JP5336049B2 - Negative electrode base material for lithium secondary battery - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an anode base material having high output voltage and high energy density and capable of realizing a battery with excellent charge/discharge cycle characteristics, a secondary battery with the use of the anode base material, a positive photoresist composition used for formation of this anode base material, and a manufacturing method of this anode base material. <P>SOLUTION: By the anode base material wherein a metal film is formed on a support having an organic film formed by a positive photoresist composition containing (A) alkali-soluble resin and (B) a quinonediazido-group-containing compound, or an anode base material equipped with a patterned organic film patterning the organic film in a predetermined shape by pattern exposure, a battery with high output voltage and high energy density as well as with excellent charge/discharge cycle characteristics can be provided. <P>COPYRIGHT: (C)2009,JPO&amp;INPIT

Description

The present invention is a lithium secondary battery anode substrate, a lithium secondary battery using the negative Gokumoto material, positive photoresist composition used for forming the negative Gokumoto material, and relates to a manufacturing method of the negative Gokumoto material, In particular, a negative electrode base material for a lithium secondary battery capable of providing a lithium secondary battery excellent in charge / discharge cycle characteristics, a lithium secondary battery using the negative electrode base material, and a positive photoresist composition used for forming the negative electrode base material And a method for producing the 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 The object is to provide a negative electrode substrate for a battery, a lithium secondary battery using the negative electrode substrate, a positive photoresist composition used for forming the negative electrode substrate, and a method for producing the negative electrode substrate.

  As a result of intensive studies in view of the above, the present inventors have formed a metal film on an organic film comprising a positive photoresist composition containing (A) an alkali-soluble resin and (B) a quinonediazide group-containing compound. According to the negative electrode substrate, the present inventors have found that a battery having a high output voltage and a high energy density and excellent charge / discharge cycle characteristics can be provided, and the present invention has been completed.

That is, the present invention comprises forming a predetermined metal film on a support provided with an organic film formed of a positive photoresist composition containing (A) an alkali-soluble resin and (B) a quinonediazide group-containing compound. for lithium secondary battery, wherein the anode substrate, a lithium secondary battery using the negative Gokumoto material, positive 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 positive 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, an organic film 12, and a metal film 13. More specifically, the present invention is characterized in that a metal film 13 is formed on a support 10 having an organic film 12 patterned in a predetermined shape by pattern exposure.

<Support>
The support 11 used for the negative electrode substrate 10 according to the present invention is not particularly limited as long as the organic film 12 can be formed 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 made of a material containing at least one element selected from copper, nickel, stainless steel, molybdenum, tungsten, titanium, and tantalum, a metal foil, a nonwoven fabric, a metal current collector having a three-dimensional structure, etc. It may serve as a current collector or may be formed on these current collectors.

<Organic film>
The organic film 12 in the negative electrode substrate 10 according to the present invention is formed by a positive photoresist composition containing (A) an alkali-soluble resin and (B) a quinonediazide group-containing compound, which will be described later. A patterned organic film obtained by patterning an organic film made of this positive photoresist composition into a predetermined shape by pattern exposure is preferable.

[Positive photoresist composition]
The positive photoresist composition used for forming the organic film 12 in the negative electrode substrate 10 according to the present invention may be a positive photoresist composition containing (A) an alkali-soluble resin and (B) a quinonediazide group-containing compound. If it does not specifically limit.

  Examples of the component (A) include phenols (phenol, m-cresol, p-cresol, xylenol, trimethylphenol, etc.) and aldehydes (formaldehyde, formaldehyde precursor, propionaldehyde, 2-hydroxybenzaldehyde, 3- Novolak resin obtained by condensing hydroxybenzaldehyde, 4-hydroxybenzaldehyde, etc.) and / or ketones (methyl ethyl ketone, acetone, etc.) in the presence of an acidic catalyst, a homopolymer of hydroxystyrene, hydroxystyrene and other styrene series Copolymers with monomers, hydroxystyrene resins such as copolymers of hydroxystyrene and acrylic acid or methacrylic acid or derivatives thereof, acrylic acid, methacrylic acid, or derivatives thereof, or these Acrylic resins such polymers, and the like.

  In particular, phenols containing at least two selected from m-cresol, p-cresol, 3,4-xylenol, and 2,3,5-trimethylphenol, formaldehyde, 2-hydroxybenzaldehyde (salicylaldehyde) and A novolak resin obtained by a condensation reaction with an aldehyde containing at least one selected from propionaldehyde is suitable for preparing a positive photoresist composition having high sensitivity and excellent resolution. (A) A component can be manufactured in accordance with a conventional method.

  The polystyrene-reduced mass average molecular weight (Mw) by gel permeation chromatography of the component (A) is preferably 2,000 to 100,000, more preferably 3,000, from the viewpoint of sensitivity and pattern formation, although it depends on the type. ~ 30,000.

  The component (A) is a novolak resin (hereinafter referred to as a fractional resin) that has been subjected to a fractionation treatment so that Mw is within a range of 3,000 to 30,000, more preferably 5,000 to 20,000. Preferably there is. By using such a fractionation resin as the component (A), a positive photoresist composition having excellent heat resistance can be obtained. The fractionation treatment can be performed, for example, by a fractional precipitation treatment utilizing the molecular weight dependency of the solubility of the polymer. In the fractional precipitation treatment, for example, the novolak resin of the condensation product obtained as described above is first dissolved in a polar solvent, and a poor solvent such as water, heptane, hexane, pentane, or cyclohexane is added to this solution. . At this time, since the low molecular weight polymer remains dissolved in the poor solvent, the fractionated resin in which the content of the low molecular weight polymer is reduced can be obtained by filtering the precipitate. Examples of the polar solvent include alcohols such as methanol and ethanol, ketones such as acetone and methyl ethyl ketone, glycol ether esters such as ethylene glycol monoethyl ether acetate, and cyclic ethers such as tetrahydrofuran.

［上記一般式（ｂ１）中、Ｒ^ｂ１〜Ｒ^ｂ８は、それぞれ独立に水素原子、ハロゲン原子、炭素原子数１〜６のアルキル基、炭素原子数１〜６のアルコキシ基、又は炭素原子数３〜６のシクロアルキル基を示し、Ｒ^ｂ１０及びＲ^ｂ１１は、それぞれ独立に水素原子、又は炭素原子数１〜６のアルキル基を示し、Ｒ^ｂ９が水素原子、又は炭素数１〜６のアルキル基の場合、Ｑ^１は水素原子、炭素数１〜６のアルキル基、又は下記化学式（ｂ２）

［上記一般式（ｂ２）中、Ｒ^ｂ１２及びＲ^ｂ１３は、それぞれ独立に水素原子、ハロゲン原子、炭素原子数１〜６のアルキル基、炭素原子数１〜６のアルコキシ基、又は炭素原子数３〜６のシクロアルキル基を示し、ｃは１〜３の整数を示す。］で表される残基を表し、Ｑ^１がＲ^ｂ９の末端と結合する場合は、Ｑ^１はＲ^ｂ９及び、Ｑ^１とＲ^ｂ９との間の炭素原子とともに、炭素原子鎖３〜６のシクロアルキレン鎖を構成し、ａ及びｂは１〜３の整数を示し、ｄは０〜３の整数を示し、ｎは０〜３の整数を示す。］で表される化合物と、１，２−ナフトキノンジアジドスルホニル化合物とのエステル化反応生成物（非ベンゾフェノン系ＰＡＣ）が、高感度であり、低ＮＡ条件下でも解像性に優れ、さらにマスクリニアリティやＤＯＦの点から好ましい。 The component (B) is a quinonediazide group-containing compound, particularly the following general formula (b1)

[In the general formula (b1), R ^{b1 to} R ^b8 are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or 3 carbon atoms. -6 represents a cycloalkyl group, R ^b10 and R ^b11 each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and R ^b9 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. In this case, Q ¹ is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or the following chemical formula (b2)

[In the general formula (b2), R ^b12 and R ^b13 each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or 3 carbon atoms. -6 represents a cycloalkyl group, and c represents an integer of 1 to 3. A residue represented by, ^{if Q 1} is bonded with the terminal of ^{R b9} is, ^{Q 1} together with the carbon atom between ^{R b9} and, ^{Q 1} and ^{R b9,} the chain of carbon atoms 3-6 A cycloalkylene chain is comprised, a and b show the integer of 1-3, d shows the integer of 0-3, n shows the integer of 0-3. The esterification reaction product (non-benzophenone-based PAC) of the compound represented by formula (1) with a 1,2-naphthoquinonediazide sulfonyl compound is highly sensitive, has excellent resolution even under low NA conditions, and has mask linearity. And preferred from the viewpoint of DOF.

As a phenol compound corresponding to the general formula (b1), for example,
[1] ^{Q 1} is not bonded with the terminal of ^{R b9, R b9} represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, a residue ^{which Q 1} is represented by Formula (b2) , trisphenol compounds n represents 0, and (2) ^{Q 1} is not bonded with the terminal of ^{R b9, R b9} represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, ^{Q 1} is hydrogen A linear polyphenol compound which represents an atom or an alkyl group having 1 to 6 carbon atoms and n represents an integer of 1 to 3 is preferable.

  More specifically, as the trisphenol type compound, tris (4-hydroxyphenyl) methane, bis (4-hydroxy-3-methylphenyl) -2-hydroxyphenylmethane, bis (4-hydroxy-2,3, 5-trimethylphenyl) -2-hydroxyphenylmethane, bis (4-hydroxy-3,5-dimethylphenyl) -4-hydroxyphenylmethane, bis (4-hydroxy-3,5-dimethylphenyl) -3-hydroxyphenyl Methane, bis (4-hydroxy-3,5-dimethylphenyl) -2-hydroxyphenylmethane, bis (4-hydroxy-2,5-dimethylphenyl) -4-hydroxyphenylmethane, bis (4-hydroxy-2, 5-dimethylphenyl) -3-hydroxyphenylmethane, bis (4-hydroxy) -2,5-dimethylphenyl) -2-hydroxyphenylmethane, bis (4-hydroxy-3,5-dimethylphenyl) -3,4-dihydroxyphenylmethane, bis (4-hydroxy-2,5-dimethylphenyl) -3,4-dihydroxyphenylmethane, bis (4-hydroxy-2,5-dimethylphenyl) -2,4-dihydroxyphenylmethane, bis (4-hydroxyphenyl) -3-methoxy-4-hydroxyphenylmethane, bis (5-cyclohexyl-4-hydroxy-2-methylphenyl) -4-hydroxyphenylmethane, bis (5-cyclohexyl-4-hydroxy-2-methylphenyl) -3-hydroxyphenylmethane, bis (5-cyclohexyl-4 -Hydroxy-2-methylphenyl) -2-hydroxyfe Rumetan, and bis (5-cyclohexyl-4-hydroxy-2-methylphenyl) -3,4-dihydroxyphenyl methane.

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

  Other than the trisphenol type compound and the linear type polyphenol compound, phenol compounds corresponding to the general formula (b1) include bis (2,3,4-trihydroxyphenyl) methane, bis (2,4-dihydroxyphenyl). Methane, 2,3,4-trihydroxyphenyl-4′-hydroxyphenylmethane, 2- (2,3,4-trihydroxyphenyl) -2- (2 ′, 3 ′, 4′-trihydroxyphenyl) propane 2- (2,4-dihydroxyphenyl) -2- (2 ′, 4′-dihydroxyphenyl) propane, 2- (4-hydroxyphenyl) -2- (4′-hydroxyphenyl) propane, 2- (3 -Fluoro-4-hydroxyphenyl) -2- (3'-fluoro-4'-hydroxyphenyl) propane, 2- (2,4-di Droxyphenyl) -2- (4′-hydroxyphenyl) propane, 2- (2,3,4-trihydroxyphenyl) -2- (4′-hydroxyphenyl) propane, 2- (2,3,4- Bisphenol type compounds such as trihydroxyphenyl) -2- (4′-hydroxy-3 ′, 5′-dimethylphenyl) propane; 1- [1- (4-hydroxyphenyl) isopropyl] -4- [1,1- Bis (4-hydroxyphenyl) ethyl] benzene, 1- [1- (3-methyl-4-hydroxyphenyl) isopropyl] -4- [1,1-bis (3-methyl-4-hydroxyphenyl) ethyl] benzene , Etc .; and condensed phenol compounds such as 1,1-bis (4-hydroxyphenyl) cyclohexane. These phenol compounds can be used alone or in combination of two or more.

  Among these components (B), the above trisphenol type compound is particularly preferable, and bis (5-cyclohexyl-4-hydroxy-2-methylphenyl) -3,4-dihydroxyphenylmethane [hereinafter abbreviated as (B1)]. To do. ], Bis (4-hydroxy-2,3,5-trimethylphenyl) -2-hydroxyphenylmethane [hereinafter abbreviated as (B3). The photoresist composition containing a naphthoquinone diazide esterified product of a trisphenol type compound is preferable because of its excellent sensitivity and resolution. In addition to the naphthoquinone diazide esterified product of the trisphenol type compound, naphthoquinone diazide esterified products of other phenol compounds, that is, naphthoquinone diazide esterified products of phenol compounds such as the above-mentioned bisphenol type compounds, polynuclear branched type compounds, and condensed type phenol compounds. Is preferably used because a resist composition excellent in total balance of resist characteristics such as resolution, sensitivity, heat resistance, DOF characteristics, mask linearity and the like can be adjusted. In particular, bisphenol type compounds, especially bis (2,4-dihydroxyphenyl) methane [hereinafter abbreviated as (B2)]. ] Is preferable. The positive photoresist composition containing the naphthoquinone diazide esterified product of the three phenol compounds (B1), (B3) and (B2) is a resist pattern having a high sensitivity, a high resolution and a good shape. Is preferable in that it can be formed.

  When using (B1) and (B3), it is preferable that the compounding quantity in (B) component is 10 mass% or more in all (B) components, respectively, and also 15 mass% or more. Moreover, when using all (B1), (B2), and (B3), from the point of an effect, each compounding quantity is 50-90 mass% in all (B) components, Preferably it is 60- 80% by mass, the blending amount of (B2) is 5 to 20% by mass, preferably 10 to 15% by mass, and the blending amount of (B3) is 5 to 20% by mass, preferably 10 to 15% by mass. .

  The method of converting all or part of the phenolic hydroxyl group of the compound represented by the general formula (b1) into naphthoquinonediazide sulfonic acid ester can be performed by a conventional method. For example, it can be obtained by condensing naphthoquinonediazide sulfonyl chloride with the compound represented by the general formula (b1). Specifically, for example, the compound represented by the general formula (b1) and naphthoquinone-1,2-diazide-4 (or 5) -sulfonyl chloride are mixed with dioxane, n-methylpyrrolidone, dimethylacetamide, tetrahydrofuran, and the like. A predetermined amount is dissolved in an organic solvent, and one or more basic catalysts such as triethylamine, triethanolamine, pyridine, alkali carbonate, alkali hydrogen carbonate and the like are added and reacted, and the resulting product is washed with water and dried. Can be prepared.

  As the component (B), as described above, in addition to these exemplified preferred naphthoquinone diazide esterified products, other naphthoquinone diazide esterified products can also be used. For example, phenol compounds such as polyhydroxybenzophenone and alkyl gallate, An esterification reaction product with a quinonediazide sulfonic acid compound or the like can also be used. The amount of these other naphthoquinone diazide esterification products is preferably 80% by mass or less, particularly 50% by mass or less in the component (B).

  The compounding amount of the component (B) in the positive photoresist composition is 20 to 70% by mass, preferably 25 to the total amount of the component (A) and an optional component (C) described later. 60% by mass. By setting the blending amount of the component (B) to the above lower limit value or more, an image faithful to the pattern can be obtained and transferability is improved. By setting it to the upper limit value or less, it is possible to prevent the sensitivity from being deteriorated, improve the homogeneity of the formed resist film, and improve the resolution.

  In such a positive photoresist composition, in addition to the components (A) and (B) described above, as a component (C), a phenolic hydroxyl group-containing compound having a molecular weight of 1,000 or less is used as a sensitizer. You may mix | blend. This component (C) is excellent in the sensitivity improvement effect, and by using the component (C), a material having high sensitivity and high resolution even under low NA conditions and further excellent in mask linearity can be obtained. . Component (C) has a molecular weight of 1,000 or less, preferably 700 or less, and is substantially 200 or more, preferably 300 or more.

［式中、Ｒ^ｃ１〜Ｒ^ｃ８は、それぞれ独立に水素原子、ハロゲン原子、炭素原子数１〜６のアルキル基、炭素原子数１〜６のアルコキシ基、又は炭素原子数３〜６のシクロアルキル基を示し、Ｒ^ｃ１０及びＲ^ｃ１１は、それぞれ独立に水素原子又は炭素原子数１〜６のアルキル基を示し、Ｒ^ｃ９が水素原子又は炭素原子数１〜６のアルキル基の場合、Ｑ^２は水素原子、炭素原子数１〜６のアルキル基、又は下記化学式（ｃ２）で表される残基

［式中、Ｒ^ｃ１２及びＲ^ｃ１３はそれぞれ独立に水素原子、ハロゲン原子、炭素原子数１〜６のアルキル基、炭素原子数１〜６のアルコキシ基、又は炭素原子数３〜６のシクロアルキル基を示し、ｇは０〜３の整数を示す。］であり、Ｑ^２がＲ^ｃ９の末端と結合する場合は、Ｑ^２がＲ^ｃ９及び、Ｑ^２とＲ^ｃ９との間の炭素原子とともに、炭素原子鎖３〜６のシクロアルキレン鎖を示し、ｅ及びｆは１〜３の整数を表し；ｈは０〜３の整数を表し；ｍは０〜３の整数を表す。］で表されるフェノール化合物が好ましい。 Such a component (C) is a phenolic hydroxyl group-containing compound generally used in a photoresist composition as a sensitivity improver or a sensitizer, and preferably satisfies the above molecular weight condition. There is no restriction | limiting and it can select and use 1 type or 2 types or more arbitrarily. And among them, the following general formula (c1)

[Wherein R ^{c1 to} R ^c8 each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a cycloalkyl having 3 to 6 carbon atoms. R ^c10 and R ^c11 each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and when R ^c9 is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, Q ² is A hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a residue represented by the following chemical formula (c2)

[ ^Wherein , R ^c12 and R ^c13 each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a cycloalkyl group having 3 to 6 carbon atoms. And g represents an integer of 0 to 3. A], ^{if Q 2} is bonded with the terminal of ^{R c9} is, ^{Q 2} is ^{R c9} and, together with the carbon atoms between ^{Q 2} and ^{R c9,} it shows a cycloalkylene chain of carbon atoms chains 3-6, e and f represent the integer of 1-3; h represents the integer of 0-3; m represents the integer of 0-3. ] The phenol compound represented by this is preferable.

  Specifically, for example, in addition to the phenol compound used in the naphthoquinonediazide esterified product of the phenol compound exemplified in the component (B), bis (3-methyl-4-hydroxyphenyl) -4-isopropylphenylmethane, bis (3-methyl-4-hydroxyphenyl) -phenylmethane, bis (2-methyl-4-hydroxyphenyl) -phenylmethane, bis (3-methyl-2-hydroxyphenyl) -phenylmethane, bis (3,5- Dimethyl-4-hydroxyphenyl) -phenylmethane, bis (3-ethyl-4-hydroxyphenyl) -phenylmethane, bis (2-methyl-4-hydroxyphenyl) -phenylmethane, bis (2-tert-butyl-4 , 5-dihydroxyphenyl) -phenylmethane It can be suitably used phenyl-type compound. Among them, bis (2-methyl-4-hydroxyphenyl) -phenylmethane, 1- [1- (4-hydroxyphenyl) isopropyl] -4- [1,1-bis (4-hydroxyphenyl) ethyl] benzene preferable.

  The blending amount of the component (C) is 10 to 70% by mass, preferably 20 to 60% by mass with respect to the component (A).

  The positive photoresist composition preferably contains an organic solvent. The organic solvent is not particularly limited as long as it is a general one used in a photoresist composition, and one or more organic solvents can be selected and used. Specific examples of such organic solvents include ketones such as acetone, methyl ethyl ketone, cyclohexanone, methyl isoamyl ketone, and 2-heptanone; ethylene glycol, propylene glycol, diethylene glycol, ethylene glycol monoacetate, propylene glycol monoacetate, and diethylene glycol. Monoacetate or polyhydric alcohols such as monomethyl ether, monoethyl ether, monopropyl ether, monobutyl ether or monophenyl ether and derivatives thereof; cyclic ethers such as dioxane; and methyl acetate, ethyl acetate, acetic acid Esters such as butyl, ethyl lactate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate, ethyl ethoxypropionate, γ-buty Lactone, and the like.

  Among the above organic solvents, use at least one organic solvent selected from propylene glycol monomethyl ether, propylene glycol monobutyl ether, propylene glycol monomethyl ether acetate, 2-heptanone, methyl lactate, ethyl lactate, and γ-butyrolactone. Is preferred. When these solvents are used, it is desirable that the total organic solvent be 50% by mass or less.

  Furthermore, in the positive photoresist composition, as long as the object of the present invention is not impaired, a compatible additive, for example, an additional resin, a plasticizer, a storage for improving the performance of the resist film, etc. Conventional additions such as stabilizers, surfactants, colorants to make the developed image more visible, sensitizers and antihalation dyes to improve the sensitization effect, adhesion improvers, etc. Products can be included.

  Examples of the antihalation dye include ultraviolet absorbers (for example, 2,2 ′, 4,4′-tetrahydroxybenzophenone, 4-dimethylamino-2 ′, 4′-dihydroxybenzophenone, 5-amino-3-methyl-1). -Phenyl-4- (4-hydroxyphenylazo) pyrazole, 4-dimethylamino-4'-hydroxyazobenzene, 4-diethylamino-4'-ethoxyazobenzene, 4-diethylaminoazobenzene, curcumin, etc.) can be used.

  The surfactant can be added, for example, to prevent striation, and the like, for example, Florard FC-430, FC431 (trade name, manufactured by Sumitomo 3M Co., Ltd.), F-top EF122A, EF122B, EF122C, EF126 (product) Fluorosurfactants such as name, manufactured by Tochem Products Co., Ltd.), XR-104, MegaFac R-08 (trade name, manufactured by Dainippon Ink & Chemicals, Inc.) and the like can be used.

[Patterned organic film]
The organic film 12 is formed by applying the positive photoresist composition on the support 11 using a spinner. Further, after such an organic film 12 is applied on the support 11, it is exposed to an active ray or radiation such as ultraviolet ray, excimer laser, X-ray, electron beam or the like through a mask, and then exposed to an image. Then, heat treatment is performed as necessary, development processing is further performed with an alkali developer to dissolve and remove unirradiated portions, and heat treatment is performed as necessary to form a patterned organic film.

  The aspect ratio of the patterned organic film obtained as described above is preferably 0.1 or more. By setting the aspect ratio of the patterned organic film to 0.1 or more, the surface area of the negative electrode substrate 10 can be increased, and the amount of the metal film formed by the plating process described later can be increased. High energy density is achieved.

<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 is not particularly limited as long as the metal film 13 can be formed on the organic film 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 organic film 12 is immersed in a phosphoric acid solution for cleaning. As the phosphate 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, and 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 organic film 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 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. A metal film 13 is formed. 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 a metal 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 organic film 12, the metal film 13 expands / contracts with the insertion / release of lithium. Is relieved by the buffering action of the organic film 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〕
As component (A), m-cresol / p-cresol / 2,3,5-trimethylphenol = 40/35/25 (molar ratio) mixed phenols, salicylaldehyde / formaldehyde = 1/5 (molar ratio) 13 g of novolak resin with Mw = 5,200 synthesized by a conventional method using mixed aldehydes, and as component (B), bis (5-cyclohexyl-4-hydroxy-2-methylphenyl) -3,4-dihydroxy 1 mol of phenylmethane (B1) and 1,2-naphthoquinonediazide-5-sulfonyl chloride [hereinafter abbreviated as (5-NQD). The esterification reaction product with 2 moles, the esterification reaction product with 1 mole of bis (2,4-dihydroxyphenyl) methane (B2) and 2 moles of 5-NQD, and bis (4-hydroxy-2,3,3) 7.5 g of a mixture of esterification reaction product of 1 mol of 5-trimethylphenyl) -2-hydroxyphenylmethane (B3) and 2 mol of 5-NQD (mass mixing ratio = B1: B2: B3 = 4: 1: 1) As a component (C), 5.5 g of bis (2-methyl-4-hydroxyphenyl) -phenylmethane and 74 g of a propylene glycol monomethyl ether acetate solvent were mixed to prepare a positive photoresist composition.

  This positive photoresist composition was applied on a silicon wafer and pre-baked to form an organic film having a thickness of 1.48 μm. The organic film is selectively exposed with an i-line exposure apparatus (product name “NSR-2005i10D”; manufactured by Tokyo Ohka Kogyo Co., Ltd.), and then an aqueous tetramethylammonium hydroxide solution having a concentration of 2.38% by mass ( The product name “NMD-3” (manufactured by Tokyo Ohka Kogyo Co., Ltd.) is subjected to a development process for 60 seconds and a rinse process for 30 seconds with pure water, followed by a drying step, and a 5 (pitch 20 μm) μm pillar-shaped pattern A formed organic film was formed.

The silicon wafer on which the patterned organic film 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.

The negative electrode substrate obtained in the example 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 115% when the plating treatment was performed in a planar shape.

According to anode substrate for a lithium secondary battery according to the present invention, it has 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 Organic film 13 Metal film

Claims (7)

A negative electrode group for a lithium secondary battery formed by forming a metal film on a support provided with an organic film formed of a positive photoresist composition containing (A) an alkali-soluble resin and (B) a quinonediazide group-containing compound. 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 negative electrode substrate for a lithium secondary battery according to claim 1, wherein the organic film is a patterned organic film patterned into a predetermined shape by pattern exposure. The negative electrode substrate for a lithium secondary battery according to claim 1 or 2 , wherein the component (A) is at least one selected from a novolak resin, a hydroxystyrene-based resin, and an acrylic resin. . The component (B) is represented by the following general formula (b1)

[In the general formula (b1), R ^{b1 to} R ^b8 are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or 3 carbon atoms. -6 represents a cycloalkyl group, R ^b10 and R ^b11 each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and R ^b9 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. In this case, Q ¹ is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or the following chemical formula (b2)

[In the general formula (b2), R ^b12 and R ^b13 each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or 3 carbon atoms. -6 represents a cycloalkyl group, and c represents an integer of 1 to 3. ]
And Q ¹ is bonded to the terminal of R ^b9 , Q ¹ is R ^b9 and a cycloalkylene having 3 to 6 carbon atoms together with the carbon atom between Q ¹ and R ^b9. It comprises a chain | strand, a and b show the integer of 1-3, d shows the integer of 0-3, n shows the integer of 0-3. ]
The negative electrode substrate for a lithium secondary battery according to any one of claims 1 to 3 , wherein the product is an esterification reaction product of a compound represented by formula (1) and a 1,2-naphthoquinonediazidosulfonyl compound. . A lithium secondary battery comprising the negative electrode base material for a lithium secondary battery according to any one of claims 1 to 4 , an electrolyte solution, and a positive electrode base material capable of inserting and extracting lithium ions. A positive photoresist composition used for forming an organic film in the negative electrode base material for a lithium secondary battery according to any one of claims 1 to 4 , comprising (A) an alkali-soluble resin and (B) a quinonediazide. A positive photoresist composition comprising a group-containing compound. A method for producing a negative electrode base material for a lithium secondary battery,
(I) forming an organic film on a support using a positive photoresist composition containing (A) an alkali-soluble resin and (B) a quinonediazide group-containing compound;
(Ii) a plating process for forming a metal film on the organic film by plating;
Including
In the plating process, after the electroless nickel plating process or the electroless copper plating process is performed on the organic film, the electroless tin plating process or the electrolytic tin plating process is further performed to form a tin plating film on the outermost surface. A method for producing a negative electrode substrate for a lithium secondary battery.

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