

In the same manner as the electrode 1a of the first embodiment, the electrode 1a of the second embodiment has a current collector 2a for taking out electric current, and a positive electrode active material layer 3a formed on the surface of the current collector 2a. In the same manner as the electrode 1b in the first embodiment, the electrode 1b of the second embodiment has a current collector 2b for taking out electric current and a negative electrode active material layer 3b formed on the surface of the current collector 2b.

The matters of the electrodes 1c-1 and 1c-2 are the same as those of the electrodes 1b and 1a in the first embodiment. For example, as shown in FIG. 4(b), the electrode 1c-1 of the negative electrode has a current collector 2c for taking out current, and is collected at the current. The negative electrode active material layer 3c-1 formed on the surface of the body 2c, and the electrode 1c-2 of the positive electrode have a current collector 2c for taking out electric current, and a positive electrode active material layer 3c-2 formed on the surface of the current collector 2c. The current collector 2c is formed into a comb shape in plan view. Further, the negative electrode active material layer 3c-1 and the positive electrode active material layer 3c-2 are formed on the surface of the comb-shaped current collector 2c, and are formed into a comb shape in plan view, similarly to the current collector 2c. However, there is a cut between the negative electrode active material layer 3c-1 and the positive electrode active material layer 3c-2 so that the negative electrode active material and the positive electrode active material are not mixed and blended. In the present specification, the term "series" also means that there is a cut between the electrode units, and the electrode units are connected through the current collector.

The current collector 2c is the same as the current collectors 2a and 2b in the first embodiment. The negative electrode active material layer 3c-1 and the positive electrode active material layer 3c-2 are the same as the negative electrode active material layer 3b and the positive electrode active material layer 3a in the first embodiment.

In the current collector forming step and the via forming step in the comb-shaped electrode manufacturing method according to the first embodiment, the comb-shaped electrode of the second embodiment can be formed by replacing the pattern corresponding to the comb-shaped electrode 100A. The pattern of the comb-shaped electrode 100 is manufactured in the same manner as the method shown in Fig. 3 . However, since a cut is formed between the anode active material layer 3c-1 and the cathode active material layer 3c-2, in the via hole forming step, a pattern in which a portion corresponding to the slit is formed may be used.

Further, in the first and second embodiments described above, the case where a plurality of electrode units are connected in parallel or in series is described. However, in the present invention, a plurality of electrode units may be connected in any combination of parallel and series. Since the secondary battery having the comb-shaped electrode to which the electrode unit is connected is connected in parallel and in series as the electrode unit, the battery capacitance and voltage can be effectively improved.

Next, a comb-shaped electrode according to a third embodiment of the present invention will be described with reference to the drawings. 5 and 6 are plan views schematically showing a comb-shaped electrode according to a third embodiment of the present invention. In the description of the embodiment, the same components as those in the first embodiment are denoted by the same reference numerals, and their description will be omitted.

The electrodes 11a and 11b formed in the present embodiment are formed on the surfaces of the comb-shaped current collectors 2a and 2b in a plurality of polygonal island structures.

A plurality of positive electrode active material layers 13a formed in a polygonal island structure are provided along one of the comb teeth of the comb-type current collector 2a. At this time, each of the positive electrode active material layers 13a is provided such that a part thereof is in contact with the current collector 2a. Thereby, the current generated by the reaction with the electrode of the positive electrode active material layer 13a is taken out by the current collector 2a.

A plurality of negative electrode active material layers 13b formed by a polygonal island structure are provided along one of the comb teeth of the comb-type current collector 2b. At this time, each of the negative electrode active material layers 13b is provided such that a part thereof is in contact with the current collector 2b. Thereby, the current generated by the reaction with the electrode of the negative electrode active material layer 13b is taken out by the current collector 2b.

Each of the positive electrode active material layer 13a and the negative electrode active material layer 13b is formed to face the surfaces of the current collectors 2a and 2b disposed to face each other in such a manner that the comb-shaped portions of the comb-shaped shape are alternately combined. Therefore, each positive active material layer 13a and each of the negative electrode active material layers 13b are arranged to face each other in such a manner that the comb-shaped portions of the comb-shaped shape are alternately shifted, and the positive electrode 11a and the negative electrode 11b are arranged to be aligned in a comb-shaped portion of the comb shape. . Therefore, the present embodiment in which the comb-shaped electrode is formed is also the first aspect of the present invention. The order in which the positive electrode 11a and the negative electrode 11b are formed is the same as that of the first embodiment described above, and thus the description thereof will be omitted. In addition, the material of the positive electrode active material layer 13a and the negative electrode active material layer 13b is the same as that of the positive electrode active material layer 3a and the negative electrode active material layer 3b in the first embodiment described above, and thus the description thereof will be omitted.

The planar shape of the positive electrode active material layer 13a and the negative electrode active material layer 13b is not particularly limited, and may be a polygonal shape as shown in FIGS. 5 and 4, or may be a circular shape or the like. When the planar shape of the positive electrode active material layer 13a and the negative electrode active material layer 13b is polygonal, the polygonal shape is exemplified by an equilateral triangle, a square, a regular pentagon, a regular hexagon, etc., but a hexagonal shape is preferable. By making the positive electrode active material layer 13a and the negative electrode active material layer 13b have a regular hexagonal shape, the positive electrode active material layer 13a and the negative electrode active material layer 13b can be arranged and arranged at substantially equal intervals, which can be shortened. The moving distance of a charge substance such as lithium ion between the active material layers. Thereby, the current obtained from the secondary battery can be made large. In addition, when the negative electrode active material layer 13b is formed of a material other than carbon, a large volume change of the negative electrode active material layer 13b occurs due to the charge and discharge of lithium ions or the like in the charge and discharge, and the volume change is caused by the volume change. Although the crack is generated in the negative electrode active material layer 13b, the shape of the above-described shape can suppress the occurrence of cracks in the negative electrode active material layer 13b as the volume changes. Further, even when the negative electrode active material layer 13b is formed of a material having a small volume change such as carbon or Li ₄ Ti ₅ O ₁₂ , since the materials do not undergo volume change due to charge and discharge, the comb-shaped electrode of the present invention is comparatively The electrode used in the past can suppress the occurrence of cracks, and the effects of the present invention can be obtained.

However, the cumulative amount of the charge substance such as lithium ions in the one negative electrode active material layer 13b varies depending on the material constituting the negative electrode active material layer 13b. Therefore, in consideration of the theoretical capacitance based on the material constituting the positive electrode active material layer 13a, and the theoretical capacitance based on the material constituting the negative electrode active material layer 13b, it is preferable to appropriately determine the positive electrode active material layer 13a and the negative electrode 11b contained in the positive electrode 11a. The mass ratio of the negative electrode active material layer 13b (hereinafter also referred to as "positive electrode/negative electrode ratio") is adjusted to balance the capacitance of the two.

The case where the positive electrode active material layer 13a is formed by LiCoO ₂ will be described as an example of the determination of the mass ratio. The theoretical theoretical capacitance of LiCoO ₂ is 140 mAh/g.

In the above example, when the negative electrode active material layer 13b is composed of carbon (the negative electrode theoretical capacitance: 360 mAh/g), the positive electrode/negative electrode ratio is preferably about 1:1, and the alloy material (Sn system, negative electrode theoretical capacity 800 to 900 mAh/g) When the negative electrode active material layer 13b is formed, the positive electrode/negative electrode ratio is preferably about 2:1 to 3:1, and when the negative electrode active material layer 13b is composed of a lanthanoid material (SiC, SiO, or the like, a theoretical capacity of the negative electrode of 2000 mAh/g), the positive electrode is formed. The ratio of the negative electrode to the negative electrode is preferably about 4:1 to 5:1.

The method of adjusting the ratio of the positive electrode to the negative electrode is not particularly limited, and an example is a method of increasing the mass of each of the positive and negative active material layers, and reducing the mass of each of the other active material layers, or making one of positive and negative active A method in which the number of material layers is larger than the number of other active material layers.

In the state in which the positive electrode/negative electrode ratio is adjusted, the number of the positive electrode active material layers 13a is larger than the number of the negative electrode active material layers 13b. In FIG. 5, the number of the positive electrode active material layer 13a and the negative electrode active material layer 13b is adjusted to the positive electrode active material layer 13a: the negative electrode active material layer 13b=2:1. In this case, the two positive electrode material layers 13a and one negative electrode active material layer 13b included in the range surrounded by a broken line in FIG. 5 are one set, and constitute one battery unit. In FIG. 6, the number of the positive electrode active material layer 13a and the negative electrode active material layer 13b is adjusted to the positive electrode active material layer 13a: the negative electrode active material layer 13b=4:1. In this case, the four positive electrode material layers 13a and one negative electrode active material layer 13b included in the range surrounded by a broken line in FIG. 6 are one set, and constitute one battery unit.

The size of each of the positive electrode active material layer 13a or the negative electrode active material layer 13b is not particularly limited. However, from the viewpoint of suppressing occurrence of cracks in the active material layer, the maximum diameter is preferably about 80 to 120 μm, preferably 100 μm. about. Further, the interval between the respective positive electrode active material layers 13a and the negative electrode active material layer 13b is not particularly limited, but is preferably about 10 to 50 μm, preferably about 20 μm. In addition, the interval between the positive electrode active material layer 13a and the negative electrode active material layer 13b in the adjacent relationship is set.

The number of battery units included in the comb-shaped electrode may be appropriately set in consideration of the installation area of the comb-shaped electrode or the necessary battery capacity. As an example of this, it is exemplified that one battery unit or more and ten battery units or more are arranged in the direction of the peak shape of the comb shape formed by the peak and the comb teeth, and the comb type is listed. The shape of the comb is arranged in one or more battery units or more than 10 battery units, but is not particularly limited.

One of the specific dimensions of the comb-shaped electrode of the present embodiment is shown in Fig. 7 . Fig. 7 is a plan view schematically showing a comb-shaped electrode according to a third embodiment of the present invention. The comb-shaped electrode shown in FIG. 7 is more easily understood for simplification, and therefore has a structure composed of only one battery unit including four positive electrode active material layers 13a and one negative electrode active material layer 13b. In the present embodiment, by providing the above-described via hole forming step and active material layer forming step, even a secondary battery having a fine comb-type electrode as shown in FIG. 7 can be produced with good reproducibility.

According to the present invention, an electrode having a comb-shaped fine structure and an active material layer on the surface thereof can be formed with good reproducibility. Since such an electrode can be formed in a small size, it can be preferably used as an assembled secondary battery in, for example, a microelectromechanical device.

[Examples]

Hereinafter, the present invention will be more specifically described by the examples, but the present invention is not limited by the following examples.

[Synthesis Example 1]

A cresol obtained by adding a mixture of m-cresol and p-cresol (m-cresol/p-cresol = 6/4 (mass ratio)) to formaldehyde in a conventional manner in the presence of an acid catalyst 70 parts by mass of a novolak resin (mass average molecular weight 30000), 1,4-bis(4-hydroxyphenylisopropylidene)benzene naphthalene as a sensitizer 15 parts by mass of 醌-1,2-azido-5-sulfonic acid diester and 15 parts by mass of polymethyl vinyl ether (mass average molecular weight 100,000) as a plasticizer so that the solid content concentration becomes 40% by mass. After adding propylene glycol monomethyl ether acetate (PGMEA) as a solvent, it was mixed and dissolved to obtain a resist composition. The resist composition is a novolak type and is a positive type.

[Example 1] A comb-type electrode 100 according to Embodiment 1 of the present invention was produced as follows.

(formation of current collector)

First, an aluminum film (thickness: 200 nm) was formed as a conductive layer on the surface of a germanium substrate having an oxide film by sputtering. The positive resist composition of Synthesis Example 1 was applied onto the substrate by spin coating to form a 1.5 μm resist layer, which was dried at 120 ° C for 1 minute. Next, the resist layer was selectively exposed (ghi mixed line, exposure amount: 100 mJ/cm ² ) using a mask having a pattern corresponding to the comb-shaped electrode 100 shown in Fig. 1. Subsequently, it was developed with a TMAH 2.38 mass% alkali developer for 1 minute. After the development, an aluminum etching solution (H ₃ PO ₄ :HNO ₃ :H ₂ O=4:1:1.6 (mass ratio)) was etched by a dipping method to form an aluminum pattern to form a comb-type current collector.

(production of guide holes)

The resist composition of Synthesis Example 1 was applied onto the surface of the tantalum wafer on which the current collector was formed by a spin coating method to form a 20 μm resist layer, which was dried at 120 ° C for 6 minutes. Subsequently, the positive-type mask having the same shape as that of the formed comb-type current collector is viewed in a plan view, and the resist layer positioned on the upper portion of the comb-type current collector is exposed (ghi mixing line, exposure amount: 300 mJ/cm ² ), And developed with an alkali developer. Thereby, a comb-shaped guide hole is formed on the surface of the crucible wafer. Further, the current collector is exposed at the bottom of the via hole.

(formation of active material layer)

38.7 g of LiFePO ₄ particles, 2.58 g of acetylene black as a conductive auxiliary agent, 0.43 g of carboxymethylcellulose as a dispersing agent, and 1.29 g of styrene butadiene rubber (SBR) as an adhesive were mixed, and 57 g was further added. The water was mixed and mixed to obtain a dispersion of 43% by mass of the solid component. The dispersion was rotated at 2000 rpm for 10 minutes using a rotation revolutionary kneading machine (trade name: AWATORY, Tatky Co., Ltd.), and then mixed. The mixture was used as a positive electrode active material.

38.7 g of Li ₄ Ti ₅ O ₁₂ particles, 2.58 g of acetylene black as a conductive auxiliary agent, 0.43 g of carboxymethylcellulose as a dispersing agent, and 1.29 g of SBR as an adhesive were mixed, and 57 g of water was further added and mixed. A dispersion of 43% by mass of the solid component was obtained. The dispersion was rotated at 2000 rpm for 10 minutes using a rotation revolutionary kneading machine (trade name: AWATORY, Tatky Co., Ltd.), and then mixed. The mixture was used as a negative electrode active material.

By using a micropipette, the positive electrode active material is dropped onto the periphery corresponding to the positive electrode in the via hole formed as described above, and the above negative electrode active material is dropped on the periphery corresponding to the negative electrode, and the inflow is cautiously In the guide holes of the comb pattern. Subsequently, drying at 100 ° C After 5 minutes, an active material layer was formed. Finally, the resist layer was peeled off with acetone to obtain a comb-shaped electrode 100.

1a‧‧‧electrode

1b‧‧‧electrode

4‧‧‧Substrate

20‧‧‧Electrode units

100‧‧‧ comb electrode

Claims (4)

A comb-shaped electrode in which a positive electrode and a negative electrode are respectively formed in a comb shape, and a plurality of electrode units arranged such that the positive electrode and the negative electrode are alternately arranged in a comb-shaped comb-tooth shape are arranged, and such Connected in parallel and / or in series. A method for manufacturing a comb-shaped electrode, wherein the positive electrode and the negative electrode are each formed in a comb shape, and a plurality of electrode units in which the positive electrode and the negative electrode are alternately arranged in a comb-shaped tooth portion are arranged in an opposite direction, and The method for manufacturing the comb-shaped electrode connected in parallel and/or in series is characterized in that the conductive layer is formed on the surface of the substrate so as to have the same shape as the comb-shaped electrode in plan view, so that the a current collector forming step of patterning the conductive layer to form a current collector, and coating a resist composition on the surface of the substrate included in the current collector portion formed in the current collector forming step to form a resist layer a coating step, and a step of forming a via hole for forming a via hole for forming a positive electrode or a negative electrode over the current collector by developing light by irradiating a surface of the resist layer with a mask, and the resist is formed The agent composition is any one of the resist compositions of the following (1) to (4), and (1) a cationic polymerization-based resist composition containing a compound having an epoxy group and a cationic polymerization initiator, (2) )phenol Novolac resist composition comprising novolac resin and a sensitizer, (3) a chemically amplified damper composition containing a dissociative group having acid dissociation, and the detachment group is detached by an action of an acid generated by a photoacid generator by exposure, thereby increasing a base a soluble resin and a photoacid generator, (4) a radical polymerization-based resist composition containing a monomer having an ethylenically unsaturated bond and/or a resin, and a radical polymerization initiator, which contains ethylene When the monomer of the unsaturated bond is used, the number of ethylenically unsaturated bonds contained in one molecule of the monomer is three or less. The method of producing a comb-shaped electrode according to claim 2, further comprising an active material layer forming step of forming an active material layer on the surface of the current collector by using a via hole formed in the via hole forming step as a mold. A secondary battery having the comb-type electrode of claim 1.