JP5237546B2 - Negative electrode base material for lithium secondary battery - Google Patents

Description

The present invention is a lithium secondary battery anode substrate, a lithium secondary battery using the negative Gokumoto material, photoresist composition used for forming the negative Gokumoto material, and relates to a manufacturing method of the negative Gokumoto material, in particular, charging and discharging can be provided a lithium secondary battery having excellent cycle characteristics anode substrate for a lithium secondary battery, a lithium secondary battery using the negative Gokumoto material, photoresist composition used for forming the negative Gokumoto material, and this The present invention relates to a method for producing a negative electrode substrate.

  Conventionally, research and development of batteries having high output voltage and high energy density have been actively promoted. In particular, a secondary battery having a low internal resistance and a low battery capacity decrease due to charge / discharge and excellent charge / discharge cycle characteristics is required. For example, a lithium secondary battery using thin-film amorphous silicon or microcrystalline silicon as a negative electrode material (negative electrode active material) is known (see Patent Document 1). Specifically, a lithium secondary battery using a negative electrode in which a negative electrode material layer made of a silicon thin film is formed on a current collector is disclosed. For the formation of a silicon thin film, a CVD method (chemical vapor deposition method, Thin film forming methods such as chemical vapor deposition and sputtering are used.

  Here, it is considered that a material such as silicon repeats expansion / contraction as the lithium is occluded / released. In the negative electrode in which the silicon thin film is formed on the current collector, the adhesion between the current collector and the negative electrode material layer is high, and thus the current collector is frequently expanded / contracted due to the expansion / contraction of the negative electrode material. Become. For this reason, there is a possibility that irreversible deformation such as wrinkles may occur in the negative electrode material layer and the current collector along with charging and discharging. In particular, when a metal foil having a high ductility such as a copper foil is used for the current collector, the degree of deformation tends to increase. When the negative electrode is deformed, the energy density of the battery may be lowered due to an increase in volume as an electrode and non-uniform electrochemical reaction. In addition, while the expansion / contraction associated with charge / discharge is repeated, the negative electrode material may be pulverized and detached from the current collector, or may be detached in a thin film in some cases. It becomes a factor to deteriorate.

  Examples of a method for suppressing deformation of the negative electrode include a method in which a material having high mechanical strength such as tensile strength and tensile elastic modulus is used as a current collector. However, when a negative electrode material layer made of a thin film negative electrode material is formed on a current collector made of such a material, the adhesion between the negative electrode material layer and the current collector becomes insufficient, and a sufficient charge / discharge cycle Characteristics may not be obtained. For this reason, in Patent Document 1, an intermediate layer made of a material that forms an alloy with the negative electrode material is disposed between the current collector and the negative electrode material layer, and a current collector having higher mechanical strength than the intermediate layer is used. Discloses a technique for suppressing the detachment of the negative electrode material during charging and discharging and suppressing the generation of soot and the like. Specifically, a copper layer is used as the intermediate layer, and a nickel foil is used as the current collector.

  In addition to Patent Document 1, a technique for suppressing expansion of the negative electrode material when lithium is occluded by using a thin film in which copper is dissolved in silicon as the negative electrode material layer and suppressing the occlusion amount of lithium is disclosed. (See Patent Document 2). Moreover, as the negative electrode material layer, an alloy thin film composed of a metal alloying with lithium and a metal not alloying with lithium is used, and by suppressing the occlusion amount of lithium, the negative electrode material expands when lithium is occluded. The technique to suppress is disclosed (refer patent document 3). Specifically, Sn, Ge, Al, In, Mg, Si, or the like is used as a metal that is alloyed with lithium to form a solid solution or an intermetallic compound. Cu, Fe, and the like that are not alloyed with lithium are used. Ni, Co, Mo, W, Ta, Mn, and the like are used.

Further, by using a current collector in which 10 or more deformed portions having a deformation amount in the thickness direction of 5 μm to 20 μm are formed per 1 cm ² and an aperture ratio by the deformed portions is 4% or less, charging is performed. A technique for suppressing deformation of an electrode accompanying discharge is disclosed (see Patent Document 4). Furthermore, a technique is disclosed in which a lithium non-occlusion material is disposed on at least one of the surface and the inside of a thin film negative electrode material layer capable of reversibly occluding / releasing lithium (see Patent Document 5).
Japanese Patent Laid-Open No. 2002-083594 JP 2002-289177 A JP 2002-373647 A JP 2003-017069 A JP 2005-196971 A

However, even with any of the various negative electrode materials described above, a battery having a sufficient output voltage, energy density, and charge / discharge cycle characteristics has not been obtained. Accordingly, an object of the present invention, the structure different from the prior art described above, has a high output voltage and a high energy density, and a lithium secondary allows the realization of excellent lithium secondary battery charge-discharge cycle characteristics primary It is providing the negative electrode base material for batteries, the lithium secondary battery using this negative electrode base material, the photoresist composition used for formation of this negative electrode base material, and the manufacturing method of this negative electrode base material.

  As a result of intensive studies in view of the above, the present inventors have a high output voltage and a high energy density according to the negative electrode substrate in which the metal film is formed on the patterned silica-based film, And it discovered that the battery excellent in charging / discharging cycling characteristics can be provided, and came to complete this invention.

That is, the present invention forms a silica-based film comprising a coating liquid for forming a silica-based film on a support on which a photoresist pattern is formed, and forms a predetermined metal film on the support from which the photoresist pattern has been removed. lithium secondary characterized by comprising Te battery for anode substrate, a lithium secondary battery using the negative Gokumoto material, photoresist composition used for forming the negative Gokumoto material, further the manufacturing method of the negative Gokumoto material I will provide a.

According to the present invention, has a high output voltage and a high energy density, and charge-discharge cycle characteristics superior anode substrate for a lithium secondary battery that allows the realization of a lithium secondary battery, use the negative Gokumoto material The present invention can provide a lithium secondary battery, a photoresist composition used for forming the negative electrode substrate, and a method for producing the negative electrode substrate.

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

<Negative electrode base material>
A schematic diagram of a negative electrode substrate 10 according to the present invention is shown in FIG. As shown in FIG. 1, the negative electrode substrate 10 according to the present invention includes a support 11, a silica-based coating 12, and a metal film 13. More specifically, the negative electrode base material 10 according to the present invention is provided with a metal film 13 on the surface of a support 11 having a patterned silica-based film 12.

  The negative electrode substrate 10 according to the present invention is obtained as follows. First, a photoresist pattern is formed on the support 11. A silica-based film is formed by applying a coating liquid for forming a silica-based film on the formed photoresist pattern. Next, an unnecessary photoresist pattern is removed to obtain a silica-based coating 12 patterned on the support 11. Finally, a metal film 13 is formed on the support 11 having the patterned silica-based film 12.

<Support>
The support 11 used for the negative electrode substrate 10 according to the present invention is not particularly limited as long as it can form a photoresist pattern or a silica-based coating 12 on the surface thereof. For example, a conventionally known substrate such as a substrate for electronic components is used. Specifically, a silicon wafer, a silicon wafer provided with an organic or inorganic antireflection film, a silicon wafer provided with a magnetic film, a metal substrate such as copper, chromium, iron, aluminum, or a glass substrate Etc. These supports are materials such as materials containing at least one element selected from copper, nickel, stainless steel, molybdenum, tungsten, titanium, and tantalum, metal foils, nonwoven fabrics, and metal current collectors having a three-dimensional structure. It may serve also as an electric current body, and may be formed on these current collectors.

<Photoresist pattern>
The photoresist pattern necessary for forming the patterned silica-based coating 12 is formed by a conventionally known photoresist composition and is not particularly limited. Specifically, the photoresist pattern is formed by applying a conventionally known photoresist composition on the support 11 and then patterning it into a predetermined shape by pattern exposure. Preferably, it is a photoresist pattern formed by a photoresist composition described later.

[Photoresist composition]
It does not specifically limit as a photoresist composition used for formation of a photoresist pattern, A conventionally well-known photoresist composition is used.

[Positive photoresist composition]
The positive chemically amplified photoresist composition includes an acid generator component (hereinafter referred to as component (A)) that generates an acid upon irradiation with actinic rays or radiation, and a resin whose solubility in an alkaline aqueous solution is changed by the action of the acid. What uses a component (henceforth (B) component) as a basic component is used preferably. As the component (B), a resin in which the hydroxyl group of the alkali-soluble resin is protected with an acid dissociable, dissolution inhibiting group and becomes insoluble in alkali is used. By using such a component (B) in combination with the component (A), an acid is generated in the exposed portion, which dissociates protection by the acid dissociable, dissolution inhibiting group. As a result, the exposed portion becomes alkali-soluble, and only the exposed portion is selectively removed during development to obtain a photoresist pattern having a predetermined shape.

(Acid generator component (A))
(A) As a component, it is a substance which generate | occur | produces an acid directly or indirectly by irradiation of actinic light or a radiation.

  As a first embodiment of such an acid generator, 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2 -(2-furyl) ethenyl] -s-triazine, 2,4-bis (trichloromethyl) -6- [2- (5-methyl-2-furyl) ethenyl] -s-triazine, 2,4-bis ( Trichloromethyl) -6- [2- (5-ethyl-2-furyl) ethenyl] -s-triazine, 2,4-bis (trichloromethyl) -6- [2- (5-propyl-2-furyl) ethenyl ] -S-triazine, 2,4-bis (trichloromethyl) -6- [2- (3,5-dimethoxyphenyl) ethenyl] -s-triazine, 2,4-bis (trichloromethyl) -6- [2 -(3,5-diethoxyphenyl) ethenyl] s-triazine, 2,4-bis (trichloromethyl) -6- [2- (3,5-dipropoxyphenyl) ethenyl] -s-triazine, 2,4-bis (trichloromethyl) -6- [2- (3-methoxy-5-ethoxyphenyl) ethenyl] -s-triazine, 2,4-bis (trichloromethyl) -6- [2- (3-methoxy-5-propoxyphenyl) ethenyl] -s-triazine, 2 , 4-Bis (trichloromethyl) -6- [2- (3,4-methylenedioxyphenyl) ethenyl] -s-triazine, 2,4-bis (trichloromethyl) -6- (3,4-methylenedi Oxyphenyl) -s-triazine, 2,4-bis-trichloromethyl-6- (3-bromo-4-methoxy) phenyl-s-triazine, 2,4-bis-trichloromethyl-6- (2-butyl) Lomo-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) ethenyl] -4,6-bis (trichloromethyl) -1,3,5-triazine 2- [2- (5-methyl-2-furyl) ethenyl] -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- [2- (3,5-dimethoxyphenyl) ethenyl ] -4, -Bis (trichloromethyl) -1,3,5-triazine, 2- [2- (3,4-dimethoxyphenyl) ethenyl] -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-triazine, tris ( Halogen-containing triazine compounds such as 2,3-dibromopropyl) -1,3,5-triazine, and halogen-containing compounds represented by the following general formula (a1) such as tris (2,3-dibromopropyl) isocyanurate A triazine compound is mentioned.

In said general formula (a1), R ^<1a> , R ^<2a> , and R ^<3a> are respectively independent halogenated alkyl groups, and the carbon atom number of the said alkyl group is 1-6.

  In addition, as a second aspect of the acid generator, α- (p-toluenesulfonyloxyimino) -phenylacetonitrile, α- (benzenesulfonyloxyimino) -2,4-dichlorophenylacetonitrile, α- (benzenesulfonyloxyimino) ) -2,6-dichlorophenylacetonitrile, α- (2-chlorobenzenesulfonyloxyimino) -4-methoxyphenylacetonitrile, α- (ethylsulfonyloxyimino) -1-cyclopentenylacetonitrile, and an oxime sulfonate group. The compound represented by the following general formula (a2) to contain is mentioned.

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

In the general formula (a2), R ^4a is particularly preferably an aromatic compound group. Examples of such an aromatic compound group include an aromatic hydrocarbon group such as a phenyl group and a naphthyl group, Heterocyclic groups such as a furyl group and a thienyl group are exemplified. These may have one or more suitable substituents such as a halogen atom, an alkyl group, an alkoxy group, and a nitro group on the ring. R ^5a is particularly preferably a lower alkyl group having 1 to 6 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, and a butyl group.

As the acid generator represented by the general formula (a2), when n = 1, R ^4a is any one of a phenyl group, a methylphenyl group, and a methoxyphenyl group, and R ^5a is a methyl group. Specifically, α- (methylsulfonyloxyimino) -1-phenylacetonitrile, α- (methylsulfonyloxyimino) -1- (p-methylphenyl) acetonitrile, α- (methylsulfonyloxyimino) -1- (p- Methoxyphenyl) acetonitrile, [2- (propylsulfonyloxyimino) -2,3-dihydroxythiophene-3-ylidene] (o-tolyl) acetonitrile, and the like. Specific examples of the acid generator represented by the above general formula when n = 2 include acid generators represented by the following chemical formulas (a2-1) to (a2-8).

  Furthermore, as a third embodiment of the acid generator, an onium salt having a naphthalene ring in the cation portion can be used. This “having a naphthalene ring” means having a structure derived from naphthalene, and means that at least two ring structures and their aromaticity are maintained. 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 (one free valence) or a divalent group (two free valences) or more, but may be a monovalent group. Desirable (however, at this time, the free valence is counted excluding the portion bonded to the substituent). The number of naphthalene rings is preferably 1 to 3.

  As a cation part of the onium salt having a naphthalene ring in such a cation part, a structure represented by the following general formula (a3) is preferable.

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 is a linear or branched chain having 1 to 6 carbon atoms. An 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 each independently a straight chain or branched chain having 1 to 6 carbon atoms. It is a chain alkylene group, and these ends may be bonded to form a ring.

In the general formula (a4), R ^9a and R ^10a are each independently a hydroxyl group, a linear or branched alkoxy group having 1 to 6 carbon atoms, or a straight chain having 1 to 6 carbon atoms or A branched alkyl group, R ^11a is a linear or branched alkylene group having 1 to 6 carbon atoms which may have a single bond or a substituent, and p and q are independent of each other. 0 or an integer of 1 to 2, and p + q is 3 or less. However, when two or more R ^<10a> exists, they may be mutually the same or different. When a plurality of R ^9a are present, they may be the same as or different from each other.

Of the above R ^6a , R ^7a , and R ^8a , the number of groups represented by the general formula (a4) is preferably one from the viewpoint of the stability of the compound, and the remainder is 1 to 6 carbon atoms. A linear or branched alkyl group or a phenyl group which may have a substituent, and these ends may be bonded to form a ring. In this case, the two alkylene groups constitute a 3- to 9-membered ring including a sulfur atom. The number of atoms (including sulfur atoms) constituting the ring is preferably 5-6.

  Examples of the substituent that the alkylene group may have include an oxygen atom (in this case, a carbonyl group is formed together with a carbon atom constituting the alkylene group), a hydroxyl group, and the like.

  In addition, examples of the substituent that the phenyl group may have include a hydroxyl group, a linear or branched alkoxy group having 1 to 6 carbon atoms, or a linear or branched chain group having 1 to 6 carbon atoms. An alkyl group etc. are mentioned.

  Suitable examples of the cation moiety include those represented by the following chemical formulas (a5) and (a6), and the structure represented by the chemical formula (a6) is particularly preferable.

  Such a cation moiety may be an iodonium salt or a sulfonium salt, but a sulfonium salt is desirable from the viewpoint of acid generation efficiency and the like.

  Therefore, an anion capable of forming a sulfonium salt is desirable as a suitable anion part for an onium salt having a naphthalene ring in the cation part.

  As such an anion portion of the photoacid generator, a fluoroalkyl sulfonate ion or an aryl sulfonate ion in which a part or all of hydrogen atoms are fluorinated is preferable.

  The alkyl group in the fluoroalkylsulfonic acid ion may be linear, branched or cyclic having 1 to 20 carbon atoms, and preferably has 1 to 10 carbon atoms from the bulk of the acid generated and its diffusion distance. . In particular, a branched or annular shape is preferable because of its short diffusion distance. Specifically, a methyl group, an ethyl group, a propyl group, a butyl group, an octyl group, and the like are preferable because they can be synthesized at a low cost.

  The aryl group in the aryl sulfonate ion is an aryl group having 6 to 20 carbon atoms, and examples thereof include an alkyl group, a phenyl group which may or may not be substituted with a halogen atom, and a naphthyl group. An aryl group having 6 to 10 carbon atoms is preferable because it can be synthesized. Specific examples include a phenyl group, a toluenesulfonyl group, an ethylphenyl group, a naphthyl group, and a methylnaphthyl group.

  In the fluoroalkyl sulfonate ion or aryl sulfonate ion, the fluorination rate when part or all of the hydrogen atoms are fluorinated is preferably 10 to 100%, more preferably 50 to 100%, In particular, those in which all hydrogen atoms are substituted with fluorine atoms are preferred because the strength of the acid is increased. Specific examples thereof include trifluoromethane sulfonate, perfluorobutane sulfonate, perfluorooctane sulfonate, and perfluorobenzene sulfonate.

  Especially, what is shown by the following general formula (a7) as a preferable anion part is mentioned.

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

In the general formula (a8), l is an integer of 1 to 4, and in the general formula (a9), R ^13a is a hydrogen atom, a hydroxyl group, a linear or branched alkyl group having 1 to 6 carbon atoms, Or a C1-C6 linear or branched alkoxy group is shown, m is an integer of 1-3. Among these, trifluoromethane sulfonate and perfluorobutane sulfonate are preferable from the viewpoint of safety.

  Moreover, as an anion part, what contains the nitrogen represented by the following chemical formula (a11) and (a12) can also be used.

In the above formulas (a11) and (a12), X ^a1 is a linear or branched alkylene group in which at least one hydrogen atom is substituted with a fluorine atom, and the alkylene group has 2 to 6 carbon atoms. Preferably 3 to 5 and most preferably 3 carbon atoms. X ^a2 and X ^a3 are each independently a linear or branched alkyl group in which at least one hydrogen atom is substituted with a fluorine atom, and the alkyl group has 1 to 10 carbon atoms. , Preferably 1-7, more preferably 1-3.

Solubility within the resist solvent is low number of carbon atoms of the alkyl group having a carbon number or X ^a2, X ^a3 alkylene group X ^a1 is also preferred for their good.

In addition, in the alkylene group of X ^a1 or the alkyl group of X ^a2 and X ^a3 , the greater the number of hydrogen atoms substituted with fluorine atoms, the stronger the acid strength, which is preferable. The proportion of fluorine atoms in the alkylene group or alkyl group, that is, the fluorination rate is preferably 70 to 100%, more preferably 90 to 100%, and most preferably all hydrogen atoms are substituted with fluorine atoms. A perfluoroalkylene group or a perfluoroalkyl group.

  Preferable examples of the onium salt having a naphthalene ring at the cation moiety include compounds represented by the following chemical formulas (a13) and (a14).

  Furthermore, as another embodiment of the acid generator, bis (p-toluenesulfonyl) diazomethane, bis (1,1-dimethylethylsulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, bis (2,4-dimethylphenylsulfonyl) Bissulfonyldiazomethanes such as diazomethane; 2-nitrobenzyl p-toluenesulfonate, 2,6-dinitrobenzyl p-toluenesulfonate, nitrobenzyl tosylate, dinitrobenzyl tosylate, nitrobenzyl sulfonate, nitrobenzyl carbonate Nitrobenzyl derivatives such as dinitrobenzyl carbonate; pyrogallol trimesylate, pyrogallol tritosylate, benzyl tosylate, benzyl sulfonate, N-methylsulfonyloxysuccinimide, N- Sulfonic acid esters such as lichloromethylsulfonyloxysuccinimide, N-phenylsulfonyloxymaleimide and N-methylsulfonyloxyphthalimide; trifluoromethanesulfonic acid esters such as N-hydroxyphthalimide and N-hydroxynaphthalimide; diphenyliodonium hexafluorophos Phat, (4-methoxyphenyl) phenyliodonium trifluoromethanesulfonate, bis (p-tert-butylphenyl) iodonium trifluoromethanesulfonate, triphenylsulfonium hexafluorophosphate, (4-methoxyphenyl) diphenylsulfonium trifluoromethanesulfonate , (P-tert-butylphenyl) diphenylsulfonium trifluoromethanesulfonate Onium salts of bets like; benzoin tosylate, benzoin tosylate such as α- methyl benzoin tosylate; other diphenyliodonium salts, triphenylsulfonium salts, phenyldiazonium salts, benzyl carbonate and the like.

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

In the above formula (a15), X ^a4 represents a sulfur atom or iodine atom having a valence of s, and s is 1 or 2. n represents a repeating unit having a structure in parentheses. R ^14a is an organic group bonded to ^{X a4,} aryl group having 6 to 30 carbon atoms, a heterocyclic group having a carbon number of 4 to 30, alkyl group having 1 to 30 carbon atoms, carbon atoms 2 Represents an alkenyl group having ˜30 or an alkynyl group having 2 to 30 carbon atoms, R ^14a is alkyl, hydroxy, alkoxy, alkylcarbonyl, arylcarbonyl, alkoxycarbonyl, aryloxycarbonyl, arylthiocarbonyl, acyloxy, arylthio, Substituted with at least one selected from the group consisting of alkylthio, aryl, heterocycle, aryloxy, alkylsulfinyl, arylsulfinyl, alkylsulfonyl, arylsulfonyl, alkyleneoxy, amino, cyano, nitro, and halogen Also good. 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 bonded directly to each other, or —O—, —S—, —SO—, —SO ₂ —, —NH—, —NR ^15a —, —CO—, —COO—, —CONH—. ^May be bonded via an alkylene group having 1 to 3 carbon atoms or a phenylene group to form a ring structure containing ^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).

In the above 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, ^a7 is at least one selected from the group consisting of alkyl having 1 to 8 carbon atoms, alkoxy having 1 to 8 carbon atoms, aryl having 6 to 10 carbon atoms, hydroxy, cyano, nitro groups, and halogen. May be substituted. X ^a8 represents —O—, —S—, —SO—, —SO ₂ —, —NH—, —NR ^15a —, —CO—, —COO—, —CONH—, an alkylene group having 1 to 3 carbon atoms, Or represents a phenylene group. n represents the number of repeating units in the structure in parentheses. The n + 1 X ^a7 and the n X ^a8 may be the same or different. R ^15a is as defined above.

^Xa6- is a counter ion of onium. The number thereof is n + 1 per molecule, and at least one of them is a fluorinated alkylfluorophosphate anion represented by the following general formula (a17), and the rest may be other anions.

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

  Preferred examples of the onium ion of the general formula (a15) include triphenylsulfonium, tri-p-tolylsulfonium, 4- (phenylthio) phenyldiphenylsulfonium, bis [4- (diphenylsulfonio) phenyl] sulfide, bis [4- {bis [4- (2-hydroxyethoxy) phenyl] sulfonio} phenyl] sulfide, bis {4- [bis (4-fluorophenyl) sulfonio] phenyl} sulfide, 4- (4-benzoyl-2-chlorophenyl) Thio) phenylbis (4-fluorophenyl) sulfonium, 4- (4-benzoylphenylthio) phenyldiphenylsulfonium, 7-isopropyl-9-oxo-10-thia-9,10-dihydroanthracen-2-yldi-p- Tolylsulfonium, 7 Isopropyl-9-oxo-10-thia-9,10-dihydroanthracen-2-yldiphenylsulfonium, 2-[(diphenyl) sulfonio] thioxanthone, 4- [4- (4-tert-butylbenzoyl) phenylthio] phenyldi- p-tolylsulfonium, 4- (4-benzoylphenylthio) phenyldiphenylsulfonium, diphenylphenacylsulfonium, 4-hydroxyphenylmethylbenzylsulfonium, 2-naphthylmethyl (1-ethoxycarbonyl) ethylsulfonium, 4-hydroxyphenylmethylphena Silsulfonium, octadecylmethylphenacylsulfonium, diphenyliodonium, di-p-tolyliodonium, bis (4-dodecylphenyl) iodonium, bis (4-methoxy Enyl) iodonium, (4-octyloxyphenyl) phenyliodonium, bis (4-decyloxy) phenyliodonium, 4- (2-hydroxytetradecyloxy) phenylphenyliodonium, 4-isopropylphenyl (p-tolyl) iodonium, or 4 -Isobutylphenyl (p-tolyl) iodonium.

The anion component of the general formula (a15) has at least one fluorinated alkyl fluorophosphate anion represented by the general formula (a17). The remaining anion component may be other anions. Other anions are not particularly limited, and conventionally known anions can be used. For example, halogen ions such as F ⁻ , Cr ⁻ , Br ⁻ and I ⁻ ; OH ⁻ ; ClO ₄ ⁻ ; FSO ₃ ⁻ , ClSO ₃ ⁻ , CH ₃ SO ₃ ⁻ , C ₆ H ₅ SO ₃ ⁻ , CF ₃ SO ₃ ^- sulfonate ion such _as; ^{HSO 4} -, _SO 4 sulfate ions of ^{_2-like; HCO} 3 -, _CO ³ carbonate ions of _{^{2-like; H 2 PO 4 -, HPO}} 4 2-, PO 4 phosphate ions of _{^{3-like; PF 6 -, PF 5 OH}} - fluorophosphate ions such _{^{as; BF 4 -, B (C}} 6 F 5) 4 -, B (C 6 H 4 CF 3) 4 - Borate ions such as AlCl ₄ ⁻ ; BiF ₆ ^{— and the} like. Other examples include fluoroantimonate ions such as SbF ₆ ⁻ and SbF ₅ OH ^— or fluoroarsenate ions such as A _S F ₆ ⁻ and AsF ₅ OH ⁻ , which are preferable because they contain toxic elements. Absent.

In the fluorinated alkylfluorophosphate anion represented by the general formula (a17), R ^16a represents an alkyl group substituted with a fluorine atom, and preferably has 1 to 8 carbon atoms, more preferably 1 to 1 carbon atoms. 4. 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; and cyclopropyl, cyclobutyl and cyclopentyl. And the ratio of the hydrogen atom of the alkyl group substituted by a fluorine atom is usually 80% or more, preferably 90% or more, and more preferably 100%. When the substitution rate of fluorine atoms is less than 80%, the acid strength of the onium fluorinated alkyl fluorophosphate represented by the general formula (a15) is lowered.

Particularly preferred R ^16a is a linear or branched perfluoroalkyl group having 1 to 4 carbon atoms and a substitution rate of 100% of fluorine atoms. 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 It is done. The number t of R ^16a is an integer of 1 to 5, preferably 2 to 4, particularly preferably 2 or 3.

Specific examples of preferred fluorinated alkyl fluorophosphate 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 ] ⁻ , and 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] - is Particularly preferred.

  Of the onium fluorinated alkyl fluorophosphates represented by the general formula (a15), diphenyl [4- (phenylthio) phenyl] sulfonium trifluorotrisfluoroalkyl phosphate represented by the following general formula (a18) is particularly preferred. Preferably used.

  In said formula (a18), u is an integer of 1-8, Preferably it is an integer of 1-4.

As the acid generator for the component (A), preferably, at least one selected from the general formulas (a2) and (a18) is used. In the general formula (a2), a preferable value of n is R ^4a is preferably a divalent substituted or unsubstituted alkylene group having 1 to 8 carbon atoms, or a substituted or unsubstituted aromatic group, and preferred R ^5a is a carbon number. 1 to 8 substituted or unsubstituted alkyl groups, or substituted or unsubstituted aryl groups.

  The component (A) as described above can be used alone or in combination of two or more.

  Moreover, it is preferable that the compounding quantity of (A) component shall be 0.05-5 mass% in a positive type photoresist composition. When the blending amount of the component (A) is 0.05% by mass or more, sufficient sensitivity can be obtained, and when it is 5% by mass or less, the solubility in a solvent is improved and a uniform solution is obtained. And storage stability tends to be improved.

(Resin component (B))
The resin component is a resin containing at least one of the novolak resin (B1), the polyhydroxystyrene resin (B2), and the acrylic resin (B3) whose solubility in alkali is increased by the action of an acid, Alternatively, it may be a mixed resin or a copolymer.

[(B1) Novolac resin]
As the novolak resin (B1) whose solubility in alkali is increased by the action of an acid, a resin represented by the following general formula (b1) can be used.

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

Furthermore, as the acid dissociable, dissolution inhibiting group represented by R ^1b , a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms represented by the following general formula (b2) or (b3): A tetrahydropyranyl group, a tetrafuranyl group, or a trialkylsilyl group is preferred.

In the general formulas (b2) and (b3), R ^4b and R ^5b are each independently a hydrogen atom or a linear or branched alkyl group having 1 to 6 carbon atoms, and R ^6b is carbon. A linear, branched or cyclic alkyl group having 1 to 10 atoms, R ^7b is a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms, and o is 0 or 1 is there.

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

  Here, as the acid dissociable, dissolution inhibiting group represented by the general formula (b2), specifically, methoxyethyl group, ethoxyethyl group, n-propoxyethyl group, iso-propoxyethyl group, n-butoxyethyl group , Iso-butoxyethyl group, tert-butoxyethyl group, cyclohexyloxyethyl group, methoxypropyl group, ethoxypropyl group, 1-methoxy-1-methyl-ethyl group, 1-ethoxy-1-methylethyl group, etc. Examples of the acid dissociable, dissolution inhibiting group of the above formula (b3) include a tert-butoxycarbonyl group and a tert-butoxycarbonylmethyl group. Examples of the trialkylsilyl group include those having 1 to 6 carbon atoms in each alkyl group such as a trimethylsilyl group and a tri-tert-butyldimethylsilyl group.

[(B2) polyhydroxystyrene resin]
As the polyhydroxystyrene resin (B2) whose solubility in alkali is increased by the action of an acid, a resin represented by the following general formula (b4) can be used.

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

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

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

  Furthermore, the polyhydroxystyrene resin (B2) whose solubility in alkali is increased by the action of the acid can contain other polymerizable compounds as constituent units for the purpose of appropriately controlling physical and chemical properties. . Examples of such polymerizable compounds include known radical polymerizable compounds and anionic polymerizable compounds. For example, monocarboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid; dicarboxylic acids such as maleic acid, fumaric acid, and itaconic acid; 2-methacryloyloxyethyl succinic acid, 2-methacryloyloxyethyl maleic acid, and 2-methacryloyloxyethyl Methacrylic acid derivatives having a carboxyl group and an ester bond such as phthalic acid and 2-methacryloyloxyethylhexahydrophthalic acid; (meth) acrylic acid such as methyl (meth) acrylate, ethyl (meth) acrylate and butyl (meth) acrylate Alkyl esters; (meth) acrylic acid hydroxyalkyl esters such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate; phenyl (meth) acrylate, benzyl (meth) acrylate (Meth) acrylic acid aryl esters such as diethylate; dicarboxylic acid diesters such as diethyl maleate and dibutyl fumarate; styrene, α-methylstyrene, chlorostyrene, chloromethylstyrene, vinyltoluene, hydroxystyrene, α-methyl Vinyl group-containing aromatic compounds such as hydroxystyrene and α-ethylhydroxystyrene; Vinyl group-containing aliphatic compounds such as vinyl acetate; Conjugated diolefins such as butadiene and isoprene; Nitrile groups such as acrylonitrile and methacrylonitrile Polymerizable compounds; chlorine-containing polymerizable compounds such as vinyl chloride and vinylidene chloride; amide bond-containing polymerizable compounds such as acrylamide and methacrylamide, and the like.

[(B3) Acrylic resin]
As the acrylic resin (B3) whose solubility in alkali is increased by the action of an acid, resins represented by the following general formulas (b5) to (b7) can be used.

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 having 1 to 6 carbon atoms, a fluorine atom, or 1 carbon atom. A linear or branched fluorinated alkyl group of ˜6 (provided that R ^11b is not a hydrogen atom), and X ^b1 has 5 to 20 carbon atoms together with the carbon atom to which it is bonded. A hydrocarbon ring is formed, X ^b2 is an ^optionally substituted aliphatic cyclic group or an alkyl group, n is a repeating unit, c is 0 to 4, and d is 0 or 1.

  In addition, as a linear or branched alkyl group having 1 to 6 carbon atoms, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, iso-butyl group, tert-butyl group, pentyl group , Isopentyl group, neopentyl group and the like, and cyclic alkyl group include cyclopentyl group, cyclohexyl group and the like. The fluorinated alkyl group is one in which part or all of the hydrogen atoms of the alkyl group are substituted with fluorine atoms.

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

Wherein X ^b1, it is to form an aliphatic cyclic group of 5 to 20 carbon atoms together with the carbon atom bonded. Specific examples of such an aliphatic cyclic group include groups in which one or more hydrogen atoms have been removed from a polycycloalkane such as monocycloalkane, bicycloalkane, tricycloalkane, and tetracycloalkane. Specifically, one or more hydrogen atoms were removed from monocycloalkanes such as cyclopentane, cyclohexane, cycloheptane, and cyclooctane, and polycycloalkanes such as adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane. Groups. In particular, a group obtained by removing one or more hydrogen atoms from cyclohexane or adamantane (which may further have a substituent) is preferable.

The alicyclic group of the X ^b1 is the case with a ring skeleton on a substituent, examples of the substituent, a hydroxyl group, a carboxyl group, a cyano group, an oxygen atom (= O) polar groups such as And a linear or branched lower alkyl group having 1 to 4 carbon atoms. As the polar group, an oxygen atom (═O) is particularly preferable.

^Xb2 is an aliphatic cyclic group or an alkyl group, and examples thereof include a group in which one or more hydrogen atoms have been removed from a polycycloalkane such as a monocycloalkane, bicycloalkane, tricycloalkane, or tetracycloalkane. . Specifically, one or more hydrogen atoms were removed from monocycloalkanes such as cyclopentane, cyclohexane, cycloheptane, and cyclooctane, and polycycloalkanes such as adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane. Groups and the like. In particular, a group in which one or more hydrogen atoms are removed from adamantane (which may further have a substituent) is preferable.

The alicyclic group of the X ^b2 is the case with a ring skeleton on a substituent, examples of the substituent, a hydroxyl group, a carboxyl group, a cyano group, an oxygen atom (= O) polar groups such as And a linear or branched lower alkyl group having 1 to 4 carbon atoms. As the polar group, an oxygen atom (═O) is particularly preferable.

Also, if X ^b2 is an alkyl group, having 1 to 20 carbon atoms, it is preferred that preferably a linear or branched alkyl group having 6 to 15. Such an alkyl group is particularly preferably an alkoxyalkyl group. Examples of such an alkoxyalkyl group include 1-methoxyethyl group, 1-ethoxyethyl group, 1-n-propoxyethyl group, 1-iso- Propoxyethyl group, 1-n-butoxyethyl group, 1-iso-butoxyethyl group, 1-tert-butoxyethyl group, 1-methoxypropyl group, 1-ethoxypropyl group, 1-methoxy-1-methyl-ethyl group And 1-ethoxy-1-methylethyl group.

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

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 those represented by the following general formulas (b6-1) to (b6-28).

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

  Further, such an acrylic resin (B3) is made of a copolymer containing structural units derived from a polymerizable compound having an ether bond with respect to the structural units of the general formulas (b5) to (b7). A resin is preferred.

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

  Furthermore, such an acrylic resin (B3) can contain other polymerizable compounds as structural units for the purpose of appropriately controlling physical and chemical properties. Examples of such polymerizable compounds include known radical polymerizable compounds and anionic polymerizable compounds. For example, monocarboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid; dicarboxylic acids such as maleic acid, fumaric acid, and itaconic acid; 2-methacryloyloxyethyl succinic acid, 2-methacryloyloxyethyl maleic acid, and 2-methacryloyloxyethyl Methacrylic acid derivatives having a carboxyl group and an ester bond such as phthalic acid and 2-methacryloyloxyethylhexahydrophthalic acid; (meth) acrylic acid such as methyl (meth) acrylate, ethyl (meth) acrylate and butyl (meth) acrylate Alkyl esters; (meth) acrylic acid hydroxyalkyl esters such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate; phenyl (meth) acrylate, benzyl (meth) acrylate (Meth) acrylic acid aryl esters such as diethylate; dicarboxylic acid diesters such as diethyl maleate and dibutyl fumarate; styrene, α-methylstyrene, chlorostyrene, chloromethylstyrene, vinyltoluene, hydroxystyrene, α-methyl Vinyl group-containing aromatic compounds such as hydroxystyrene and α-ethylhydroxystyrene; Vinyl group-containing aliphatic compounds such as vinyl acetate; Conjugated diolefins such as butadiene and isoprene; Nitrile groups such as acrylonitrile and methacrylonitrile Polymerizable compounds; chlorine-containing polymerizable compounds such as vinyl chloride and vinylidene chloride; amide bond-containing polymerizable compounds such as acrylamide and methacrylamide, and the like.

  Furthermore, among such acrylic resins (B3), 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, It is preferable that it is a copolymer which has a structural unit which consists of meth) acrylic-acid alkylesters.

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

In the general formula (b8), R ^20b is a hydrogen atom or a methyl group, R ^21b is a linear or branched alkyl group or alkoxyalkyl group having 1 to 6 carbon atoms, and R ^22b is , A linear or branched alkyl group having 2 to 4 carbon atoms, and ^Xb1 is as defined above.

  Furthermore, in the copolymer represented by the general formula (b8), e, f and g are each in a mass ratio, e is 1 to 30% by mass, f is 20 to 70% by mass, g Is 20-70 mass%.

  Moreover, the polystyrene conversion mass 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. is there. By adopting such a mass average molecular weight, sufficient resist film strength can be maintained without lowering the peelability from the substrate, and further, profile swelling and cracking may occur during plating. Disappear.

  Furthermore, the component (B) is preferably a resin having a dispersity of 1.05 or more. Here, the degree of dispersion is a value obtained by dividing the mass average molecular weight by the number average molecular weight. By setting it as such a dispersion degree, the problem that the stress tolerance with respect to desired plating and the metal layer obtained by a plating process become easy to swell can be avoided.

  It is preferable that the compounding quantity of such (B) component shall be 5-60 mass% in a positive type photoresist composition.

(Alkali-soluble resin (C))
Furthermore, an alkali-soluble resin can be appropriately blended in the positive photoresist composition of the present invention. Such component (C) is at least one selected from alkali-soluble novolak resin (C1), polyhydroxystyrene resin (C2), acrylic resin (C3), and vinyl resin (C4). preferable.

[(C1) alkali-soluble novolak resin]
The alkali-soluble novolak resin (C1) preferably has a polystyrene-reduced mass average molecular weight of 1,000 to 50,000.

  Such a novolak resin (C1) can be obtained, for example, by addition condensation of an aromatic compound having a phenolic hydroxyl group (hereinafter simply referred to as “phenols”) and an aldehyde in the presence of an acid catalyst. Examples of phenols used in this case include 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-xylenol, 2,3,5-trimethylphenol, 3, 4,5-trimethylphenol, p-phenylphenol, resorcinol, hydroquinone, hydroquinone monomethyl ether, pyrogallol, phloroglicinol, hydroxydiphenyl, bisphenol A, gallic acid, gallic acid ester, α-naphthol, β-naphthol, etc. The

  Examples of aldehydes include formaldehyde, furfural, benzaldehyde, nitrobenzaldehyde, and acetaldehyde. The catalyst for the addition condensation reaction is not particularly limited. For example, hydrochloric acid, nitric acid, sulfuric acid, formic acid, oxalic acid, acetic acid and the like are used as the acid catalyst.

  In the present invention, the flexibility of the resin can be further improved by using o-cresol, substituting the hydrogen atom of the hydroxyl group in the resin with another substituent, or using bulky aldehydes. Is possible.

[(C2) alkali-soluble polyhydroxystyrene resin]
The alkali-soluble polyhydroxystyrene resin (C2) preferably has a mass average molecular weight of 1,000 to 50,000.

  Examples of the hydroxystyrene compound constituting the polyhydroxystyrene resin (C2) include p-hydroxystyrene, α-methylhydroxystyrene, α-ethylhydroxystyrene and the like. Further, the polyhydroxystyrene resin is preferably a copolymer with a styrene resin. Examples of the styrene compound constituting the styrene resin include styrene, chlorostyrene, chloromethylstyrene, vinyltoluene, α-methyl. Examples include styrene.

[(C3) alkali-soluble acrylic resin]
The alkali-soluble acrylic resin (C3) preferably has a mass average molecular weight of 50,000 to 800,000.

  Such an acrylic resin (C3) preferably contains a monomer derived from a polymerizable compound having an ether bond and a monomer derived from a polymerizable compound having a carboxyl group.

  Examples of the polymerizable compound having an ether bond include 2-methoxyethyl (meth) acrylate, methoxytriethylene glycol (meth) acrylate, 3-methoxybutyl (meth) acrylate, ethyl carbitol (meth) acrylate, phenoxypolyethylene glycol ( Examples include (meth) acrylic acid derivatives having an ether bond and an ester bond such as (meth) acrylate, methoxypolypropylene glycol (meth) acrylate, and tetrahydrofurfuryl (meth) acrylate, preferably 2-methoxyethyl acrylate. And methoxytriethylene glycol acrylate. These compounds can be used alone or in combination of two or more.

  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 itaconic acid, 2-methacryloyloxyethyl succinic acid, and 2-methacryloyloxy. Examples include ethyl maleic acid, 2-methacryloyloxyethyl phthalic acid, 2-methacryloyloxyethyl hexahydrophthalic acid and other compounds having a carboxyl group and an ester bond, and acrylic acid and methacrylic acid are preferred. These compounds can be used alone or in combination of two or more.

[(C4) alkali-soluble polyvinyl resin]
The alkali-soluble polyvinyl resin (C4) preferably has a mass average molecular weight of 10,000 to 200,000, and more preferably 50,000 to 100,000.

Such a polyvinyl resin (C4) is poly (vinyl lower alkyl ether), and is obtained by polymerizing a vinyl lower alkyl ether represented by the following general formula (c1) alone or a mixture of two or more kinds ( Co) polymer.

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

  Such a polyvinyl resin (C4) is a polymer obtained from a vinyl-based compound. Specific examples of such a polyvinyl resin include polyvinyl chloride, polystyrene, polyhydroxystyrene, polyvinyl acetate, and polyvinyl benzoate. Examples thereof include acids, polyvinyl methyl ether, polyvinyl ethyl ether, polyvinyl alcohol, polyvinyl pyrrolidone, polyvinyl phenol, and copolymers thereof. Among these, polyvinyl methyl ether is preferable in view of the low glass transition point.

  The blending amount of the (C) alkali-soluble resin is preferably 5 to 95 parts by mass, more preferably 10 to 90 parts by mass with respect to 100 parts by mass of the component (B). When the amount is 5 parts by mass or more, crack resistance can be improved, and when the amount is 95 parts by mass or less, there is a tendency that film loss during development can be prevented.

(Other ingredients)
The positive photoresist composition is preferably used in the form of a solution in which the above components are dissolved in a solvent. Examples of such solvents include ketones such as acetone, methyl ethyl ketone, cyclohexanone, methyl isoamyl ketone, 2-heptanone; ethylene glycol, ethylene glycol monoacetate, diethylene glycol, diethylene glycol monoacetate, propylene glycol, propylene glycol monoacetate, di Polyhydric alcohols such as propylene glycol and dipropylene glycol monoacetate monomethyl ether, monoethyl ether, monopropyl ether, monobutyl ether, or monophenyl ether and derivatives thereof; cyclic ethers such as dioxane; ethyl formate; Methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, methyl acetoacetate, ethyl acetoacetate, Ethyl rubinate, ethyl ethoxyacetate, methyl methoxypropionate, ethyl ethoxypropionate, methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, 2-hydroxy-3-methylbutane Examples thereof include esters such as methyl acid, 3-methoxybutyl acetate, and 3-methyl-3-methoxybutyl acetate; and aromatic hydrocarbons such as toluene and xylene. These may be used alone or in combination of two or more.

  The amount of these organic solvents used is such that the film thickness of the photoresist layer obtained by using the chemically amplified positive photoresist composition according to the present invention (for example, spin coating method) is 1 μm or more. Is preferably in the range of 30% by mass or more. More preferably, the film thickness of the photoresist layer obtained using the composition according to the present invention is in the range of 1 μm to 200 μm.

  The positive chemically amplified photoresist composition may further contain miscible additives as desired, for example, additional resins, sensitizers, acid diffusion control agents, adhesion aids for improving the performance of the resist film, Commonly used stabilizers, colorants, surfactants and the like can be added.

[Negative photoresist composition]
On the other hand, the negative photoresist composition is based on an acid generator component that generates an acid upon irradiation with actinic rays or radiation (similar to the component (A) above) and a polyfunctional epoxy resin (hereinafter referred to as the component (D)). What is used as a component is preferably used. When the component (D) is used in combination with an acid generator, the acid generated in the exposed part is cationically polymerized to become alkali-insoluble, and only the unexposed part is selectively removed during the development. This photoresist pattern can be obtained.

(Polyfunctional epoxy resin (D))
Although it does not specifically limit as a polyfunctional epoxy resin (D), The epoxy resin which has sufficient epoxy group in 1 molecule for forming the pattern of a thick film is preferable. Examples of such polyfunctional epoxy resins include polyfunctional phenol / novolak type epoxy resins, polyfunctional orthocresol novolac type epoxy resins, polyfunctional triphenyl type novolac type epoxy resins, polyfunctional bisphenol A novolac type epoxy resins and the like. . Of these, polyfunctional bisphenol A novolac type epoxy resins are preferably used. The functionality is preferably 5 or more. For example, “Epicoat 157S70” manufactured by Japan Epoxy Resin Co., Ltd. and “Epicron N-775” manufactured by Dainippon Ink & Chemicals, Inc. are commercially available and particularly preferably used. .

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

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

  The content of the polyfunctional epoxy resin in the photoresist composition is preferably 80% by mass to 99.9% by mass, and more preferably 92% by mass to 99.4% by mass. As a result, a photoresist film having high sensitivity and appropriate hardness can be obtained when the support 11 is coated.

(Acid generator component (A))
The acid generator component (A) is the same as the acid generator used in the positive type. This acid generator component (A) produces a cation component by irradiation with actinic rays or radiation, and the cation component acts as a polymerization initiator.

  The said (A) component may be used independently 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 setting the content of the component (A) within the above range, the permanent film characteristics can be maintained while maintaining sufficient sensitivity.

(Other ingredients)
In the negative photoresist composition, a conventionally known solvent component is used as in the positive type. Also, lactone solvents such as γ-butyrolactone, β-propiolactone, γ-valerolactone, δ-valerolactone, γ-caprolactone, and ε-caprolactone are opened by the heat treatment during photoresist pattern formation. As a result of reacting with a functional group in the polymer, it is preferably used because it has a property of being incorporated into a photoresist film. Hydroxy carboxylic acid ester solvents such as glycolic acid alkyl esters, lactic acid alkyl esters, and 2-hydroxybutyric acid alkyl esters are preferably used because they have the property of improving coating properties and leveling properties.

  The negative photoresist composition may use an aromatic polycyclic compound having at least two substituents capable of crosslinking with the polyfunctional epoxy resin as a sensitizer. Such a sensitization function of the aromatic polycyclic compound can increase the sensitivity of the photoresist composition. Specifically, aromatic polycyclic compounds such as naphthalene compounds, dinaphthalene compounds, anthracene compounds, and phenanthroline compounds having two or more hydroxyl groups, carboxyl groups, amino groups, and the like are preferably used. Among these, naphthalene compounds are more preferable, and 1,5-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, and 2,6-dihydroxynaphthalene are particularly preferably used from the viewpoint of improving the crosslinking efficiency.

  The negative photoresist composition may contain a polymer linear bifunctional epoxy resin for improving film formability. From the viewpoint of improving the flexibility of the resist composition before curing without reducing the physical properties after curing, an oxetane derivative or an epoxy derivative may be contained. Further, if desired, miscible additives such as additional resins for improving pattern performance, plasticizers, stabilizers, colorants, surfactants, coupling agents, and the like can be used as appropriate. It can be included.

  As the chemically amplified photoresist composition used in the present invention, for example, a conventional photoresist pattern forming method using a positive resist composition or a negative resist composition can be applied. Specifically, a photoresist composition prepared in the form of a solution is applied on the above-described support 11 with a spinner or the like, and prebaked to form a photoresist film. Alternatively, both surfaces may be protected with a protective film to form a dry film, and this may be attached to the support 11 to form a photoresist film. If it is a dry film, the application | coating and drying on the support body 11 can be abbreviate | omitted, and a photoresist pattern can be formed more simply.

Next, an exposure process is selectively performed on the photoresist film. For the exposure process, g, h, i-line, KrF excimer laser light, ArF excimer laser light, F ₂ excimer laser light, EUV (Extreme ultraviolet extreme ultraviolet light), electron beam (EB), soft X-ray, X-ray, etc. Can be used, and irradiation through a desired mask pattern or direct drawing is performed. Preferably, KrF excimer laser light is used. Subsequently, post-exposure heat treatment (post-exposure baking, hereinafter sometimes referred to as PEB) is performed. After the PEB treatment, development is performed using a developer such as an alkaline aqueous solution, and a photoresist pattern is obtained by performing treatments such as washing with water and drying as necessary. A developing solution is not specifically limited, A conventionally well-known alkaline aqueous solution etc. can be used.

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

  The aspect ratio of the photoresist pattern is preferably 0.1 or more. By setting the aspect ratio of the photoresist pattern to 0.1 or more, the aspect ratio of the patterned silica-based film 12 can be increased. Therefore, since the surface area of the negative electrode base material 10 can be increased, the amount of a metal film described later can be increased. As a result, higher output and higher energy density can be achieved.

<Silica-based coating>
The silica-based coating 12 in the negative electrode substrate 10 according to the present invention is formed from a coating solution for forming a silica-based coating. Specifically, the silica-based coating 12 that remains on the support 11 when the photoresist pattern is removed after applying a coating solution for forming a silica-based coating on the photoresist pattern formed on the negative electrode substrate 10. is there. The coating liquid for forming a silica-based film comprises a composition for forming a silica-based film that contains a siloxane polymer and a solvent.

[Siloxane polymer]
As the siloxane polymer, a reaction product obtained by hydrolyzing at least one selected from silane compounds represented by the following general formula (I) is preferably used.

  In the said 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 the integer of 2-4. When a plurality of R are bonded to Si, the plurality of R may be the same or different. The plurality of (OR ′) groups bonded to Si may be the same or different. The alkyl group as 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 as R ′ is preferably a linear or branched alkyl group having 1 to 5 carbon atoms. The alkyl group as R ′ preferably has 1 or 2 carbon atoms from the viewpoint of hydrolysis rate.

When n in the general formula (I) is 4, the silane compound (i) is represented by the following general formula (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 the above R ′. a, b, c, and d are integers that satisfy 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).

In the general formula (III), ^{R 5} is a hydrogen atom, the same alkyl group as the R, or a phenyl group. R ⁶ , R ⁷ , and R ⁸ each independently represent the same alkyl group or phenyl group as the above R ′. e, f, and g are integers that satisfy 0 ≦ e ≦ 3, 0 ≦ f ≦ 3, 0 ≦ g ≦ 3, and satisfy the condition of 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).

In the general formula (IV), R ⁹ and R ^{10 each} represent a hydrogen atom, the same alkyl group as that for R, or a phenyl group. R ¹¹ and R ¹² each independently represent the same alkyl group or phenyl group as R ′ described above. h and i are integers satisfying 0 ≦ h ≦ 2, 0 ≦ i ≦ 2 and satisfying the condition of h + i = 2.

  Specific examples of the silane compound (i) include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, tetrapentyloxysilane, tetraphenyloxysilane, trimethoxymonoethoxysilane, dimethoxydiethoxysilane, tri Ethoxymonomethoxysilane, trimethoxymonopropoxysilane, monomethoxytributoxysilane, monomethoxytripentyloxysilane, monomethoxytriphenyloxysilane, dimethoxydipropoxysilane, tripropoxymonomethoxysilane, trimethoxymonobutoxysilane, dimethoxydi Butoxysilane, triethoxymonopropoxysilane, diethoxydipropoxysilane, tributoxymonopropoxysilane, dimethoxymonoethoxymolybdenum Butoxysilane, diethoxymonomethoxymonobutoxysilane, diethoxymonopropoxymonobutoxysilane, dipropoxymonomethoxymonoethoxysilane, dipropoxymonomethoxymonobutoxysilane, dipropoxymonoethoxymonobutoxysilane, dibutoxymonomethoxymonoethoxysilane And tetraalkoxysilanes such as dibutoxymonoethoxymonopropoxysilane and monomethoxymonoethoxymonopropoxymonobutoxysilane. Among them, tetramethoxysilane and tetraethoxysilane are preferable.

  Specific examples of the silane compound (ii) include trimethoxysilane, triethoxysilane, tripropoxysilane, tripentyloxysilane, triphenyloxysilane, dimethoxymonoethoxysilane, diethoxymonomethoxysilane, dipropoxymonomethoxysilane. , Dipropoxymonoethoxysilane, dipentyloxylmonomethoxysilane, dipentyloxymonoethoxysilane, dipentyloxymonopropoxysilane, diphenyloxylmonomethoxysilane, diphenyloxymonoethoxysilane, diphenyloxymonopropoxysilane, methoxyethoxypropoxysilane, monopropoxy Dimethoxysilane, monopropoxydiethoxysilane, monobutoxydimethoxysilane, monopentyloxydiethoxysilane Monophenyloxydiethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyltripentyloxysilane, ethyltrimethoxysilane, ethyltripropoxysilane, ethyltripentyloxysilane, ethyltriphenyloxysilane, Propyltrimethoxysilane, propyltriethoxysilane, propyltripentyloxysilane, propyltriphenyloxysilane, butyltrimethoxysilane, butyltriethoxysilane, butyltripropoxysilane, butyltripentyloxysilane, butyltriphenyloxysilane, methyl Monomethoxydiethoxysilane, ethylmonomethoxydiethoxysilane, propylmonomethoxydiethoxysilane, butylmonomethoxydi Toxisilane, Methylmonomethoxydipropoxysilane, Methylmonomethoxydipentyloxysilane, Methylmonomethoxydiphenyloxysilane, Ethylmonomethoxydipropoxysilane, Ethylmonomethoxydipentyloxysilane, Ethylmonomethoxydiphenyloxysilane, Propylmonomethoxydipropoxysilane , Propylmonomethoxydipentyloxysilane, propylmonomethoxydiphenyloxysilane, butylmonomethoxydipropoxysilane, butylmonomethoxydipentyloxysilane, butylmonomethoxydiphenyloxysilane, methylmethoxyethoxypropoxysilane, propylmethoxyethoxypropoxysilane, butylmethoxy Ethoxypropoxysilane, methyl monomethoxy monoethoxy mono Toxisilane, ethyl monomethoxymonoethoxymonobutoxysilane, propylmonomethoxymonoethoxymonobutoxysilane, butylmonomethoxymonoethoxymonobutoxysilane and the like can be mentioned, among which trimethoxysilane, triethoxysilane and methyltrimethoxysilane are preferable.

  Specific examples of the silane compound (iii) include dimethoxysilane, diethoxysilane, dipropoxysilane, dipentyloxysilane, diphenyloxysilane, methoxyethoxysilane, methoxypropoxysilane, methoxypentyloxysilane, methoxyphenyloxysilane, ethoxy Propoxysilane, ethoxypentyloxysilane, ethoxyphenyloxysilane, methyldimethoxysilane, methylmethoxyethoxysilane, methyldiethoxysilane, methylmethoxypropoxysilane, methylmethoxypentyloxysilane, methylmethoxyphenyloxysilane, ethyldipropoxysilane, ethyl Methoxypropoxysilane, ethyldipentyloxysilane, ethyldiphenyloxysilane, propyldimethoxysila , Propylmethoxyethoxysilane, propylethoxypropoxysilane, propyldiethoxysilane, propyldipentyloxysilane, propyldiphenyloxysilane, butyldimethoxysilane, butylmethoxyethoxysilane, butyldiethoxysilane, butylethoxypropoxysilane, butyldipropoxysilane , Butylmethyldipentyloxysilane, butylmethyldiphenyloxysilane, dimethyldimethoxysilane, dimethylmethoxyethoxysilane, dimethyldiethoxysilane, dimethyldipentyloxysilane, dimethyldiphenyloxysilane, dimethylethoxypropoxysilane, dimethyldipropoxysilane, diethyldimethoxysilane , Diethylmethoxypropoxysilane, diethyldiethoxysilane, Ethylethoxypropoxysilane, dipropyldimethoxysilane, dipropyldiethoxysilane, dipropyldipentyloxysilane, dipropyldiphenyloxysilane, dibutyldimethoxysilane, dibutyldiethoxysilane, dibutyldipropoxysilane, dibutylmethoxypentyloxysilane, dibutylmethoxy Phenyloxysilane, methylethyldimethoxysilane, methylethyldiethoxysilane, methylethyldipropoxysilane, methylethyldipentyloxysilane, methylethyldiphenyloxysilane, methylpropyldimethoxysilane, methylpropyldiethoxysilane, methylbutyldimethoxysilane, methyl Butyldiethoxysilane, methylbutyldipropoxysilane, methylethylethoxypropoxysilane , Ethylpropyldimethoxysilane, ethylpropylmethoxyethoxysilane, dipropyldimethoxysilane, dipropylmethoxyethoxysilane, propylbutyldimethoxysilane, propylbutyldiethoxysilane, dibutylmethoxyethoxysilane, dibutylmethoxypropoxysilane, dibutylethoxypropoxysilane, etc. Among them, dimethoxysilane, diethoxysilane, methyldimethoxysilane, and methyldiethoxysilane are preferable.

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

  The siloxane polymer preferably has a mass average molecular weight in the range of 1,000 to 10,000. This is mainly because it becomes easy to secure film formability and film flatness and is excellent in etching rate resistance. In particular, if the molecular weight is too low, the siloxane polymer volatilizes, and film formation may not be possible.

[solvent]
Examples of the solvent include monohydric alcohols such as methyl alcohol, ethyl alcohol, propyl alcohol, and butyl alcohol, polyhydric alcohols such as ethylene glycol, diethylene glycol, propylene glycol, glycerin, trimethylolpropane, and 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 monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomer Monoethers of polyhydric alcohols such as propyl ether and propylene glycol monobutyl ether, esters such as methyl acetate, ethyl acetate and butyl acetate, ketones such as acetone, methyl ethyl ketone, cycloalkyl ketone and methyl isoamyl ketone, ethylene glycol dimethyl ether, Of polyhydric alcohols such as 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 ethyl ether, and diethylene glycol diethyl ether. All hydroxyl groups are alkylate And the like phased polyhydric alcohols ethers. Among these, cycloalkyl ketone or alkylene glycol dialkyl ether is more preferable. Furthermore, as alkylene glycol dimethyl ether, PGDM (propylene glycol dimethyl ether) is preferable. These organic solvents may be used alone or in combination of two or more. The blending amount is preferably in the range of 70 to 99% by mass in the silica-based film forming composition.

[Others]
The composition for forming a silica-based film may contain components other than the siloxane polymer and the solvent. For example, a cyclic basic compound may be contained. As this cyclic basic compound, a cyclic amine is preferable, and more specifically, DBU (1,8-diazabicyclo (5,4,0) undec-7-ene) is preferably used.

  The addition amount of the cyclic basic compound is preferably 10 ppm to 1% with respect to the solid content of the siloxane polymer. If the addition amount is within this range, polymerization of the siloxane polymer can be promoted, and the amount of water in the coating can be reduced. Moreover, the liquid stability of the composition for forming a silica-based film is increased, and the coating property is improved.

  Furthermore, porogen may be contained in the composition for forming a silica-based film. Porogen is a material that is decomposed during firing of a coating film made of a composition for forming a silica-based film and forms pores in the silica-based film 12 that is finally formed. Examples of this porogen include polyalkylene glycol and its terminal alkylated product.

  1-5 are preferable and, as for carbon number of the alkylene group of the said polyalkylene glycol, 1-3 are more preferable. Specific examples of the polyalkylene glycol include lower alkylene glycols such as polyethylene glycol and polypropylene glycol.

  The terminal alkylated product of polyalkylene glycol is a product in which the hydroxyl group at one or both ends of polyalkylene glycol is alkoxylated with an alkyl group. The alkyl group used for terminal alkoxylation may be a linear or branched alkyl group, preferably having 1 to 5 carbon atoms, more preferably 1 to 3 carbon atoms. In particular, a linear alkyl group such as a methyl group, an ethyl group, or a propyl group is preferable.

  The polyalkylene glycol has a mass average molecular weight (Mw) of preferably from 100 to 10,000, more preferably from 200 to 5,000, and even more preferably from 400 to 4,000. By setting the mass average molecular weight to be not more than the upper limit of the above range, good coating properties can be obtained without impairing the compatibility in the coating solution, and the film thickness uniformity of the silica-based coating 12 becomes good. By setting it to be equal to or more than the lower limit of the above range, the silica-based coating 12 can be made porous, and a larger buffering effect can be obtained.

The amount of the porogen are solids in composition for forming a silica-based film with respect to (Si0 ₂ in terms of mass) is preferably from 25 to 100 wt%, more preferably 30 to 70 mass%. By making the usage-amount of a solvent component more than the lower limit of the said range, it can be made porous, and the silica type coating 12 of sufficient intensity | strength can be obtained by making it the upper limit of the said range or less.

  The silica-based film 12 is obtained by applying a silica-based film-forming coating solution on a support 11 on which a photoresist pattern is formed, heating and drying and baking, and then removing the photoresist pattern. The method for applying the silica-based coating forming coating solution 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 can be used.

  Heat drying is preferably performed at 80 to 300 ° C. over a period of 1 to 6 minutes, and more preferably three or more steps. For example, after the first drying treatment at 70 to 120 ° C. for 30 seconds to 2 minutes in the atmosphere or an inert gas atmosphere such as nitrogen, the second drying is performed at 130 to 220 ° C. for 30 seconds to 2 minutes. Then, a third drying process is performed at 150 to 300 ° C. for 30 seconds to 2 minutes. Thus, the surface of the coating film can be made uniform by performing stepwise drying treatment of three or more stages, preferably about 3 to 6 stages.

  The firing is preferably performed at a temperature of about 300 to 400 ° C. in a nitrogen atmosphere.

  The silica-based film formed on the upper part of the resist pattern can be appropriately removed by etching the entire support (etchback) or the like. Note that the etching process at this time is performed by using a known etching method.

The stripping solution used for removing the photoresist pattern is not particularly limited, and a conventionally known stripping solution for photoresist is used. For example, any of organic stripping solution, aqueous stripping solution, and O ₂ ashing treatment can be used.

<Metal film>
The metal film 13 in the negative electrode substrate 10 according to the present invention is preferably formed by plating, but is not particularly limited. A conventionally known plating process is used, and there is no particular limitation as long as the metal film 13 can be formed on the silica-based coating 12 described above. Further, the metal film 13 may be composed of a plurality of layers by a multistage plating process. The process of forming such a metal film, that is, the plating process, is preferably followed by an electroless nickel plating or an electroless copper plating process following the cleaning process and the catalyzing process, and further an electroless tin plating process Or an electrolytic tin plating process.

  The plating process suitable for the present invention will be specifically described below.

[Washing process]
First, the support 11 provided with the silica coating 12 is immersed in a phosphoric acid solution for cleaning. As the phosphoric acid solution, sodium phosphate or the like is used. The immersion time is preferably 30 to 180 seconds, and more preferably 45 to 90 seconds.

[Catalysis process]
The support 11 that has undergone the cleaning step is immersed in a tin chloride (SnCl ₂ ) aqueous solution having a predetermined concentration for a predetermined time. The concentration of tin chloride is ^preferably from ^{0.01g / dm 3 ~0.10g / dm 3} , 0.03g / dm 3 ~0.07g / dm 3 are more preferred. Further, the immersion time is preferably 15 to 180 seconds, and more preferably 30 to 60 seconds.

Next, the support 11 immersed in a tin chloride (SnCl ₂ ) aqueous solution for a predetermined time is immersed in a palladium chloride (PdCl ₂ ) aqueous solution having a predetermined concentration for a predetermined time. The concentration of palladium chloride is ^preferably from ^{0.01g / dm 3 ~0.3g / dm 3} , 0.03g / dm 3 ~0.07g / dm 3 are more preferred. Further, the immersion time is preferably 15 to 180 seconds, and more preferably 30 to 60 seconds.

[Electroless nickel plating process]
Nickel plating is performed by immersing the support 11 that has undergone the catalyzing step in a nickel plating bath. A conventionally known nickel plating bath is used. For example, nickel sulfate 0.05M-0.20M, sodium hypophosphite 0.10M-0.30M, lead ions 0.05ppm-0.30ppm, complexing agent 0.05M-0.30M An example is a nickel plating bath. As the complexing agent, a complexing agent of carboxylic acids is preferably used. The temperature of the nickel plating bath is preferably 50 ° C to 70 ° C, and the pH is preferably 4.0 to 5.5. Sodium hydroxide and sulfuric acid are used to adjust the pH.

  In place of the electroless nickel plating, electroless copper plating may be performed. A conventionally well-known thing is used as a copper plating bath.

[Electroless copper plating process]
The support 11 that has undergone the catalyzing step is dipped in a copper plating bath to perform copper plating. A conventionally well-known thing is used as a copper plating bath. For example, 0.02 M to 0.10 M of copper sulfate, 0.10 M to 0.40 M of formalin, 1.0 ppm to 20.0 ppm of 2,2′-bipyridyl, 50.0 ppm of surfactant (polyethylene glycol, etc.) An example is a copper plating bath containing ˜500 ppm and a complexing agent of 0.20 M to 0.40 M. As the complexing agent, an ethylene-amine complexing agent is preferably used. The temperature of the copper plating bath is preferably 50 ° C to 70 ° C, and the pH is preferably 11.5 to 12.5. Moreover, it is preferable to perform stirring by air ventilation. For adjusting the pH, potassium hydroxide and sulfuric acid are used.

[Electroless tin plating process]
The metal film 13 is formed on the silica coating 12 by immersing the support 11 that has undergone the electroless nickel plating or electroless copper plating process in a tin plating bath and performing tin plating. A conventionally well-known thing is used as a tin plating bath. For example, 0.02M to 0.20M tin chloride, 0.02M to 0.08M reducing agent such as titanium trichloride, trisodium citrate, disodium ethylenediaminetetraacetate (EDTA-2Na), nitrilotriacetic acid (NTA) An example is a tin plating bath containing 0.10 M to 0.50 M of a complexing agent such as The temperature of the tin plating bath is preferably 45 ° C to 70 ° C, and the pH is preferably 6.5 to 8.5. Sodium carbonate or ammonia and hydrochloric acid are used to adjust the pH. The tin plating process is preferably performed in a nitrogen atmosphere.

[Electrolytic tin plating process]
In place of the electroless tin plating, electrolytic tin plating may be performed. As such a tin plating process, the support 11 that has undergone the above electroless nickel plating or electroless copper plating process is immersed in a tin plating bath and energized to perform electrolytic tin plating, thereby producing a silica-based coating 12. A metal film 13 is formed thereon. A conventionally well-known thing is used as an electrolytic tin plating bath. Examples thereof include a commercial plating solution manufactured by Reybold Co., Ltd. and a starter Kurumo tin plating bath. The temperature of the tin plating bath is preferably 10 ° C to 28 ° C, and the pH is preferably 1.0 to 1.5. The applied current density is preferably 0.5 A / dm ^{2 to} 6.0 A / dm ² .

<Secondary battery>
The said negative electrode base material 10 is used suitably as a negative electrode base material for secondary batteries, especially a negative electrode base material for lithium secondary batteries. A lithium secondary battery is a secondary battery that uses an organic solvent and a lithium salt as an electrolytic solution, and is charged and discharged by transfer of charge by movement of lithium ions (Li ⁺ ) performed between a negative electrode and a positive electrode. , It has the advantages of high output voltage and high energy density. In conventional lithium secondary batteries, carbon is usually used as the negative electrode and a transition metal oxide lithium compound is used as the positive electrode. However, in recent years, studies on negative electrode materials have been conducted in search of higher power and higher energy density. . The negative electrode material needs to be capable of forming a thin film and reversibly occluding / releasing lithium, and the negative electrode base material 10 is preferably used because it satisfies these requirements. Here, “occlusion” means reversibly encapsulating lithium, reversibly forming an alloy or solid solution with lithium, or reversibly chemically bonding with lithium.

  When the negative electrode substrate 10 is used as a negative electrode material for a lithium secondary battery, it is necessary to form the negative electrode by laminating the negative electrode substrate 10 on a current collector. However, it is not necessary if the support 11 has conductivity, and the support 11 can be a current collector. The current collector is not particularly limited as long as it has conductivity, and its material, structure, and the like are not particularly limited. A current collector used for a conventional lithium secondary battery is used. Preferably, the adhesiveness with the negative electrode substrate 10 is good. Moreover, it is preferable that it is a material which does not alloy with lithium. Specifically, a material containing at least one element selected from the group consisting of copper, nickel, stainless steel, molybdenum, tungsten, titanium, and tantalum can be given. Moreover, structures, such as metal foil, a nonwoven fabric, and the metal electrical power collector which has a three-dimensional structure, are preferable. In particular, a metal foil is preferably used, and specifically, a copper foil or the like is preferably used. The thickness of the current collector is not particularly limited.

  Generally, in a negative electrode formed by laminating a thin film negative electrode material layer on a current collector, the internal resistance can be reduced compared to a negative electrode in which a particulate negative electrode material is laminated on a current collector together with a binder or the like. . That is, according to the negative electrode formed by laminating the negative electrode substrate 10 on the current collector, a lithium secondary battery having high power generation characteristics can be obtained. However, in a negative electrode in which a thin-film negative electrode material layer is laminated on a current collector, the adhesion between the negative electrode material layer and the current collector is large, and therefore the negative electrode material layer is expanded or contracted due to charge / discharge. There is a risk of deformation such as wrinkles in the current collector. In particular, when a metal foil rich in ductility such as copper foil is used for the current collector, the degree of deformation tends to be greater. For this reason, simply laminating a thin-film negative electrode material layer on the current collector may reduce the energy density of the battery or deteriorate the charge / discharge cycle characteristics.

  On the other hand, since the negative electrode substrate 10 according to the present invention has a structure in which the metal film 13 is laminated on the silica-based film 12, the metal film 13 expands / contracts as lithium is occluded / released. The stress caused by this is relieved by the buffering action of the silica-based coating 12. For this reason, as a result of being able to suppress the increase in the stress which arises at the time of charging / discharging, generation | occurrence | production of deformation | transformation, such as a flaw in a negative electrode base material or a collector, can be suppressed. As a result, cracking of the negative electrode substrate and peeling from the current collector can be suppressed. That is, according to the negative electrode formed by laminating the negative electrode substrate 10 on the current collector, a lithium secondary battery having a high output voltage, a high energy density, and excellent charge / discharge cycle characteristics can be obtained. .

  In addition, it is not specifically limited about structures other than a negative electrode, The structure similar to a conventionally well-known lithium secondary battery may be sufficient. Specifically, it is mainly composed of a positive electrode capable of reversibly inserting / extracting lithium and an electrolyte having lithium conductivity. The electrolyte is held by a separator as necessary, and in contact with the negative electrode and the positive electrode while being held by the separator, lithium is exchanged.

  The positive electrode is not particularly limited as long as lithium can be reversibly occluded / released, and a positive electrode generally used for a lithium secondary battery is used. Specifically, a positive electrode in which a positive electrode material layer is stacked over a current collector may be used. For example, it is formed by dispersing a positive electrode material, a conductive agent, and a binder in a dispersion solvent to form a slurry, coating the current collector, and drying. The thicknesses of the current collector and the positive electrode material layer are not particularly limited, and are arbitrarily set according to the battery design capacity and the like.

The positive electrode material is not particularly limited, and a conventionally known material such as an oxide containing lithium and a transition element is used. _{Specifically, LiCoO 2, LiNiO 2, LiMnO} 2, LiMn 2 O 4, LiCo 0.5 Ni 0.5 O 2 or the like is used. The conductive agent is not particularly limited as long as it is a material having electrical conductivity. For example, acetylene black, carbon black, graphite powder, or the like is used. The binder is not particularly limited as long as it can maintain the shape of the positive electrode material layer after forming the positive electrode, and a rubber-based binder or a resin-based binder such as a fluororesin is used.

  The separator is 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 thin film such as a porous polypropylene thin film or a porous polyethylene thin film, or a resin nonwoven fabric containing polyolefin or the like is used.

The electrolyte is not particularly limited as long as it has lithium conductivity. For example, a nonaqueous electrolyte solution in which an electrolyte containing lithium is dissolved in a nonaqueous solvent is used. As the electrolyte containing lithium, for example, a lithium salt such as LiPF ₆ , LiBF ₄ , LiClO ₄ , LiAsF ₆ , LiCF ₃ SO ₃ is used. Examples of the non-aqueous solvent include propylene carbonate, ethylene carbonate, dimethyl carbonate, methyl ethyl carbonate, diethyl carbonate, γ-butyrolactone, 1,2-dimethoxyethane, 1,2-diethoxyethane, ethoxymethoxyethane, and the like. A mixed solvent of a nonaqueous solvent is used. The concentration of the non-aqueous electrolyte solution is not particularly limited, and a so-called polymer electrolyte or solid electrolyte may be used.

  The lithium secondary battery using the negative electrode substrate 10 according to the present invention as a negative electrode can have various shapes such as a coin-shaped battery, a cylindrical battery, a rectangular battery, or a flat battery. Further, the capacity is not particularly limited, and it can be applied from a small battery used for precision equipment to a large battery used for a hybrid vehicle or the like.

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

〔Example〕
Resin whose solubility in alkali is increased by the action of an acid represented by the following structural formula (z1) (K-1S (trade name): manufactured by San Apro Co., Ltd.) and an acid represented by the following structural formula (z2) 40 parts by mass, 60 parts by mass of novolak 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 were mixed with propylene glycol monomethyl ether acetate. And the solution was filtered through a membrane filter having a pore diameter of 1 μm to obtain a positive resist composition having a solid content mass concentration of 20 mass%.

  This positive resist composition was applied onto a silicon wafer with a spin coater and then dried to obtain a photosensitive resin composition layer having a thickness of 2 μm. This positive resist composition layer was pre-baked at 130 ° C. for 1 minute using a hot plate. Then, pattern exposure (soft contact, GHI line) is performed using PLA-501F (contact aligner: manufactured by Canon), post-exposure heating (PEB) is performed at 75 ° C. for 5 minutes using a hot plate, and 3 mass% tetra Development processing was performed for 2 minutes by an immersion method using methylammonium hydroxide. A hole-shaped photoresist pattern having a diameter of 1 μm (pitch: 2 μm) was obtained on a silicon wafer.

  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, 204.0 g of water and 52 μL of 60% nitric acid were added, and the mixture was further stirred for 3 hours. Then, it was made to react at 26 degreeC for 2 days. 8.0 g of the reaction product, 11.8 g of propylene glycol monopropyl ether, and 0.2 g of a 0.1% propylene glycol monopropyl ether solution of DBU were mixed to obtain a composition for forming a silica-based film.

  The resulting silica-based film-forming composition was applied onto a silicon wafer on which the photoresist pattern was formed by spin coating, and heated for 1 minute each on a hot plate at 80 ° C., 150 ° C., and 200 ° C. . Furthermore, it was immersed in 70 ° C. for 20 minutes using exfoliation 104 (manufactured by Tokyo Ohka Kogyo Co., Ltd.) and then baked in a nitrogen atmosphere at 400 ° C. for 30 minutes to form a silica-based film having a thickness of about 2 μm. Formed.

The silicon wafer on which the silica-based film on this pattern was formed was immersed in a sodium phosphate solution for 60 seconds for cleaning treatment. Subsequently, the silicon wafer that has undergone the above cleaning step is immersed in a 0.05 g / dm ³ tin chloride (SnCl ₂ ) aqueous solution for 60 seconds, and further in a 0.05 g / dm ³ palladium chloride (PdCl ₂ ) aqueous solution. The catalyzing process was performed by immersing the film in 60 seconds.

  Next, the silicon wafer that has undergone the catalyzing step is immersed in a nickel plating bath comprising 0.20M nickel sulfate, 0.30M sodium hypophosphite, 0.30ppm lead ion, and 0.30M carboxylic acid complexing agent. And nickel plating treatment was performed. The temperature of the nickel plating bath at this time was 70 ° C., and the pH was adjusted to 5.5.

  Further, the silicon wafer that has undergone the electroless nickel plating step is immersed in a tin plating bath made of 0.20M tin chloride, 0.08M reducing agent such as titanium trichloride, and 0.50M trisodium citrate. A tin plating process was performed. At this time, the temperature of the tin plating bath was 70 ° C., and the pH was adjusted to 8.5.

  Using the negative electrode substrate obtained in the above example, a non-aqueous electrolyte secondary battery was produced by the following method. The discharge capacity after 1 to 3 cycles of this battery was measured by the following method. The results are shown in Table 1 below.

Each negative electrode substrate obtained in Example 1 was used as a working electrode, LiCoO ₂ was used as a counter electrode (positive electrode), and both electrodes were opposed to each other through a separator. A nonaqueous electrolyte secondary battery was produced by a conventional method using a mixed solution (1: 1 volume ratio) of LiPF ₆ / ethylene carbonate and dimethyl carbonate as a nonaqueous electrolyte. In this non-aqueous electrolyte secondary battery, the capacity ratio between the positive electrode and the negative electrode was 1: 1.

The discharge capacity per unit volume (mAh / cm ² ) was measured as each discharge capacity after 1 to 3 cycles. The discharge capacity per unit volume was based on the volume of the negative electrode. However, the expansion of the negative electrode during charging was not considered.

  The surface area of the negative electrode base material subjected to the tin plating treatment of the example with respect to the negative electrode base material was about 190% when the plating treatment was performed in a planar shape.

According to anode substrate for a lithium secondary battery according to the present invention, you have a high output voltage and a high energy density, is and can be realized an excellent lithium secondary battery charge-discharge cycle characteristics, for example, a portable device The battery can be used for various purposes regardless of the capacity, from a small battery used in a battery to a large battery used in a hybrid vehicle or the like.

It is a schematic diagram of the negative electrode base material which concerns on this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 10 Negative electrode base material 11 Support body 12 Silica-type film 13 Metal film

Claims (10)

A negative electrode for a lithium secondary battery in which a silica-based coating composed of a coating solution for forming a silica-based coating is formed on a support on which a photoresist pattern is formed, and a metal film is formed on the support from which the photoresist pattern has been removed A base material,
The metal film is formed by performing an electroless nickel plating process or an electroless copper plating process, and then performing an electroless tin plating process or an electrolytic tin plating process. A tin plating film is formed on the outermost surface. A negative electrode base material for a lithium secondary battery, comprising: The Hotorejisu DOO pattern is the photoresist pattern formed by using actinic rays or radiation a compound capable of generating an acid upon irradiation, and positive photoresist composition containing a resin component which exhibits increased solubility in an alkali by the action of an acid The negative electrode base material for lithium secondary batteries according to claim 1 . The Hotorejisu DOO pattern, a radical polymerization initiator, and a lithium secondary battery according to claim 1, characterized in that a photoresist pattern formed by using a negative photoresist composition containing a polyfunctional epoxy resin Negative electrode substrate. The silica film-forming coating solution, a lithium secondary battery according to any one of claims 1 3, characterized in that the silica-based coating film forming composition comprising a siloxane polymer and a solvent use the anode substrate. The lithium siloxane according to claim 4 , wherein the siloxane polymer is a reaction product obtained by hydrolyzing at least one selected from silane compounds represented by the following general formula (I). Negative electrode base material for secondary battery .

[In 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. ] The negative electrode substrate for a lithium secondary battery according to claim 5 , wherein the silane compound comprises methyltrialkoxysilane and tetraalkoxysilane. The claims 1 to 6 for a lithium secondary battery negative electrode substrate according to any one of an electrolyte solution, the lithium secondary battery, characterized in that it comprises a Seikyokumoto material lithium ions can occlude and release . It is a photoresist composition used for formation of the photoresist pattern in the negative electrode base material for lithium secondary batteries of any one of Claim 1 to 6 ,
A positive photoresist composition comprising a compound that generates an acid upon irradiation with actinic rays or radiation, and a resin component that increases alkali solubility by the action of the acid. It is a photoresist composition used for formation of the photoresist pattern in the negative electrode base material for lithium secondary batteries of any one of Claim 1 to 6 ,
A negative photoresist composition comprising a radical polymerization initiator and a polyfunctional epoxy resin. A method for producing a negative electrode base material for a lithium secondary battery ,
(I) forming a photoresist pattern on the support;
(Ii) forming a silica-based film comprising a coating liquid for forming a silica-based film on the photoresist pattern;
(Iii) removing the photoresist pattern;
(Iv) a plating process for forming a metal film by plating on a support on which a silica-based film processed into a pattern is formed;
Only including,
In the plating process, after the electroless nickel plating process or the electroless copper plating process is performed on the support on which the silica-based film processed into the pattern is formed, the electroless tin plating process or the electrolytic tin plating is further performed. The manufacturing method of the negative electrode base material for lithium secondary batteries characterized by forming a tin plating film in the outermost surface by processing .

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