CN101569036B

CN101569036B - Negative electrode base member

Info

Publication number: CN101569036B
Application number: CN2007800456686A
Authority: CN
Inventors: 三隅浩一; 齐藤宏二; 渡边充广; 本间英夫
Original assignee: Tokyo Ohka Kogyo Co Ltd; Kanto Gakuin University Surface Engineering Research Institute
Current assignee: Kanto Institute University Inc; Tokyo Ohka Kogyo Co Ltd
Priority date: 2006-12-15
Filing date: 2007-12-11
Publication date: 2011-12-28
Anticipated expiration: 2027-12-11
Also published as: JP5237546B2; JP2008153033A; CN101569036A

Abstract

The present invention aims to realize a battery having high output voltage, high energy density and excellent charge/discharge characteristics through a constitution different from those of conventional batteries. Specifically, one of the following negative electrode base members is used as a negative electrode base member for lithium ion secondary batteries: a negative electrode base member wherein a metal film is formed on a support having an organic film; such a negative electrode base member wherein the surface layer of the organic film is covered with a metal oxide film; a negative electrode base member wherein a metal film is formed on a support having a composite film made from a composite film-forming material containing an organic component and an inorganic component; and a negative electrode base member wherein a silica coating is formed, on a support having a photoresist pattern, from a silica film-forming coating liquid and a metal film is formed on the support after removing the photoresist pattern.

Description

Base material of cathode

Technical field

The present invention relates to a kind of base material of cathode, use the secondary cell of this base material of cathode, the photoresistance composition, the metal oxide film that are used to form this base material of cathode form material, compound film formation material, and the manufacture method of this base material of cathode, particularly relate to a kind of base material of cathode that the battery of excellent charge can be provided, use the secondary cell of this base material of cathode, the photoresistance composition, the metal oxide film that are used to form, make this base material of cathode form material, compound film formation material, and the manufacture method of this base material of cathode.

Background technology

In the past, very in vogue to the research and development of the battery that has high output voltage and high-energy-density concurrently.Particularly seek a kind of internal resistance battery capacitor lower, that cause because of charge/discharge secondary cell less, excellent charge that descends.For example, the known lithium secondary battery (referring to patent documentation 1) that has use film like amorphous silicon or microcrystal silicon to be used as negative material (negative electrode active material).Particularly, disclosed and used the lithium secondary battery that on collector body, forms the negative pole of the negative electrode material layer that comprises silicon thin film, silicon thin film is to use film formation methods such as CVD method (chemical vapor deposition method is also referred to as chemical vapour deposition technique, chemical vapor deposition method) or sputtering method and forms.

Wherein, it is generally acknowledged that materials such as silicon can carry out expansion repeatedly along with occlusion/release lithium.Form in the negative pole of silicon thin film on collector body, because the adhesiveness of collector body and negative electrode material layer is higher, so collector body carries out expansion continually along with the expansion of negative material.So along with the carrying out of charge/discharge, negative electrode material layer and collector body may produce expendable distortion such as fold.Particularly when collector body used Copper Foil etc. to be rich in the metal forming of ductility, the degree of distortion will increase.The negative pole distortion can cause as the volume of electrode and increase, and makes electrochemical reaction become inhomogeneous etc., and therefore, the energy density of battery might descend.In addition, carry out during the expansion repeatedly along with charge/discharge, negative material might micronizing and break away from from collector body, perhaps according to circumstances also may break away from from collector body with the state of film like, and this is the principal element that causes the charge of battery to worsen.

As the method that suppresses the negative pole distortion, can enumerate the method that the higher materials of mechanical strength such as using hot strength or stretch modulus is used as collector body.But, when on by the formed collector body of this material, constituting the formed negative electrode material layer of negative material by film like, might negative electrode material layer and the adhesiveness of collector body insufficient, and can not obtain sufficient charge.Therefore, in patent documentation 1, disclosed following technology: will be by meeting and the formed intermediate layer of the material of negative material alloying, be configured between collector body and the negative electrode material layer, and using mechanical strength to be higher than the collector body in intermediate layer, negative material breaks away from and suppresses to produce fold etc. when suppressing charge/discharge with this.Particularly, use the copper layer to be used as the intermediate layer, use nickel foil to be used as collector body.

In the document beyond described patent documentation 1, also disclosed following technology: make copper be solid-solubilized in that the film of gained is used as negative electrode material layer on the silicon, with the occlusion amount of inhibition lithium, the expansion of the negative material when suppressing the occlusion lithium thus (referring to patent documentation 2).In addition, disclosed following technology: use comprise can be with the metal of lithium alloyage, and can not be used as negative electrode material layer with the alloy firm of the metal of lithium alloyage, to suppress the occlusion amount of lithium, the expansion of the negative material when suppressing the occlusion lithium thus (referring to patent documentation 3).Particularly, form the metal of solid solution or intermetallic compound etc. with lithium alloyage as meeting, be to use tin (Sn), germanium (Ge), aluminium (Al), indium (In), magnesium (Mg) and silicon (Si) etc., as not can with the metal of lithium alloyage, be to use copper (Cu), iron (Fe), nickel (Ni), cobalt (Co), molybdenum (Mo), tungsten (W), tantalum (Ta) and manganese (Mn) etc.

In addition, disclosed following technology: by using collector body as described below, suppress electrode and produce distortion along with charge/discharge, be i.e. every 1cm of this collector body ²In the deflection that formed on the thickness direction more than 10 be the variant part of 5 μ m～20 μ m, and the numerical aperture of variant part is (referring to a patent documentation 4) below 4%.In addition, disclosed following technology: on the surface of the negative electrode material layer of the film like of reversibly occlusion/release lithium with inner at least in one of them, the configuration non-occlusion material of lithium (referring to patent documentation 5).

[patent documentation 1] Japan Patent spy opens the 2002-083594 communique

[patent documentation 2] Japan Patent spy opens the 2002-289177 communique

[patent documentation 3] Japan Patent spy opens the 2002-373647 communique

[patent documentation 4] Japan Patent spy opens the 2003-017069 communique

[patent documentation 5] Japan Patent spy opens the 2005-196971 communique

Summary of the invention

[inventing problem to be solved]

But present situation is to use any in the described various negative material, the battery of all failing to obtain to have sufficient output voltage, energy density and charge.So, the object of the present invention is to provide a kind of formation different of utilizing with described conventional art, and can realize having the base material of cathode of the battery of high output voltage and high-energy-density and excellent charge, secondary cell with this base material of cathode, the manufacture method of this base material of cathode, be used to form the compound film formation material of this base material of cathode, the metal oxide film that is used to form this base material of cathode forms material, be used to form the eurymeric photoresistance composition of this base material of cathode, and the photoresistance composition that is used to form this base material of cathode.

[technological means of dealing with problems]

Present inventors concentrate on studies repeatedly in view of described situation, found that, utilize base material of cathode as described below to provide and have the battery of high output voltage and high-energy-density and excellent charge, thereby finish the present invention: lamination forms the base material of cathode of metal film on organic membrane; On the composite membrane that organic principle and inorganic constituents are composited, form the base material of cathode of metal film; On the organic membrane of top layer, form the base material of cathode of metal film by the metal oxide film lining; Form the base material of cathode of metal film on by overlay film patterning silica-based; And, form the base material of cathode of metal film by containing (A) alkali soluble resins and (B) containing on the formed organic membrane of eurymeric photoresistance composition of compound of quinone diazido.

That is to say, the invention provides a kind of base material of cathode that forms metal film on the supporter of organic membrane possessing that is characterised in that.In addition, the invention provides: be characterised in that the base material of cathode that forms described organic membrane by the photoresistance film; Perhaps be characterised in that by pattern exposure, and with the base material of cathode of this photoresistance film patterning established practice setting shape.In addition, the invention provides a kind of photoresistance composition that has the manufacture method of the secondary cell of described base material of cathode, described base material of cathode and be used to make described base material of cathode.

The invention provides a kind of being characterised in that and possessing on the supporter of top layer by the organic membrane of metal oxide film lining, form the base material of cathode of metal film.In addition, provide: described organic membrane is by the film formed base material of cathode of photoresistance; By pattern exposure with the base material of cathode of this photoresistance film patterning established practice setting shape; And described metal oxide film is silica-based by the base material of cathode of overlay film.In addition, the invention provides a kind of secondary cell of base material of cathode, the metal oxide film formation material that is used to form this base material of cathode and manufacture method of photoresistance composition and base material of cathode used.

The invention provides a kind of base material of cathode that on the supporter that possesses by the formed composite membrane of compound film formation material that comprises organic principle and inorganic constituents, forms metal film that is characterised in that, use the secondary cell of this base material of cathode, be used to form the compound film formation material of this base material of cathode, and the manufacture method of this base material of cathode.

The invention provides a kind of being characterised in that on the supporter that forms the photoresistance pattern, formation is formed with coating fluid formed silica-based by overlay film by silica-based by overlay film, and on the supporter of having removed described photoresistance pattern, form the base material of cathode of metal film, use the secondary cell of this base material of cathode, be used to form the photoresistance composition of this base material of cathode, and the manufacture method of this base material of cathode.

[invention effect]

According to the present invention, can provide a kind of can the realization to have high output voltage and high-energy-density, and the base material of cathode of the battery of excellent charge, secondary cell with this base material of cathode, the manufacture method of this base material of cathode, be used to form the compound film formation material of this base material of cathode, the metal oxide film that is used to form this base material of cathode forms uses composition, and the photoresistance composition that is used to form this base material of cathode.

Description of drawings

Fig. 1 is the schematic diagram of the base material of cathode of embodiments of the invention 1.

Fig. 2 is the schematic diagram of the base material of cathode of embodiments of the invention 2.

Fig. 3 is the schematic diagram of the base material of cathode of embodiments of the invention 3.

Fig. 4 is the schematic diagram of the base material of cathode of embodiments of the invention 4.

[explanation of symbol]

10,20,30,40 base material of cathode

11,21,31,41 supporters

12,22 organic membrane

13,24,33,43 metal films

23 metal oxide film films

32 composite membranes

42 is silica-based by overlay film

Embodiment

Below, with reference to accompanying drawing, describe example of the present invention in detail.

(first example)

＜base material of cathode 〉

Fig. 1 represents the schematic diagram of the base material of cathode 10 of this example.As shown in Figure 1, the base material of cathode 10 of this example comprises: supporter 11, organic membrane 12 and metal film 13.More specifically, the base material of cathode 10 of present embodiment is characterised in that: the supporter 11 enforcement platings that possess organic membrane 12 are handled forming metal film 13.

＜supporter 〉

As long as employed supporter 11 can form organic membrane 12 in the base material of cathode of this example 10 on its surface, be not particularly limited.For example, the well-known in the past supporters such as substrate that can use electronic component to use.Particularly, can enumerate: silicon chip, be provided with organic system or inorganic be the silicon chip of anti-reflective film, formed the silicon chip of magnetic film, metal substrates such as copper, chromium, iron, aluminium, or glass substrate etc.In addition, these supporters can comprise the material that is selected from least a element in copper, nickel, stainless steel, molybdenum, tungsten, titanium and the tantalum by double as, metal forming, and adhesive-bonded fabric, the collector bodies such as metal current collector with three-dimensional structure also can be formed on these collector bodies.

＜organic membrane 〉

Organic membrane 12 in the base material of cathode 10 of this example is to be formed by well-known organic compound or organic resin in the past, is not particularly limited.The preferred organic membrane 12 that is formed by following photoresistance composition more preferably is patterned to the photoresistance pattern of regulation shape by pattern exposure.

[photoresistance composition]

Photoresistance composition for the base material of cathode 10 that is used to form this example is not particularly limited, and can use well-known in the past photoresistance composition.The photoresistance composition that preferably has hydrophilic group.So long as, as mentioned above, just can on it, form with the photoresistance pattern and adhere to the metal oxide film 13 that density is higher and mechanical strength is higher securely by the formed photoresistance pattern of the photoresistance composition with hydrophilic group.

[eurymeric photoresistance composition]

As the chemical amplification type photoresistance composition of eurymeric, the preferred use with the photoresistance composition of following compositions as basis: by irradiation active ray or radioactive ray and acidic acid producing agent composition (hereinafter referred to as (A) composition) and to the dissolubility of alkaline aqueous solution because the resinous principle (hereinafter referred to as (B) composition) that the effect of acid changes.(B) composition is to use the hydroxyl of alkali soluble resins to be subjected to the protection of acid disassociation property dissolving inhibition base and is the insoluble resin of alkali.By this (B) composition and the combination of described (A) composition are used, exposed portion produces acid, and the acid that this produced makes the dissolving of described acid disassociation property suppress the protection disassociation of base.This exposed portion is alkali solubility as a result, during development only exposed portion optionally removed, obtain the photoresistance pattern of regulation shape.

(acid producing agent composition (A))

(A) composition is acidic directly or indirectly material by shining active ray or radioactive ray.

First form of this acid producing agent can be enumerated: 2, two (the trichloromethyl)-6-piperonyls-1 of 4-, 3, the 5-triazine, 2, two (trichloromethyl)-6-[2-(2-furyl) vinyl of 4-]-s-triazine, 2, two (trichloromethyl)-6-[2-(5-methyl-2-furyl) vinyl of 4-]-s-triazine, 2, two (trichloromethyl)-6-[2-(5-ethyl-2-furyl) vinyl of 4-]-s-triazine, 2, two (trichloromethyl)-6-[2-(5-propyl group-2-furyl) vinyl of 4-]-s-triazine, 2, two (the trichloromethyl)-6-[2-(3 of 4-, the 5-Dimethoxyphenyl) vinyl]-s-triazine, 2, two (the trichloromethyl)-6-[2-(3 of 4-, 5-diethoxy phenyl) vinyl]-s-triazine, 2, two (the trichloromethyl)-6-[2-(3 of 4-, 5-dipropoxy phenyl) vinyl]-s-triazine, 2, two (trichloromethyl)-6-[2-(3-methoxyl group-5-ethoxyl phenenyl) vinyl of 4-]-s-triazine, 2, two (trichloromethyl)-6-[2-(3-methoxyl group-5-propoxyl group phenyl) vinyl of 4-]-s-triazine, 2, two (the trichloromethyl)-6-[2-(3 of 4-, the 4-methylenedioxyphenyl) vinyl]-s-triazine, 2, two (the trichloromethyl)-6-(3 of 4-, the 4-methylenedioxyphenyl)-s-triazine, 2,4-pair-trichloromethyl-6-(3-bromo-4-methoxyl group) phenyl-s-triazine, 2,4-pair-trichloromethyl-6-(2-bromo-4-methoxyl group) phenyl-s-triazine, 2,4-pair-trichloromethyl-6-(2-bromo-4-methoxyl group) styryl phenyl-s-triazine, 2,4-pair-trichloromethyl-6-(3-bromo-4-methoxyl group) styryl phenyl-s-triazine, 2-(4-methoxyphenyl)-4, two (trichloromethyl)-1 of 6-, 3, the 5-triazine, 2-(4-methoxyl group naphthyl)-4, two (trichloromethyl)-1 of 6-, 3, the 5-triazine, 2-[2-(2-furyl) vinyl]-4, two (trichloromethyl)-1 of 6-, 3, the 5-triazine, 2-[2-(5-methyl-2-furyl) vinyl]-4, two (trichloromethyl)-1 of 6-, 3, the 5-triazine, 2-[2-(3, the 5-Dimethoxyphenyl) vinyl]-4, two (trichloromethyl)-1 of 6-, 3, the 5-triazine, 2-[2-(3, the 4-Dimethoxyphenyl) vinyl]-4, two (trichloromethyl)-1 of 6-, 3, the 5-triazine, 2-(3, the 4-methylenedioxyphenyl)-4, two (trichloromethyl)-1 of 6-, 3, the 5-triazine, three (1, the 3-dibromopropyl)-1,3, the 5-triazine, three (2, the 3-dibromopropyl)-1,3, halogen-containing triaizine compounds such as 5-triazine, and three (2, the 3-dibromopropyl) isocyanuric acid ester etc. is with the represented halogen-containing triaizine compounds of following general formula (a1).

[changing 1]

In the described general formula (a1), R ^1a, R ^2a, and R ^3aFor distinguishing independently haloalkyl, the carbon number of this alkyl is 1～6.

In addition, second form of acid producing agent can be enumerated: α-(tolysulfonyl oxygen base imino group)-phenylacetonitrile, α-(phenylsulfonyloxy imino group)-2,4-dichlorophenyl acetonitrile, α-(phenylsulfonyloxy imino group)-2,6-dichlorophenyl acetonitrile, α-(2-chlorobenzene sulfonyloxy imino group)-4-methoxyphenyl acetonitrile, α-(ethyl sulfonyloxy imino group)-1-cyclopentenyl acetonitrile, and contain the oxime sulfonates base with the represented compound of following general formula (a2).

[changing 2]

In the described general formula (a2), R ^4aBe monovalence, divalence or trivalent organic group, in addition, R ^5aFor be substituted, unsubstituted saturated hydrocarbyl, unsaturated alkyl or phenolic compound base, n is 1～6 integer.

In the described general formula (a2), R ^4aSpecial preferred fragrance compound-base, this phenolic compound base for example can be enumerated: aromatic hydrocarbyls such as phenyl, naphthyl, or heterocyclic radicals such as furyl, thienyl.Can have substituting group suitable more than 1 on the ring of these groups, for example halogen atom, alkyl, alkoxyl, nitro etc.In addition, R ^5aPreferred especially carbon number is 1～6 low alkyl group, can enumerate: methyl, ethyl, propyl group, butyl etc.

With the represented acid producing agent of described general formula (a2) is when the n=1, R ^4aBe the arbitrary group in phenyl, aminomethyl phenyl, the methoxyphenyl, R ^5aCompound for methyl, particularly can enumerate: α-(sulfonyloxy methyl oxygen base imino group)-1-phenylacetonitrile, α-(sulfonyloxy methyl oxygen base imino group)-1-(p-methylphenyl) acetonitrile, α-(sulfonyloxy methyl oxygen base imino group)-1-(p-methoxyphenyl) acetonitrile, [2-(sulfonyl propyl oxygen base imino group)-2,3-dihydroxy thiophene-3-subunit] (o-tolyl) acetonitrile etc.During n=2, specifically can enumerate the represented acid producing agent of following chemical formula (a2-1)～(a2-8) with the represented acid producing agent of described general formula.

[changing 3]

In addition, the 3rd form of acid producing agent can use cation portion to have the salt of naphthalene nucleus.This what is called " has naphthalene nucleus ", is meant to have the structure that is derived from naphthalene, and expression contains the structure of at least two rings, and these rings are maintained armaticity.It is that 1～6 straight chain shape or alkyl, hydroxyl, the carbon number that props up chain are 1～6 straight chain shape or the substituting groups such as alkoxyl that prop up chain that this naphthalene nucleus can have carbon number.The structure that is derived from naphthalene nucleus can be 1 valency base (1 free valency), also can it is desirable to 1 valency base (being to remove external to the free valency counting with the part of described substituting group bonding at this moment still) for more than the divalent base (2 free valency).Preferred 1～3 of the number of naphthalene nucleus.

This cation portion has the cation quality award from the ministry choosing of salt of naphthalene nucleus with the represented structure of following general formula (a3).

[changing 4]

In the described general formula (a3), R ^6a, R ^7a, R ^8aIn at least one be with the represented group of following general formula (a4), remain for carbon number be a straight chain shape of 1～6 or a chain alkyl, can to have substituent phenyl, hydroxyl or carbon number be 1～6 the straight chain shape or the alkoxyl of a chain.Perhaps, R ^6a, R ^7a, R ^8aIn one be with the represented group of following general formula (a4), remaining two independent of respectively carbon number is 1～6 straight chain shape or the alkylene that props up chain, the end of these groups can bonding and form ring-type.

[changing 5]

In the described general formula (a4), R ^9a, R ^10aIndependent of respectively hydroxyl, carbon number are that the alkoxyl of a straight chain shape of 1～6 or a chain or carbon number are 1～6 the straight chain shape or the alkyl of a chain, R ^11aFor singly-bound or can have the alkylene that substituent carbon number is a straight chain shape of 1～6 or a chain, p and q independently are respectively 0 or 1～2 integer, and p+q is below 3.Wherein, when there being a plurality of R ^10aThe time, these R ^10aCan be mutually the same also can be different.In addition, when there being a plurality of R ^9aThe time, these R ^9aCan be mutually the same also can be different.

Consider described R from the stable aspect of compound ^6a, R ^7a, R ^8aIn, be preferably one with the number of the represented group of described general formula (a4), remain for carbon number be a straight chain shape of 1～6 or a chain alkyl, can have substituent phenyl, the end of these groups can bonding and form ring-type.At this moment, described two alkylenes comprise sulphur atom and constitute 3～9 Yuans rings.The number that constitutes the atom (comprising sulphur atom) of ring is preferably 5～6.

In addition, the described alkylene substituting group that can have can be enumerated: oxygen atom (at this moment, forming carbonyl with the carbon atom that constitutes alkylene), hydroxyl etc.

In addition, the phenyl substituting group that can have can be enumerated: hydroxyl, carbon number are that the alkoxyl of a straight chain shape of 1～6 or a chain or carbon number are 1～6 the straight chain shape or the alkyl of a chain etc.

In these cation portions, preferred cation portion can enumerate with represented structure of following chemical formula (a5), (a6) etc., especially preferably with the represented structure of chemical formula (a6).

[changing 6]

Described cation portion can also can be sulfonium salt for salt compounded of iodine, produces aspect such as efficient from acid and considers, it is desirable to sulfonium salt.

Therefore, for the anion portion of salt that preferred cation portion has naphthalene nucleus, comparatively ideal is the anion that can form sulfonium salt.

Fluoroalkyl azochlorosulfonate acid ion or aryl sulfonic acid ion that the anion quality award from the ministry of this smooth acid producing agent selects part or all hydrogen atom to be fluoridized.

Alkyl in the fluoroalkyl azochlorosulfonate acid ion can be 1～20 straight chain shape, chain or ring-type for carbon number, considers that from the volume of the acid that produces and its diffusion length the preferred carbon number of described alkyl is 1～10.Diffusion length was shorter when particularly described alkyl was a chain or ring-type, thereby preferred the use.Particularly, consider that preferred alkyl can be enumerated: methyl, ethyl, propyl group, butyl, octyl group etc. from the aspect can be synthesized at an easy rate.

Aryl in the aryl sulfonic acid ion is that carbon number is 6～20 aryl, can enumerate and can be considered from synthesizing the aspect at an easy rate that by alkyl, halogen atom replacement or unsubstituted phenyl, naphthyl preferred carbon number is 6～10 aryl.Particularly, preferred aryl groups can be enumerated: phenyl, tosyl, ethylphenyl, naphthyl, methyl naphthyl etc.

For described fluoroalkyl azochlorosulfonate acid ion or aryl sulfonic acid ion, when part or all hydrogen atom is fluoridized, the rate of fluoridizing preferred 10～100%, more preferably 50～100%, special when whole hydrogen atoms are all replaced by fluorine atom, the intensity grow of acid, thereby preferred the use.Particularly, this fluoroalkyl azochlorosulfonate acid ion or aryl sulfonic acid ion can be enumerated: triflate, perfluor fourth sulphonic acid ester, perfluorooctane sulfonate ester, perfluor benzene sulfonate etc.

Wherein, preferred anionic surfactants portion can enumerate with the represented structure of following general formula (a7).

[changing 7]

R ^12aSO ₃ ^-(a7)

In the described general formula (a7), R ^12aCan enumerate: with following general formula (a8), (a9) represented structure, or with the represented structure of chemical formula (a10).

[changing 8]

-C ₁F _2l+1

(a8) (a9) (a10)

In the described general formula (a8), 1 is 1～4 integer, in the general formula (a9), and R ^13aExpression hydrogen atom, hydroxyl, carbon number are that the alkyl of a straight chain shape of 1～6 or a chain or carbon number are 1～6 the straight chain shape or the alkoxyl of a chain, and m is 1～3 integer.Wherein, consider preferred triflate, perfluor fourth sulphonic acid ester from the viewpoint of fail safe.

In addition, anion portion also can use with following chemical formula (a11) and reach (a12) the represented structure that contains nitrogen.

[changing 9]

Among described formula (a11), (a12), X ^A1The straight chain shape that is replaced by fluorine atom at least one hydrogen atom or the alkylene of a chain, the carbon number of this alkylene is 2～6, and is preferred 3～5, most preferably carbon number is 3.In addition, X ^A2, X ^A3The independent respectively straight chain shape that is replaced by fluorine atom at least one hydrogen atom or the alkyl of a chain, the carbon number of this alkyl is 1～10, and is preferred 1～7, more preferably 1～3.

X ^A1The carbon number or the X of alkylene ^A2, X ^A3The carbon number of alkyl more little, then the dissolubility in the photoresistance solvent is also good more, therefore preferred the employing.

In addition, X ^A1Alkylene or X ^A2, X ^A3Alkyl in the number of the hydrogen atom that replaced by fluorine atom many more, then Suan intensity is strong more, thereby preferred the employing.The ratio of the fluorine atom in this alkylene or the alkyl, promptly to fluoridize rate preferred 70～100%, and more preferably 90～100%, whole perfluor alkylene or perfluoroalkyls of all being replaced of hydrogen atoms most preferably by fluorine atom.

This cation portion has the preferred following chemical formula of salt (a13) of naphthalene nucleus, the compound of (a14).

[changing 10]

In addition, other forms of acid producing agent can be enumerated: two (p-toluenesulfonyl) diazomethane, two (1,1-dimethyl ethyl sulfonyl) two sulfonyl diazomethane classes such as diazomethane, two (cyclohexyl sulfonyl) diazomethane, two (2,4-3,5-dimethylphenyl sulfonyl) diazomethane; P-methyl benzenesulfonic acid-2-nitrobenzyl ester, p-methyl benzenesulfonic acid-2, nitrobenzyl derivatives such as 6-dinitro benzyl ester, toluenesulfonic acid nitrobenzyl ester, toluenesulfonic acid dinitro benzyl ester, sulfonic acid nitrobenzyl ester, carbonic acid nitrobenzyl ester, carbonic acid dinitro benzyl ester; Sulphonic acid esters such as pyrogallol three methanesulfonates, pyrogallol trimethylbenzene sulphonic acid ester, toluenesulfonic acid benzyl ester, sulphur acid benzyl ester, N-sulfonyloxy methyl oxygen base succimide, N-trichloromethyl sulfonyloxy succimide, N-phenyl sulfonyloxy maleimide, N-sulfonyloxy methyl oxygen base phthalimide; Triflate classes such as N-hydroxyphthalimide, N-hydroxyl naphthalimide; Salt such as diphenyl iodine hexafluorophosphate, (4-methoxyphenyl) phenyl-iodide fluoroform sulphonate, two (to tert-butyl-phenyl) iodine fluoroform sulphonate, triphenylsulfonium hexafluorophosphate, (4-methoxyphenyl) diphenyl sulfonium fluoroform sulphonate, (to tert-butyl-phenyl) diphenyl sulfonium fluoroform sulphonate; Styrax tosylate classes such as styrax tosylate, Alpha-Methyl styrax tosylate; Other diphenyl iodnium, triphenyl sulfonium salt, phenyl diazol, carbon acid benzyl ester etc.

In addition, the 4th form of acid producing agent can be used with the represented compound of following general formula (a15).

[changing 11]

In the described formula (a15), X ^A4The expression valence is sulphur atom or the iodine atom of s, and s is 1 or 2.N represents the repetitive of the structure in the bracket.R ^14aBe and X ^A4The organic group of bonding, expression carbon number are that 6～30 aryl, carbon number are that 4～30 heterocyclic radical, carbon number are that 1～30 alkyl, carbon number are that 2～30 thiazolinyl or carbon number are 2～30 alkynyl, and, R ^14aAt least a replacement in the group that can selected free following radicals forms: each group and the halogen of alkyl, hydroxyl, alkoxyl, alkyl-carbonyl, aryl carbonyl, alkoxy carbonyl, aryloxycarbonyl, arylthio carbonyl, acyloxy, arylthio, alkylthio group, aryl, heterocycle, aryloxy group, alkyl sulphinyl, aryl sulfonyl kia, alkyl sulphonyl, aryl sulfonyl, epoxy alkyl, amino, cyano group, nitro.R ^14aNumber be s+n (s-1)+1, R ^14aCan distinguish mutually the same also can be different.In addition, the R more than 2 ^14aCan be each other directly or via-O-,-S-,-SO-,-SO ₂-,-NH-,-NR ^15a-,-CO-,-COO-,-CONH-, carbon number are 1～3 alkylene or penylene and bonding, form to comprise X ^A4Ring structure.R ^15aBe that carbon number is that 1～5 alkyl or carbon number are 6～10 aryl.

X ^A5For with the represented structure of following general formula (a16).

[changing 12]

In the described formula (a16), X ^A7The expression carbon number is that 1～8 alkylene, carbon number are that 6～20 arlydene or carbon number are the divalent base of 8～20 heterocyclic compound, X ^A7Can be selected from carbon number is that 1～8 alkyl, carbon number are that 1～8 alkoxyl, carbon number are at least a replacement in each group of 6～10 aryl, hydroxyl, cyano group, nitro and the group that halogen is formed.X ^A8Expression-O-,-S-,-SO-,-SO ₂-,-NH-,-NR ^15a-,-CO-,-COO-,-CONH-, carbon number are 1～3 alkylene or penylene.N represents the number of repeat unit of the structure in the bracket.N+1 X ^A7And n X ^A8Can distinguish identical also can be different.R ^15aIdentical with the definition described in the preamble.

X ^A6-The counter ion that is.Its number is that n+1 is arranged in per 1 molecule, and wherein at least 1 is with the represented fluorinated alkyl fluorophosphoric acid anion of following general formula (a17), remainingly can be other anion.

[changing 13]

|(R ^16a) _tPF _6-t| ^- (a17)

In the described formula (a17), R ^16aThe alkyl that the hydrogen atom of expression more than 80% replaced by fluorine atom.T represents R ^16aNumber, be 1～5 integer.T R ^16aCan distinguish identical also can be different.

The preferred concrete example of the ion of described general formula (a15) can be enumerated: triphenylsulfonium; three-p-methylphenyl sulfonium; 4-(thiophenyl) phenyl diphenyl sulfonium; two [4-(diphenyl sulfonium base) phenyl] sulfide; two [two [4-(2-hydroxyl-oxethyl) phenyl] the sulfonium bases of 4-{ } phenyl] sulfide; two two (4-fluorophenyl) the sulfonium bases of 4-[] and phenyl } sulfide; two (4-fluorophenyl) sulfoniums of 4-(4-benzoyl-2-chlorobenzene sulfenyl) phenyl; 4-(4-benzoyl thiophenyl) phenyl diphenyl sulfonium; 7-isopropyl-9-oxo-10-thia-9; 10-dihydroanthracene-2-base two-p-methylphenyl sulfonium; 7-isopropyl-9-oxo-10-thia-9,10-dihydroanthracene-2-base diphenyl sulfonium; the 2-[(diphenyl) sulfonium base] thioxanthones; 4-[4-(4-tert-butyl benzene formoxyl) thiophenyl] phenyl two-p-methylphenyl sulfonium; 4-(4-benzoyl thiophenyl) phenyl diphenyl sulfonium; diphenyl phenacyl sulfonium; 4-hydroxy phenyl methyl-benzyl sulfonium; 2-naphthyl methyl (1-ethoxy carbonyl) ethyl sulfonium; 4-hydroxy phenyl toluyl methyl sulfonium; octadecyl methyl phenacyl sulfonium; diphenyl iodine; two (p-methylphenyl) iodine; two (4-dodecylphenyl) iodine; two (4-methoxyphenyl) iodine; (4-octyloxyphenyl) phenyl-iodide; two (4-oxygen in last of the ten Heavenly stems base) phenyl-iodide; 4-(2-hydroxyl tetradecyloxyaniline) phenyl iodine; 4-isopropyl phenyl (p-methylphenyl) iodine; or 4-isobutyl phenenyl (p-methylphenyl) iodine.

The anion component of described general formula (a15) has at least 1 with the represented fluorinated alkyl fluorophosphoric acid anion of described general formula (a17).Remaining anion component can be other anion.Be not particularly limited for other anion, can use well-known in the past anion.For example, can enumerate: F ^-, Cr ^-, Br ^-, I ^-Deng halide ion; OH ^-ClO ₄ ^-FSO ₃ ^-, ClSO ₃ ^-, CH ₃SO ₃ ^-, C ₆H ₅SO ₃ ^-, CF ₃SO ₃ ^-Deng the azochlorosulfonate acid ion class; HSO ₄ ^-, SO ₄ ^2-Deng the sulfate ion class; HCO ₃ ^-, CO ₃ ^2-Deng the carbonic acid ionic species; H ₂PO ₄ ^-, HPO ₄ ^2-, PO ₄ ^3-Deng the phosphate ion class; PF ₆ ^-, PF ₅OH ^-Deng the fluorophosphoric acid ionic species; BF ₄ ^-, B (C ₆F ₅) ₄ ^-, B (C ₆H ₄CF ₃) ₄ ^-Deng the borate ion class; AlCl ₄ ^-And BiF ₆ ^-Deng.In addition, also can enumerate SbF ₆ ^-, SbF ₅OH ^-Deng fluorine metaantimmonic acid ionic species, or A _sF ₆ ^-, A _sF ₅OH ^-Deng fluorine arsenic acid ionic species, but these ionic species contain toxic element, and are therefore not good.

In the represented fluorinated alkyl fluorophosphoric acid anion of described general formula (a17), R ^16aThe alkyl that expression is replaced by fluorine atom, preferred carbon number is 1～8, more preferably carbon number is 1～4.The concrete example of alkyl can be enumerated straight chained alkyls such as methyl, ethyl, propyl group, butyl, amyl group, octyl group; Branched alkyls such as isopropyl, isobutyl group, sec-butyl, the tert-butyl group; Cycloalkyl such as cyclopropyl, cyclobutyl, cyclopenta, cyclohexyl etc. in addition, the ratio of the hydrogen atom that is replaced by fluorine atom in the alkyl is generally more than 80%, and is preferred more than 90%, and more preferably 100%.The replacement rate of fluorine atom was less than 80% o'clock, and the acid strength of the fluorinated alkyl fluorophosphate that described general formula (a15) is represented descends.

R ^16aPreferred especially carbon number be 1～4 and the replacement rate of fluorine atom be 100% the straight chain shape or the perfluoroalkyl of a chain, concrete example can be enumerated: CF ₃, CF ₃CF ₂, (CF ₃) ₂CF, CF ₃CF ₂CF ₂, CF ₃CF ₂CF ₂CF ₂, (CF ₃) ₂CFCF ₂, CF ₃CF ₂(CF ₃) CF, (CF ₃) ₃C.R ^16aNumber t be 1～5 integer, preferred 2～4, preferred especially 2 or 3.

The preferred anionic concrete example of fluorinated alkyl fluorophosphoric acid can be enumerated [(CF ₃CF ₂) ₂PF ₄] ^-, [(CF ₃CF ₂) ₃PF ₃] ^-, [((CF ₃) ₂CF) ₂PF ₄] ^-, [((CF ₃) ₂CF) ₃PF ₃] ^-, [(CF ₃CF ₂CF ₂) ₂PF ₄] ^-, [(CF ₃CF ₂CF ₂) ₃PF ₃] ^-, [((CF ₃) ₂CFCF ₂) ₂PF ₄] ^-, [((CF ₃) ₂CFCF ₂) ₃PF ₃] ^-, [(CF ₃CF ₂CF ₂CF ₂) ₂PF ₄] ^-, or [(CF ₃CF ₂CF ₂) ₃PF ₃] ^-, in these, preferred especially [(CF ₃CF ₂) ₃PF ₃] ^-, [(CF ₃CF ₂CF ₂) ₃PF ₃] ^-, [((CF ₃) ₂CF) ₃PF ₃] ^-, [((CF ₃) ₂CF) ₂PF ₄] ^-, [((CF ₃) ₂CFCF ₂) ₃PF ₃] ^-, or [((CF ₃) ₂CFCF ₂) ₂PF ₄] ^-

In the represented fluorinated alkyl fluorophosphate of described general formula (a15), especially preferably use with the represented diphenyl of following general formula (a18) [4-(thiophenyl) phenyl] sulfonium trifluoro trifluoroalkyl phosphate.

[changing 14]

In the described formula (a18), u is 1～8 integer, preferred 1～4 integer.

Described (A) composition acid producing agent preferably use be selected from general formula (a2), and general formula (a18) at least a, in the general formula (a2), the n value is preferred 2, in addition, R ^4aThe carbon number of preferred divalence is 1～8 is substituted or unsubstituted alkylene or be substituted or unsubstituted aromatic group, in addition, and R ^5aPreferred carbon number is 1～8 is substituted or unsubstituted alkyl or replacement or unsubstituted aryl.

Aforesaid (A) composition can use separately, also can be used in combination of two or more.

In addition, in the eurymeric photoresistance composition, (A) preferred 0.05～5 quality % of the allotment amount of composition.By the allotment amount that makes (A) composition is more than the 0.05 quality %, can obtain sufficient sensitivity, in addition, be below the 5 quality % by making the allotment amount, can improve this (A) thus composition obtains uniform solution with respect to the dissolubility of solvent, storage stability is improved.

(resinous principle (B))

Described resinous principle can be comprise phenolic resins (B1), polyhydroxystyrene resin (B2), and acrylic resin (B3) at least a resin, perhaps also can be hybrid resin or copolymer, these resinous principles can increase owing to the effect of acid with respect to the dissolubility of alkali.

[(B1) phenolic resins]

With respect to the dissolubility of alkali owing to the phenolic resins (B1) that the effect of acid increases can use with the represented resin of following general formula (b1).

[changing 15]

In the described general formula (b1), R ^1bFor the dissolving of acid disassociation property suppresses base, R ^2bAnd R ^3bIndependent respectively is that hydrogen atom or carbon number are 1～6 alkyl, and n represents repetitive.

In addition, with described R ^1bThe dissolving of represented acid disassociation property suppress base preferably with following general formula (b2) or (b3) represented carbon number be the alkyl of 1～6 straight chain shape, a chain or ring-type, THP trtrahydropyranyl, four furyls or trialkylsilkl.

[changing 16]

In described general formula (b2) and the general formula (b3), R ^4bAnd R ^5bIndependent respectively is that hydrogen atom or carbon number are 1～6 straight chain shape or the alkyl that props up chain, R ^6bBe that carbon number is the alkyl of 1～10 straight chain shape, a chain or ring-type, R ^7bBe that carbon number is the alkyl of 1～6 straight chain shape, a chain or ring-type, o is 0 or 1.

In addition, carbon number is that 1～6 straight chain shape or the alkyl that props up chain can be enumerated methyl, ethyl, propyl group, isopropyl, normal-butyl, isobutyl group, the tert-butyl group, amyl group, isopentyl, neopentyl etc., and the alkyl of ring-type can be enumerated cyclopenta, cyclohexyl etc.

Wherein, particularly, suppress base with the represented acid disassociation property dissolving of described general formula (b2) and can enumerate methoxy ethyl, ethoxyethyl group, positive propoxy ethyl, isopropoxy ethyl, n-butoxy ethyl, isobutoxy ethyl, tert-butoxy ethyl, cyclohexyloxy ethyl, methoxy-propyl, ethoxycarbonyl propyl, 1-methoxyl group-1-methyl-ethyl, 1-ethyoxyl-1-Methylethyl etc., the acid disassociation property dissolving of described formula (b3) suppresses base and for example can enumerate tert-butoxycarbonyl, tert-butoxycarbonyl methyl etc.In addition, described trialkylsilkl can be enumerated: the carbon number of each alkyl such as trimethyl silyl, three-t-butyldimethylsilyl is 1～6 trialkylsilkl.

[(B2) polyhydroxystyrene resin]

With respect to the dissolubility of alkali owing to the polyhydroxystyrene resin (B2) that the effect of acid increases can use with the represented resin of following general formula (b4).

[changing 17]

In the described general formula (b4), R ^8bFor hydrogen atom or carbon number are 1～6 alkyl, R ^9bFor the dissolving of acid disassociation property suppresses base, n represents repetitive.

With described R ^9bRepresented acid disassociation property dissolving suppresses base and can use with described general formula (b2) and illustrative identical acid disassociation property dissolving inhibition base (b3).

In addition, in the polyhydroxystyrene resin (B2) that described dissolubility with respect to alkali increases owing to the effect of acid, can contain other polymerizable compounds and be used as construction unit, so that physics, chemical characteristic are controlled to be appropriateness.This polymerizable compound can be enumerated well-known free-radical polymerised compound or anionic polymerization compound.For example, can enumerate: monocarboxylic acid classes such as acrylic acid, methacrylic acid, butenoic acid; Omega-dicarboxylic acids such as maleic acid, fumaric acid, methylene-succinic acid; 2-methacryloxyethyl butanedioic acid, 2-methacryloxyethyl maleic acid, 2-methacryloxyethyl phthalic acid, 2-methacryloxyethyl hexahydrophthalic acid etc. have the methacrylic acid derivative class of carboxyl and ester bond; (methyl) alkyl-acrylates such as (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) butyl acrylate; (methyl) 2-Hydroxy ethyl acrylate, (methyl) acrylic acid-(methyl) acrylic acid hydroxyalkyl acrylate classes such as 2-hydroxy propyl ester; (methyl) acrylic acid aryl ester classes such as (methyl) phenyl acrylate, (methyl) benzyl acrylate; Dicarboxylic diester such as diethyl maleate, dibutyl fumarate class; Styrene, AMS, chlorostyrene, 1-chloro-4-methyl-benzene, vinyltoluene, hydroxy styrenes, Alpha-Methyl hydroxy styrenes, α-ethyl hydroxy styrenes etc. contain the aromatic compound class of vinyl; Vinyl acetates etc. contain the aliphatic compound class of vinyl; Butadiene, isoprene equiconjugate alkadiene; The polymerizable compound class of nitrile group-containing such as acrylonitrile, methacrylonitrile; The polymerizable compound that vinyl chloride, vinylidene chloride etc. are chloride; And the polymerizable compound class of amide containing key such as acrylamide, Methacrylamide etc.

[(B3) acrylic resin]

With respect to the dissolubility of alkali owing to the acrylic resin (B3) that the effect of acid increases can use with the represented resin of following general formula (b5)～(b7).

[changing 18]

In the described general formula (b5)～(b7), R ^10b～R ^17bIndependent respectively is that hydrogen atom or carbon number are that 1～6 straight chain shape or alkyl, fluorine atom or the carbon number that props up chain are 1～6 straight chain shape or fluorinated alkyl (wherein, the R that props up chain ^11bBe not hydrogen atom), X ^B1Forming carbon number with bonding carbon atom thereon is 5～20 hydrocarbon ring, X ^B2For having substituent aliphat cyclic group or alkyl, n represents repetitive, and c is 0～4, and d is 0 or 1.

In addition, carbon number is that 1～6 straight chain shape or the alkyl that props up chain can be enumerated methyl, ethyl, propyl group, isopropyl, normal-butyl, isobutyl group, the tert-butyl group, amyl group, isopentyl, neopentyl etc., and the alkyl of ring-type can be enumerated cyclopenta, cyclohexyl etc.In addition, so-called fluorinated alkyl is meant that part or all hydrogen atom of described alkyl is replaced by fluorine atom.

For described R ^11b, higher from contrast, and described R is considered in good aspect such as resolution, the depth of focus and width ^11bPreferred carbon number is 2～4 straight chain shape or branched-chain alkyl, described R ^13b, R ^14b, R ^16bAnd R ^17bPreferred hydrogen atom or methyl.

Described X ^B1With bonding carbon atom thereon, the formation carbon number is 5～20 aliphat cyclic group.The concrete example of this aliphat cyclic group can be enumerated: from monocycle alkane, remove the group of gained behind 1 above hydrogen atom on the polycyoalkanes such as dicyclo alkane, three cycloalkane, Fourth Ring alkane.Particularly, can enumerate:, or remove the group of gained behind 1 above hydrogen atom on the polycyoalkane such as adamantane, norcamphane, isocamphane, tristane, Fourth Ring dodecane from monocycle alkane such as pentamethylene, cyclohexane, cycloheptane, cyclooctane.Especially preferably remove the group (can further have substituting group) of gained behind 1 above hydrogen atom from cyclohexane, adamantane.

In addition, described X ^B1The aliphat cyclic group when its ring has substituting group on skeleton, as this substituent example, can enumerate: (=O) isopolarity base, or carbon number is 1～4 the straight chain shape or the low alkyl group of a chain for hydroxyl, carboxyl, cyano group, oxygen atom.As polar group, special preferred oxygen atom (=O).

Described X ^B2Be aliphat cyclic group or alkyl, can illustration: remove the group of 1 above hydrogen atom etc. from polycyoalkanes such as monocycle alkane, dicyclo alkane, three cycloalkane, Fourth Ring alkane.Particularly, can enumerate:, or remove group of 1 above hydrogen atom etc. on the polycyoalkane such as adamantane, norcamphane, isocamphane, tristane, Fourth Ring dodecane from monocycle alkane such as pentamethylene, cyclohexane, cycloheptane, cyclooctane.Especially preferably remove the group (further can have substituting group) of 1 above hydrogen atom from adamantane.

In addition, as described X ^B2The ring skeleton of aliphat cyclic group on when having substituting group, this substituent example can be enumerated: (=O) isopolarity base, perhaps carbon number is 1～4 the straight chain shape or the low alkyl group of a chain for hydroxyl, carboxyl, cyano group, oxygen atom.The special preferred oxygen atom of polar group (=O).

In addition, work as X ^B2During for alkyl, preferred carbon number is 1～20, preferred 6～15 straight chain shape or the alkyl that props up chain.The preferred especially alkoxyalkyl of this alkyl, this alkoxyalkyl can be enumerated: 1-methoxy ethyl, 1-ethoxyethyl group, 1-positive propoxy ethyl, 1-isopropoxy ethyl, 1-n-butoxy ethyl, 1-isobutoxy ethyl, 1-tert-butoxy ethyl, 1-methoxy-propyl, 1-ethoxycarbonyl propyl, 1-methoxyl group-1-methyl-ethyl, 1-ethyoxyl-1-Methylethyl etc.

As preferred concrete example, can enumerate with the represented acrylic resin of following general formula (b5-1)～(b5-3) with the represented acrylic resin of described general formula (b5).

[changing 19]

R in the described general formula (b5-1)～(b5-3) ^18bBe hydrogen atom or methyl, n is a repetitive.

As preferred concrete example, can enumerate with the represented acrylic resin of following general formula (b6-1)～(b6-28) with the represented acrylic resin of described general formula (b6).

[changing 20]

[changing 21]

As preferred concrete example, can enumerate with the represented acrylic resin of following general formula (b7-1)～(b7-22) with the represented acrylic resin of described general formula (b7).

[changing 22]

[changing 23]

[changing 24]

In addition, described acrylic resin (B3) preferably comprises the resin of following copolymer, that is, this copolymer comprises by the construction unit with respect to described general formula (b5)～(b7), further has the construction unit that the polymerizable compound of ehter bond is derived.

Described construction unit is the construction unit of being derived by the polymerizable compound with ehter bond.Polymerizable compound with ehter bond can illustration (methyl) acrylic acid-2-methoxyl group ethyl ester, (methyl) acrylic acid-2-ethoxy ethyl ester, methoxyl group triethylene glycol (methyl) acrylate, (methyl) acrylic acid-3-methoxyl group butyl ester, ethyl carbitol (methyl) acrylate, phenoxy group polyethylene glycol (methyl) acrylate, methoxyl group polypropylene glycol (methyl) acrylate, (methyl) tetrahydrofurfuryl acrylate etc. has the free-radical polymerised compounds such as (methyl) acrylic acid derivative of ehter bond and ester bond, preferred (methyl) acrylic acid-2-methoxyl group ethyl ester, (methyl) acrylic acid-2-ethoxy ethyl ester, methoxyl group triethylene glycol (methyl) acrylate.These compounds can use separately or be used in combination of two or more.

In addition, can comprise other polymerizable compounds in the described acrylic resin (B3) and be used as construction unit, so that physics, chemical characteristic are controlled to be appropriateness.This polymerizable compound can be enumerated: well-known free-radical polymerised compound or anionic polymerization compound.For example, can enumerate: monocarboxylic acid classes such as acrylic acid, methacrylic acid, butenoic acid; Omega-dicarboxylic acids such as maleic acid, fumaric acid, methylene-succinic acid; 2-methacryloxyethyl butanedioic acid, 2-methacryloxyethyl maleic acid, 2-methacryloxyethyl phthalic acid, 2-methacryloxyethyl hexahydrophthalic acid etc. have the methacrylic acid derivative class of carboxyl and ester bond; (methyl) alkyl-acrylates such as (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) butyl acrylate; (methyl) 2-Hydroxy ethyl acrylate, (methyl) acrylic acid-(methyl) acrylic acid hydroxyalkyl acrylate classes such as 2-hydroxy propyl ester; (methyl) acrylic acid aryl ester classes such as (methyl) phenyl acrylate, (methyl) benzyl acrylate; Dicarboxylic diester such as diethyl maleate, dibutyl fumarate class; Styrene, AMS, chlorostyrene, 1-chloro-4-methyl-benzene, vinyltoluene, hydroxy styrenes, Alpha-Methyl hydroxy styrenes, α-ethyl hydroxy styrenes etc. contain the aromatic compound class of vinyl; Vinyl acetates etc. contain the aliphatic compound class of vinyl; Butadiene, isoprene equiconjugate alkadiene; The polymerizable compound class of nitrile group-containing such as acrylonitrile, methacrylonitrile; The polymerizable compound that vinyl chloride, vinylidene chloride etc. are chloride; And the polymerizable compound class of amide containing key such as acrylamide, Methacrylamide etc.

And, among the described acrylic resin (B3), preferably have the construction unit of deriving, (methyl) acrylic acid units with the represented construction unit of described general formula (b7), by polymerizable compound with ehter bond, and by the copolymer of (methyl) construction unit that alkyl-acrylates was constituted.

This copolymer is preferably with the represented copolymer of following general formula (b8).

[changing 25]

In the described general formula (b8), R ^20bBe hydrogen atom or methyl, R ^21bBe that carbon number is 1～6 straight chain shape or alkyl or the alkoxyalkyl that props up chain, R ^22bBe that carbon number is 2～4 straight chain shape or the alkyl that props up chain, X ^B1Identical with the definition described in the preamble.

In addition, in the represented copolymer of described general formula (b8), e, f and g distinguish by quality ratio, and e is 1～30 quality %, and f is 20～70 quality %, and g is 20～70 quality %.

In addition, (B) the polystyrene conversion weight average molecular weight of composition is preferred 10,000～600,000, and more preferably 50,000～600,000, more preferably 230,000～550,000.Polystyrene conversion weight average molecular weight by making (B) composition as mentioned above, under the situation that can not descend at the fissility of photoresistance film and substrate, make the photoresistance film keep full intensity, and carry out can not occurring when plating is handled the problem that profile (profile) expands or produces be full of cracks.

In addition, (B) the preferred decentralization of composition is a resin more than 1.05.Wherein, so-called decentralization is meant with the value of weight average molecular weight divided by the number-average molecular weight gained.By adopting this decentralization, can avoid the photoresistance film that required plating is possessed anti-stress, perhaps handle the easy problem that expands of the metal level that obtains by plating.

In the eurymeric photoresistance composition, preferred 5～60 quality % of the allotment amount of this (B) composition.

(alkali soluble resins (C))

In addition, can allocate alkali soluble resins aptly in the eurymeric photoresistance composition of this example.This (C) composition be preferably selected from alkali-soluble phenolic resins (C1a), polyhydroxystyrene resin (C1b), acrylic resin (C1c), and vinyl (C1d) at least a.

[(C1a) alkali solubility phenolic resins]

The preferred polystyrene conversion weight average molecular weight of described alkali solubility phenolic resins (C1a) is 1,000～50,000.

This phenolic resins (C1a) for example can make the aromatic compound (being designated hereinafter simply as " phenols ") with phenol hydroxyl obtain with the aldehydes addition condensation by under acid catalyst.This moment, employed phenols for example can be enumerated: phenol, orthoresol, metacresol, paracresol, o-ethyl phenol, m-ethylphenol, paraethyl phenol, adjacent butylphenol, between butylphenol, p-butylphenol, 2, the 3-xylenols, 2, the 4-xylenols, 2, the 5-xylenols, 2, the 6-xylenols, 3, the 4-xylenols, 3, the 5-xylenols, 2,3, the 5-pseudocuminol, 3,4, the 5-pseudocuminol, p-phenyl phenol, resorcinol, hydroquinones, the hydroquinone monomethyl ether, pyrogallol, phloroglucin, xenol, bisphenol-A, gallic acid, gallate, alpha-Naphthol, betanaphthol etc.

In addition, aldehydes for example can be enumerated: formaldehyde, furfural, benzaldehyde, nitrobenzaldehyde, acetaldehyde etc.Catalyst during to addition condensation reaction is not particularly limited, if for example acid catalyst then can use hydrochloric acid, nitric acid, sulfuric acid, formic acid, oxalic acid, acetate etc.

In this example, by using orthoresol, the hydrogen atom of the hydroxyl in the resin is replaced to other substituting groups, perhaps uses the bigger aldehydes of volume, can further improve the flexibility of resin.

[(C1b) alkali solubility polyhydroxystyrene resin]

Described alkali solubility polyhydroxystyrene resin (C1b) preferable weight-average molecular weight is 1,000～50,000.

The hydroxy styrenes based compound that constitutes this polyhydroxystyrene resin (C1b) can be enumerated: para hydroxybenzene ethene, Alpha-Methyl hydroxy styrenes, α-ethyl hydroxy styrenes etc.And, the copolymer of preferred hydroxy styrenes based compound of described polyhydroxystyrene resin and styrene resin, the polystyrene compound that constitutes this styrene resin can be enumerated: styrene, chlorostyrene, 1-chloro-4-methyl-benzene, vinyltoluene, AMS etc.

[(C1c) alkali solubility acrylic resin]

Described alkali solubility acrylic resin (C1c) preferable weight-average molecular weight is 50,000～800,000.

Described acrylic resin (C1c) preferably contains following monomer: monomer of being derived by the polymerizable compound with ehter bond and the monomer of being derived by the polymerizable compound with carboxyl.

(methyl) acrylic acid derivative that described polymerizable compound with ehter bond can illustration (methyl) acrylic acid-2-methoxyl group ethyl ester, methoxyl group triethylene glycol (methyl) acrylate, (methyl) acrylic acid-3-methoxyl group butyl ester, ethyl carbitol (methyl) acrylate, phenoxy group polyethylene glycol (methyl) acrylate, methoxyl group polypropylene glycol (methyl) acrylate, (methyl) tetrahydrofurfuryl acrylate etc. have ehter bond and ester bond etc., preferred acrylic acid-2-methoxyl group ethyl ester, methoxyl group triethylene glycol acrylate.These compounds can use separately, also can be used in combination of two or more.

Described polymerizable compound with carboxyl can illustration: monocarboxylic acids such as acrylic acid, methacrylic acid, butenoic acid, dicarboxylic acids such as maleic acid, fumaric acid, methylene-succinic acid, 2-methacryloxyethyl butanedioic acid, 2-methacryloxyethyl maleic acid, 2-methacryloxyethyl phthalic acid, 2-methacryloxyethyl hexahydrophthalic acid etc. have the compound of carboxyl and ester bond etc., preferred acrylic acid, methacrylic acid.These compounds can use separately, also can be used in combination of two or more.

[(C1d) alkali solubility polyvinyl resin]

Described alkali solubility polyvinyl resin (C1d) preferable weight-average molecular weight is 10,000～200,000, more preferably 50,000～100,000.

Described polyvinyl resin (C1d) is poly-(ethene lower alkyl ether), comprise make the represented ethene lower alkyl ether of following general formula (c1) separately or two or more polymerization of mixtures obtain (being total to) polymer.

[changing 26]

In the described general formula (c1), R ^1cBe that carbon number is 1～6 straight chain shape or the alkyl that props up chain.

Described polyvinyl resin (C1d) is the polymer that is obtained by vinyl compound, particularly, this polyvinyl resin can be enumerated: polyvinyl chloride, polystyrene, polycarboxylated styrene, polyvinyl acetate, polyethylene benzoic acid, polyvinyl methyl ether, polyvinyl ethyl ether, polyvinyl alcohol, polyvinylpyrrolidone, polyethylene phenol and these copolymer etc.Wherein, lower in view of making glass transition point, the preferably polyethylene methyl ether.

With respect to described (B) composition 100 mass parts, preferred 5～95 mass parts of allotment amount of this (C) alkali soluble resins, more preferably 10～90 mass parts.By the allotment amount that makes (C) alkali soluble resins is more than 5 mass parts, can improve crack resistance, is below 95 mass parts by making the allotment amount, and the film in the time of can preventing to develop reduces.

(other compositions)

During use, described eurymeric photoresistance composition is preferably to be dissolved in the form of the solution in the solvent with described each composition and to use.The example of this solvent can be enumerated: ketones such as acetone, methyl ethyl ketone, cyclohexanone, methyl isoamyl ketone, 2-heptanone; Polyalcohols and derivatives thereof such as the monomethyl ether of ethylene glycol, ethylene glycol acetate, diethylene glycol, diethylene glycol monoacetate, propylene glycol, propylene glycol monoacetate, DPG and DPG monoacetate, single ether, single propyl ether, monobutyl ether or monophenyl ether; Ring-type ethers such as dioxanes; Ethyl formate, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, methyl acetoacetate, ethyl acetoacetate, ethyl pyruvate, ethoxy ethyl acetate, methoxypropionic acid methyl esters, ethoxyl ethyl propionate, 2 hydroxy propanoic acid methyl esters, 2 hydroxy propanoic acid ethyl ester, 2-hydroxy-2-methyl ethyl propionate, 2-hydroxy-3-methyl methyl butyrate, acetic acid 3-methoxyl group butyl ester, acetic acid 3-methyl-ester classes such as 3-methoxyl group butyl ester; And toluene, dimethylbenzene etc. are aromatic hydrocarbon based.These solvents can use separately, also can be use mixing two or more in addition.

It is the above scopes of 30 quality % that the use amount of these organic solvents preferably makes solid component concentration, and the thickness of the photoresist layer that obtains is more than the 1 μ m so that make the chemical amplification positive photoresistance composition (for example, spin-coating method) that utilizes this example.The thickness of the photoresist layer that utilizes the composition of this example and obtain is the scope of 1 μ m～200 μ m more preferably.

In the described eurymeric chemical amplification type photoresistance composition, can be further add as required and contain additive, for example: the habitual additives such as addition resin, sensitizer, acid diffusion inhibitor, bonding auxiliary agent, stabilizer, colouring agent, surfactant that are used for improving the performance of photoresistance film with miscibility.

Organic membrane 12 in the base material of cathode 10 of this example preferably by following containing (A2) alkali soluble resins, and (B2) contain the formed organic membrane of eurymeric photoresistance composition of the compound of quinone diazido, more preferably by pattern exposure, and make the formed organic membrane of eurymeric photoresistance composition thus be patterned to the patterning organic membrane of regulation shape.

Described (A2) composition for example can be enumerated: have down the phenolic resins that make phenols (phenol, metacresol, paracresol, xylenols, pseudocuminol etc.), obtains with aldehydes (formaldehyde, formaldehyde presoma, propionic aldehyde, 2-hydroxy benzaldehyde, 3-hydroxy benzaldehyde, 4-hydroxy benzaldehyde etc.) and/or ketone (methyl ethyl ketone, acetone etc.) condensation in acidic catalyst; The hydroxy styrenes such as copolymer of the copolymer of the homopolymers of hydroxy styrenes, hydroxy styrenes and other styrenic monomers, hydroxy styrenes and acrylic or methacrylic acid or its derivative are resin; Acrylic resins such as the derivative of acrylic acid, methacrylic acid or acrylic acid and methacrylic acid or these copolymer etc.

Particularly contain and be selected from metacresol, paracresol, 3,4-xylenols and 2,3, at least two kinds phenols in the 5-pseudocuminol, with contain that at least a aldehydes that is selected from formaldehyde, 2-hydroxy benzaldehyde (salicylide) and the propionic aldehyde carries out condensation reaction and the phenolic resins that obtains is suitable for preparing the eurymeric photoresistance composition that sensitivity is higher and analyticity is excellent.(A2) composition can be made according to well-established law.

(A2) the polystyrene conversion weight average molecular weight (Mw) of utilizing gel permeation chromatography to measure of composition also depends on the kind of (A2) composition, but considers preferred 2 from sensitivity or pattern formation aspect, 000～100,000, more preferably 3,000～30,000.

In addition, (A2) composition preferably carries out the classification processing so that Mw is 3,000～30,000, more preferably 5,000～20, the phenolic resins in 000 scope (below, be called the classification resin).Use this classification resin to be used as (A2) composition, can obtain the eurymeric photoresistance composition of excellent heat resistance.The fractional precipitation that molecular weight dependence that can be by utilizing the polymer dissolution degree is for example handled in classification is handled and is carried out.It for example is at first will be in this way and the condensation product that obtains is that phenolic resins is dissolved in the polar solvent that fractional precipitation is handled, and adds poor solvents such as water, heptane, hexane, pentane, cyclohexane then in this solution.At this moment, low-molecular-weight polymer is dissolved in the poor solvent always, therefore takes out precipitate by filtering, and can obtain the classification resin of the content reduction of low-molecular weight polymer.Polar solvent for example can be enumerated: alcohol such as methyl alcohol, ethanol, ketone such as acetone, methyl ethyl ketone, glycol ether-ethers such as ethylene glycol monoethylether acetate, cyclic ethers such as oxolane etc.

Described (B2) composition is the compound that contains the quinone diazido, even particularly from sensitivity higher under low sodium (NA) condition analyticity also very excellent, and mask linearity or DOF (depth of focus, depth of focus) aspect consider, preferably with following general formula (b2a)

[changing 27]

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

[changing 28]

[in the described general formula (b2b), R ^B12And R ^B13Independent respectively expression hydrogen atom, halogen atom, carbon number are that 1～6 alkyl, carbon number are that 1～6 alkoxyl or carbon number are 3～6 cycloalkyl, and c represents 1～3 integer] represented residue, work as Q ¹With R ^B9Terminal bonding the time, Q ¹With R ^B9, and Q ¹With R ^B9Between carbon atom to constitute carbon atom chain together be 3～6 ring alkylene chain; a and b represent 1～3 integer; d represents 0～3 integer, and n represents 0～3 integer] represented compound and 1, the esterification reaction product of 2-naphthoquinones diazido sulfonyl compound (non-benzophenone series PAC).

The phenolic compounds that meets described general formula (b2a), for example preferred:

[1] Q ¹With R ^B9End bonding not, R ^B9Expression hydrogen atom or carbon number are 1～6 alkyl, Q ¹Expression is with the represented residue of described chemical formula (b2), and n is 0 triphenol type compound; And

[2] Q ¹With R ^B9End bonding not, R ^B9Expression hydrogen atom or carbon number are 1～6 alkyl, Q ¹Expression hydrogen atom or carbon number are 1～6 alkyl, and n is the line style polyphenolic substance of 1～3 integer.

Triphenol type compound more specifically can be enumerated: three (4-hydroxy phenyl) methane, two (4-hydroxy-3-methyl phenyl)-2-hydroxy phenyl methane, two (4-hydroxyls-2,3, the 5-trimethylphenyl)-2-hydroxy phenyl methane, two (4-hydroxyls-3, the 5-3,5-dimethylphenyl)-4-hydroxy phenyl methane, two (4-hydroxyls-3, the 5-3,5-dimethylphenyl)-3-hydroxy phenyl methane, two (4-hydroxyls-3, the 5-3,5-dimethylphenyl)-2-hydroxy phenyl methane, two (4-hydroxyls-2, the 5-3,5-dimethylphenyl)-4-hydroxy phenyl methane, two (4-hydroxyls-2, the 5-3,5-dimethylphenyl)-3-hydroxy phenyl methane, two (4-hydroxyls-2, the 5-3,5-dimethylphenyl)-2-hydroxy phenyl methane, two (4-hydroxyls-3, the 5-3,5-dimethylphenyl)-3,4-dihydroxy benzenes methylmethane, two (4-hydroxyls-2, the 5-3,5-dimethylphenyl)-3,4-dihydroxy benzenes methylmethane, two (4-hydroxyls-2, the 5-3,5-dimethylphenyl)-2,4-dihydroxy benzenes methylmethane, two (4-hydroxy phenyl)-3-methoxyl groups-4-hydroxy phenyl methane, two (5-cyclohexyl-4-hydroxy-2-methyl phenyl)-4-hydroxy phenyl methane, two (5-cyclohexyl-4-hydroxy-2-methyl phenyl)-3-hydroxy phenyl methane, two (5-cyclohexyl-4-hydroxy-2-methyl phenyl)-2-hydroxy phenyl methane, two (5-cyclohexyl-4-hydroxy-2-methyl phenyl)-3,4-dihydroxy benzenes methylmethane etc.

The line style polyphenolic substance more specifically can be enumerated: 2, and two (3,5-dimethyl-4-the hydroxybenzyl)-5-hydroxyl phenols, 2 of 4-, two (2,5-dimethyl-4-hydroxybenzyl)-line styles such as the 4-methylphenol three nuclear phenolic compounds of 6-; 1, two [3-(2-hydroxy-5-methyl base benzyl)-4-hydroxyl-5-cyclohexyl phenyl] the different propane of 1-, two [2,5-dimethyl-3-(4-hydroxy-5-methyl base benzyl)-4-hydroxy phenyl] methane, two [2,5-dimethyl-3-(4-hydroxybenzyl)-4-hydroxy phenyl] methane, it is two that [3-(3,5-dimethyl-4-hydroxybenzyl)-and 4-hydroxy-5-methyl base phenyl] methane, it is two that [3-(3,5-dimethyl-4-hydroxybenzyl)-and 4-hydroxyl-5-ethylphenyl] methane, it is two that [3-(3,5-diethyl-4-hydroxybenzyl)-and 4-hydroxy-5-methyl base phenyl] methane, it is two that [3-(3,5-diethyl-4-hydroxybenzyl)-and 4-hydroxyl-5-ethylphenyl] methane, two [2-hydroxyl-3-(3,5-dimethyl-4-hydroxybenzyl)-and the 5-aminomethyl phenyl] methane, two [2-hydroxyl-3-(2-hydroxy-5-methyl base benzyl)-5-aminomethyl phenyl] methane, two [4-hydroxyl-3-(2-hydroxy-5-methyl base benzyl)-5-aminomethyl phenyl] methane, line styles such as two [2,5-dimethyl-3-(2-hydroxy-5-methyl base benzyl)-4-hydroxy phenyl] methane four nuclear phenolic compounds; And 2, two [2-hydroxyl-3-(4-hydroxybenzyl)-5-the methyl-benzyl]-6-cyclohexylphenol, 2 of 4-, two [4-hydroxyl-3-(4-hydroxybenzyl)-5-the methyl-benzyl]-6-cyclohexylphenol, 2 of 4-, two [2,5-dimethyl-3-(2-hydroxy-5-methyl base benzyl)-4-hydroxybenzyl]-line styles such as the 4-methylphenol five nuclear phenolic compounds of 6-etc.

In addition, except triphenol type compound and line style polyphenolic substance, the phenolic compounds of general molecular formula (b2a) can also be enumerated: two (2,3,4-trihydroxy phenyl) methane, two (2, the 4-dihydroxy phenyl) methane, 2,3,4-trihydroxy phenyl-4 '-hydroxy phenyl methane, 2-(2,3,4-trihydroxy phenyl)-2-(2 ', 3 ', 4 '-the trihydroxy phenyl) propane, 2-(2, the 4-dihydroxy phenyl)-2-(2 ', 4 '-dihydroxy phenyl) propane, 2-(4-hydroxy phenyl)-2-(4 '-hydroxy phenyl) propane, 2-(3-fluoro-4-hydroxy phenyl)-2-(3 '-fluoro-4 '-hydroxy phenyl) propane, 2-(2, the 4-dihydroxy phenyl)-2-(4 '-hydroxy phenyl) propane, 2-(2,3,4-trihydroxy phenyl)-2-(4 '-hydroxy phenyl) propane, 2-(2,3,4-trihydroxy phenyl)-2-(4 '-hydroxyl-3 ', 5 '-3,5-dimethylphenyl) bisphenol type compound such as propane; 1-[1-(4-hydroxy phenyl) isopropyl]-4-[1, two (4-hydroxy phenyl) ethyls of 1-] benzene, 1-[1-(3-methyl-4-hydroxy phenyl) isopropyl]-4-[1, two (3-methyl-4-hydroxy phenyl) ethyls of 1-] multinuclear ramiform compound such as benzene; 1, condensed type phenolic compounds such as 1-bis(4-hydroxyphenyl)cyclohexane etc.These phenolic compounds can use a kind of or be used in combination of two or more.

Among described (B2) composition, preferred especially described triphenol type compound, wherein, contain two (5-cyclohexyl-4-hydroxy-2-methyl phenyl)-3,4-dihydroxy benzenes methylmethane [being designated hereinafter simply as (B2a)], two (4-hydroxyl-2,3,5-trimethylphenyl)-the photoresistance composition of the naphthoquinones two nitrine carboxylates of these triphenol type compounds of 2-hydroxy phenyl methane [being designated hereinafter simply as (B2c)] is also very excellent aspect sensitivity, analyticity, thereby preferred the use.In addition, if in the naphthoquinones two nitrine carboxylates that use this triphenol type compound, use the naphthoquinones two nitrine carboxylates of other phenolic compounds, that is to say described bisphenol type compound, multinuclear ramiform compound with and the naphthoquinones two nitrine carboxylates of phenolic compounds such as condensed type phenolic compounds, just can prepare the photoresistance composition of the population equilibrium excellence of photoresistance characteristics such as analyticity, sensitivity, thermal endurance, DOF characteristic, mask linearity, thus preferred.Preferred especially bisphenol type compound, wherein preferred again two (2, the 4-dihydroxy phenyl) methane [being designated hereinafter simply as (B2b)].In addition, consider, preferably contain described (B2a), (B2c) and (B2b) the eurymeric photoresistance composition of the naphthoquinones two nitrine carboxylates of these three kinds of phenolic compounds from forming the photoresistance pattern aspect that sensitivity is higher, analyticity is higher and shape is good.

When using (B2a), (B2c), (B2) (B2a) in the composition and allotment amount (B2c) preferably account for more than the 10 quality % in total (B2) composition respectively, more preferably more than the 15 quality %.In addition, consider from the effect aspect, with (B2a), (B2b), (B2c) when all using, allotment amount separately is preferably as follows in total (B2) composition: allotment amount (B2a) is 50～90 quality %, preferred 60～80 quality %, allotment amount (B2b) is 5～20 quality %, preferred 10～15 quality %, (B2c) allotment amount is 5～20 quality %, preferred 10～15 quality %.

Can use well-established law, make with all or part of phenol hydroxyl of the represented compound of described general formula (b2a) and realize the naphthalene quinone di-azide sulfonic acid esterization.For example, can be by making naphthoquinones two nitrine sulfonic acid chlorides and obtaining described (B2) composition with the represented compound condensation of described general formula (b2a).Particularly, described (B2) composition for example can prepare by following manner: will with the represented compound of described general formula (b2a), with naphthoquinones-1,2-diazido-4 (or 5)-sulfonic acid chloride is dissolved in ormal weight in the organic solvents such as dioxanes, N-methyl pyrrolidone, dimethylacetylamide, oxolane, and in wherein adding base catalysts such as triethylamine, triethanolamine, pyridine, alkali carbonate, alkali metal hydrogencarbonate more than one react, to the product that is obtained wash, drying.

As mentioned above, (B2) composition is except preferred naphthoquinones two nitrine carboxylates illustrated above, also can use other naphthoquinones two nitrine carboxylates, for example also can use phenolic compounds such as polyhydroxy benzophenone or alkyl gallates, with the esterification reaction product of naphthoquinones two nitrine sulfoacid compounds etc.The use amount of these other naphthoquinones two nitrine carboxylates preferably is below the 80 quality %, below the preferred especially 50 quality % in (B2) composition.

With respect to the total amount of (A2) composition with aftermentioned (C2) composition of allocating arbitrarily, the allotment amount of (B2) composition in the eurymeric photoresistance composition is 20～70 quality %, preferred 25～60 quality %.By the allotment amount that makes (B2) composition is more than the described lower limit, can obtain the image of faithful to pattern, improves transfer printing.By the allotment amount that makes (B2) composition is below the described higher limit, can obtain following effect: can prevent the sensitivity variation, improve the homogenieity of formed photoresistance film, improve analyticity.

In the described eurymeric photoresistance composition,, can further allocate molecular weight as sensitizer and be the compound that contains the phenol hydroxyl below 1,000, be used as (C2) composition except described (A2) composition and (B2) the composition.This (C2) composition is the effect excellence aspect raising sensitivity, by using (C2) composition, even can obtain under low NA condition, also to possess high sensitivity, high image resolution, and the also very excellent material of mask linearity.(C2) molecular weight of composition is below 1,000, and is preferred below 700, is essentially more than 200, preferred more than 300.

Described (C2) composition is the compound that contains the phenol hydroxyl that is generally used for as sensitivity improving agent or sensitizer in the photoresistance composition, just is not particularly limited as long as preferably satisfy described molecular weight condition, can select one or more to use arbitrarily.And, wherein preferably with following general formula (c2a)

[changing 29]

[in the formula, R ^C1～R ^C8Independent respectively expression hydrogen atom, halogen atom, carbon number are that 1～6 alkyl, carbon number are that 1～6 alkoxyl or carbon number are 3～6 cycloalkyl, R ^C10And R ^C11Independent respectively expression hydrogen atom or carbon number are 1～6 alkyl, work as R ^C9When being 1～6 alkyl for hydrogen atom or carbon number, Q ²For hydrogen atom, carbon number are 1～6 alkyl or with the represented residue of following chemical formula (c2b)

[changing 30]

[in the formula, R ^C12And R ^C13Independent respectively expression hydrogen atom, halogen atom, carbon number are that 1～6 alkyl, carbon number are that 1～6 alkoxyl or carbon number are 3～6 cycloalkyl, and g represents 0～3 integer], work as Q ²With R ^C9Terminal bonding the time, Q ²With R ^C9, and Q ²With R ^C9Between carbon atom represent that together carbon atom chain is 3～6 ring alkylene chain, e and f represent 1～3 integer; H represents 0～3 integer; M represents 0～3 integer] represented phenolic compounds.

Particularly, the employed phenolic compounds of naphthoquinones two nitrine carboxylates of described (C2) composition illustrated phenolic compounds in can using for example described (B2) composition, can also use two (3-methyl-4-hydroxy phenyl)-4-cumene methylmethanes aptly, two (3-methyl-4-hydroxy phenyl)-phenylmethanes, two (2-methyl-4-hydroxy phenyl)-phenylmethanes, two (3-methyl-2-hydroxy phenyl)-phenylmethanes, two (3,5-dimethyl-4-hydroxy phenyl)-phenylmethane, two (3-ethyl-4-hydroxy phenyl)-phenylmethanes, two (2-methyl-4-hydroxy phenyl)-phenylmethanes, two (the 2-tert-butyl group-4,5-dihydroxy phenyl)-triphen fundamental mode compounds such as phenylmethane.Wherein, preferred two (2-methyl-4-hydroxy phenyl)-phenylmethanes, 1-[1-(4-hydroxy phenyl) isopropyl]-4-[1, two (4-hydroxy phenyl) ethyls of 1-] benzene.

With respect to described (A2) composition, the allotment amount of described (C2) composition is the scope of 10～70 quality %, the scope of preferred 20～60 quality %.

And, preferably comprise organic solvent in the eurymeric photoresistance composition.Organic solvent can select one or more to use so long as the common employed solvent of photoresistance composition does not then have special restriction.Particularly, this organic solvent can be enumerated: ketones such as acetone, methyl ethyl ketone, cyclohexanone, methyl isoamyl ketone, 2-heptanone; Ethylene glycol, propylene glycol, diethylene glycol, ethylene glycol acetate, propylene glycol monoacetate, diethylene glycol monoacetate, perhaps polyalcohols and derivatives thereof such as these monomethyl ether, single ether, single propyl ether, monobutyl ether or monophenyl ether; Ring-type ethers such as dioxanes; And ester class such as methyl acetate, ethyl acetate, butyl acetate, ethyl lactate, methyl pyruvate, ethyl pyruvate, methoxypropionic acid methyl esters, ethoxyl ethyl propionate; Gamma-butyrolacton etc.

Among the described organic solvent, the preferred at least a organic solvent that is selected from propylene glycol monomethyl ether, propylene glycol monobutyl ether, propylene glycol methyl ether acetate, 2-heptanone, methyl lactate, ethyl lactate and the gamma-butyrolacton that uses.When using these solvents, comparatively ideal is that these solvents are below the 50 quality % in total organic solvent.

In addition, eurymeric photoresistance composition can be in the scope of not damaging purpose of the present invention, contain additive as required with compatibility, for example: be used for improving the performance etc. of photoresistance film addition resin, plasticizer, preserving stabilizer, surfactant, be used for making the development gained the more obvious visible colouring matter of image, be used for making sensitizer that the sensitization effect further improves or antihalation with habitual additives such as dyestuff, adhesiveness improver.

Described antihalation can use ultra-violet absorber (for example 2 with dyestuff, 2 ', 4,4 '-tetrahydroxybenzophenone, 4-dimethylamino-2 ', 4 '-dihydroxy benaophenonel, 5-amino-3-methyl isophthalic acid-phenyl-4-(4-hydroxy phenyl azo) pyrazoles, 4-dimethylamino-4 '-hydroxyazobenzene, 4-diethylamino-4 '-ethyoxyl azobenzene, 4-DEAB, curcumin etc.) etc.

Described surfactant for example can be in order preventing to produce striped etc. and to be added, for example can use: FluoradFC-430, Fluorad FC-431 (trade name, Sumitomo 3M limited company makes) and F-Top EF122A, F-Top EF122B, F-Top EF122C, F-Top EF126 (trade name, Tohkem Products limited company makes) etc. fluorine be surfactant, XR-104, Megafac R-08 (trade name, big Japanese ink chemical industry limited company makes) etc.

[patterning organic membrane]

Organic membrane 12 is to use circulator, described eurymeric photoresistance composition is coated on the supporter 11 and forms.In addition, described organic membrane 12 can form the patterning organic membrane by following manner: after being coated on described eurymeric photoresistance composition on the supporter 11, carry out image exposure via mask irradiation ultraviolet radiation, excimer laser (excimer laser), X ray, electron beam (electron beam) isoreactivity light or radioactive ray, then carry out heat treated as required, use alkaline-based developer to implement development treatment then, the dissolving of irradiation portion is not removed, and carries out heat treated as required.

In addition, the aspect ratio of the patterning organic membrane that obtains in this way is preferred more than 0.1.By the aspect ratio that makes the patterning organic membrane is more than 0.1, and the surface area of base material of cathode 10 is increased, and can make aftermentioned handle the metal film amount increase that forms by plating, can realize higher output and higher energy density thus.

[minus photoresistance composition]

On the other hand, minus photoresistance composition preferably uses to pass through irradiation active ray or radioactive ray acidic acid producing agent composition (identical with described (A) composition), reaches the composition of polyfunctional epoxy resin (hereinafter referred to as (D) composition) as basis.If (D) composition and acid producing agent are used in combination, then the exposed portion utilization is carried out cationic polymerization and to be alkali insoluble in the acid that this part produced, during development only unexposed portion optionally removed, thereby obtain the photoresistance pattern of regulation shape.

(polyfunctional epoxy resin (D))

(D) is not particularly limited for polyfunctional epoxy resin, in order to form thicker pattern, the epoxy resin that has enough epoxy radicals in preferred 1 molecule.This polyfunctional epoxy resin can be enumerated: multifunctional phenol-phenol aldehyde type epoxy resin, multifunctional orthoresol phenolic aldehyde type epoxy resin, multifunctional triphen fundamental mode phenol aldehyde type epoxy resin, multifunctional bisphenol-A phenolic type epoxy resin etc.Among these, preferably use multifunctional bisphenol-A phenolic type epoxy resin.More than the preferred 5 official's energy of the functionality of this multifunctional bisphenol-A phenolic type epoxy resin, for example, " Epiclon N-775 " that " the Epikote 157S70 " that japan epoxy resin (Japan Epoxy Resins) company makes, big Japanese ink chemical industry limited company make can obtain sales item from the market, especially preferably uses.

Described multifunctional bisphenol-A phenolic type epoxy resin is to represent with following general formula (d1).

[changing 31]

The epoxy radicals of the bisphenol-A phenolic type epoxy resin of described formula (d1) can be the polymer with bisphenol A type epoxy resin or bisphenol-A phenolic type polymerization of epoxy resins.In the described formula (d1), R ^1d～r ^6dBe H or CH ₃, v is a repetitive.

In the photoresistance composition, the preferred 80 quality % of the content of described polyfunctional epoxy resin～99.9 quality %, more preferably 92 quality %～99.4 quality %.Thus, when being coated on described photoresistance composition on the described supporter 11, can obtain the photoresistance film that sensitivity is higher and hardness is suitable.

(acid producing agent composition (A))

Acid producing agent composition (A) can use and the same acid producing agent of the described employed acid producing agent of eurymeric photoresistance composition.This acid producing agent composition (A) produces cation constituent by irradiation active ray or radioactive ray, the effect of this cation constituent performance polymerization initiator.

Described (A) composition can use separately, also can use two or more simultaneously.With respect to described polyfunctional epoxy resin 100 mass parts, preferred 0.5～20 mass parts of content of described (A) composition.Content by making (A) composition is in described scope, and the photoresistance film can keep sufficient sensitivity, and can keep the permanent film characteristic.

(other compositions)

Same with described eurymeric photoresistance composition, described minus photoresistance composition can use well-known in the past solvent composition.In addition, lactone series solvents such as gamma-butyrolacton, beta-propiolactone, gamma-valerolactone, δ-Wu Neizhi, γ-Ji Neizhi, 6-caprolactone, have the lactone utilization when forming the photoresistance pattern heat treated and open loop and with polymer in functional group's reaction, the result is organized the character in the photoresistance film, thereby preferred the use.Hydroxycarboxylic acid esters series solvents such as alkyl glycolate ester (glycolic acid), lactic acid alkyl ester, 2-hydroxybutyric acid Arrcostab have the character that coating and equal voltinism are improved, thereby preferably just use.

In the described minus photoresistance composition, can use to have to form crosslinked substituent aromatic series polycyclic compound as sensitizer with described polyfunctional epoxy resin more than at least 2.Utilize the sensitization function of this aromatic series polycyclic compound, the sensitivity that can improve the photoresistance composition.Particularly, the preferred aromatic series polycyclic compounds such as naphthalene compound with hydroxyl, carboxyl and amino etc. more than 2, dinaphthalene compound, anthracene compound, phenanthroline compounds that use.Among these, more preferably naphthalene compound is particularly considered from the viewpoint that improves cross-linking efficiency, preferably uses 1,5-dihydroxy naphthlene, 2,3-dihydroxy naphthlene, 2,6-dihydroxy naphthlene.

In addition, in order to improve film forming, can contain macromolecule straight chain bifunctional epoxy resin in the described minus photoresistance composition.Under the prerequisite of the decline of the rerum natura after not making sclerosis, improve the viewpoint of the flexibility of presclerotic photoresistance composition and consider, can contain oxetanes derivative or epoxides in the described minus photoresistance composition.And, described minus photoresistance composition also can contain the additive with miscibility as required and suitably, for example: the well-known in the past additive such as addition resin, plasticizer, stabilizer, colouring agent, surfactant, coupling agent that is used for improving pattern performance.

[photoresistance pattern]

For employed described eurymeric in this example and minus photoresistance composition, for example can be suitable in the past use eurymeric photoresistance composition or the photoresistance pattern formation method of minus photoresistance composition.Particularly, use circulator etc., the photoresistance composition that is prepared into the solution shape is coated on the described supporter 11, carry out prebake conditions and form the photoresistance film.Perhaps, also can protect the two sides of photoresistance composition and make dry film, this dry film is attached on the supporter 11 and forms the photoresistance film with diaphragm.If make dry film, just can omit the step of coating on supporter 11, drying, can form the photoresistance pattern more easily.

Then, optionally the photoresistance film is carried out exposure-processed.Exposure-processed can be used g line, h line, i line, KrF excimer laser beam, ArF excimer laser beam, F ₂(extreme ultraviolet Extremeultraviolet), electron beam (EB), grenz ray, X ray etc., can shine via required mask pattern, perhaps directly inscribes for excimer laser beam, EUV.The preferred KrF excimer laser beam of using.Then, the back heat treated (postexposure bake, below also be sometimes referred to as PEB (post exposure bake)) of exposing.After PEB handled, developer solutions such as use alkaline aqueous solution carried out development treatment, implement processing as required such as washing, drying, obtain the photoresistance pattern.Be not particularly limited for developer solution, can use well-known alkaline aqueous solution etc. in the past.

The heating-up temperature of the heating-up temperature of prebake conditions and exposure back heating (PEB) is 70～160 ℃, preferred 100～150 ℃.Be set in 40～180 seconds scope heating time, preferred 60～90 seconds scope.In addition, according to circumstances, after developing, described alkali can comprise the back baking procedure.

In addition, the aspect ratio of described photoresistance pattern is preferred more than 0.1.By the aspect ratio that makes the photoresistance pattern is more than 0.1, and the surface area of base material of cathode 10 is increased, and can make aftermentioned handle the metal film amount increase that forms by plating, realizes higher output and higher energy density thus.

＜metal film 〉

Metal film in the base material of cathode of this example is preferably handled by plating and is formed, and is not particularly limited.Plating is handled and can be adopted well-known in the past processing, if can described organic membrane, composite membrane, silica-based be to form metal film on the organic membrane of metal oxide film by overlay film or top layer, then be not particularly limited.In addition, metal film can be handled by the multistage plating and comprise multilayer.The step that forms this metal film be the plating treatment step preferably after cleaning step, catalysis thinner treatment step, carry out electroless plating nickel or electroless plating copper step, further comprise electroless plating tin step or electrolytic tinning step.

Below, the plating processing that is fit to this example is specifically described.

[cleaning step]

At first, will possess organic membrane, composite membrane, it is silica-based that to be immersed in phosphoric acid by overlay film or top layer by the supporter of the organic membrane of metal oxide film lining be to clean in the solution.Phosphoric acid is that solution uses sodium phosphate etc.Preferred 30～180 seconds of dip time, more preferably 45～90 seconds.

[catalysis thinner step]

Will be through the supporter of described cleaning step stannic chloride (SnCl in normal concentration ₂) flood the stipulated time in the aqueous solution.The preferred 0.01g/dm of the concentration of stannic chloride ³～0.10g/dm ³, more preferably 0.03g/dm ³～0.07g/dm ³In addition, preferred 15～180 seconds of dip time, more preferably 30～60 seconds.

Then, will be at stannic chloride (SnCl ₂) flooded the supporter of stipulated time in the aqueous solution, at the palladium bichloride (PdCl of normal concentration ₂) flood the stipulated time in the aqueous solution.The preferred 0.01g/dm of the concentration of palladium bichloride ³～0.3g/dm ³, more preferably 0.03g/dm ³～0.07g/dm ³In addition, preferred 15～180 seconds of dip time, more preferably 30～60 seconds.

[electroless plating nickel step]

To be immersed in nickel plating in the nickel plating bath through the supporter of described catalysis thinner step.Nickel plating bath can use well-known in the past nickel plating bath.Lift an example, for example can use the nickel plating bath of complexing agent of lead ion, the 0.05M～0.30M of sodium hypophosphite, the 0.05ppm～0.30ppm of the nickelous sulfate that contains 0.05M～0.20M, 0.10M～0.30M.Complexing agent preferably uses the carboxylic acids complexing agent.Preferred 50 ℃～70 ℃ of the temperature of nickel plating bath, pH value preferred 4.0～5.5.Can use NaOH, sulfuric acid to adjust the pH value.

In addition, can carry out electroless plating copper and replace described electroless plating nickel.Copper plating solution can use well-known in the past copper plating solution.

[electroless plating copper step]

To be immersed in copper facing in the copper plating solution through the supporter of described catalysis thinner step.Copper plating solution uses well-known in the past copper plating solution.Lift an example, for example can use the copper sulphate that contains 0.02M～0.10M, 0.10M～0.40M formalin, 1.0ppm～20.0ppm 2,2 '-copper plating solution of the surfactant (polyethylene glycol etc.) of bipyridine, 50.0ppm～500ppm, the complexing agent of 0.20M～0.40M.Complexing agent preferably uses the complexing agent of polyethylene polyamine system.Preferred 50 ℃～70 ℃ of the temperature of copper plating solution, pH value preferred 11.5～12.5.In addition, preferably stir by bubbling air.Can use potassium hydroxide, sulfuric acid to adjust the pH value.

[electroless plating tin step]

To be immersed in the zinc-plated bath through the supporter of described electroless plating nickel or electroless plating copper step zinc-plated, with this at organic membrane, composite membrane, silica-basedly formed metal film on the organic membrane by the metal oxide film lining by overlay film or top layer.Zinc-plated bath can be used well-known in the past zinc-plated bath.Lift an example, for example can use the stannic chloride that contains 0.02M～0.20M, 0.02M reducing agents such as the titanium trichloride of～0.08M, and the trisodium citrate of 0.10M～0.50M, disodium ethylene diamine tetraacetate (EDTA-2Na), nitrilotriacetic acid (nitrilotriacetic acid NTA) waits the zinc-plated bath of complexing agent.Preferred 45 ℃～70 ℃ of the temperature of zinc-plated bath, pH value preferred 6.5～8.5.Can use sodium carbonate or ammonia and hydrochloric acid to adjust the pH value.In addition, preferably under nitrogen environment, carry out zinc-plated processing.

[electrolytic tinning step]

In addition, can carry out electrolytic tinning and replace described electroless plating tin.In this zinc-plated step, to be immersed in the zinc-plated bath through the supporter of described electroless plating nickel or electroless plating copper step, energising and carry out electrolytic tinning, thus at organic membrane, composite membrane, silica-basedly formed metal film on the organic membrane by the metal oxide film lining by overlay film or top layer.Electrolytic tinning is bathed and can be used well-known in the past electrolytic tinning to bathe.Lift an example, the electroplate liquid that for example can use Leybold limited company to sell, the i.e. zinc-plated bath of Starter Curumo.Preferred 10 ℃～28 ℃ of the temperature of zinc-plated bath, pH value preferred 1.0～1.5.In addition, be suitable for the preferred 0.5A/dm of current density ²～6.0A/dm ²

＜secondary cell 〉

Described base material of cathode can be used as secondary battery cathode base material, particularly negative electrode for lithium secondary battery base material aptly.Lithium secondary battery is to use organic solvent and lithium salts to be used as electrolyte, by because lithium ion (Li ⁺) between negative pole and positive pole, move and the electric charge that causes is given and accepted and realized the secondary cell of charge/discharge, have output voltage height, advantage that energy density is high.In the lithium secondary battery in the past, use carbon always, use the transition metal oxide lithium compound as positive pole as negative pole, but in recent years in order to realize higher output and higher energy density, and launched research at negative material.Requiring negative material is to form film, and the material of reversibly occlusion/release lithium, and described base material of cathode satisfies these requirements, therefore can use aptly.Wherein, so-called " occlusion " is meant wrapping lithium in the reversible mode, to form alloy, solid solution etc. with the reversible mode of lithium, perhaps with the chemical bonding with the reversible mode of lithium.

When utilizing described base material of cathode to be used as the negative material of lithium secondary battery, need be on collector body and form negative pole with the base material of cathode lamination.But, if having conductivity, described supporter just do not need so, can be with supporter as collector body.As long as collector body has conductivity, its material or structure etc. is not particularly limited.Can use employed collector body in the common lithium secondary battery in the past.Preferably with the collector body of the good adhesion of described base material of cathode.In addition, preferred not can with the material of lithium alloyage.Particularly, can enumerate and comprise the material that is selected from least a element in the group that copper, nickel, stainless steel, molybdenum, tungsten, titanium and tantalum form.In addition, preferable alloy paper tinsel, adhesive-bonded fabric, have the structures such as metal current collector of three-dimensional structure.Especially preferably use metal forming, particularly, preferably use Copper Foil etc.Thickness for collector body is not particularly limited.

Usually, the negative electrode material layer of laminated film shape on collector body and the negative pole that forms, with laminations such as emboliform negative material and adhesives on collector body and the negative pole that forms is compared and can be reduced internal resistance.That is to say, utilize described base material of cathode lamination on collector body and the negative pole that forms can obtain the higher lithium secondary battery of power generation characteristics.But, in the negative pole that forms owing to the negative electrode material layer of laminated film shape on collector body, the adhesiveness of negative electrode material layer and collector body is bigger, thus negative electrode material layer along with charge/discharge expansion, might make negative electrode material layer or collector body produce distortion such as fold.Particularly when collector body used Copper Foil etc. to be rich in the metal forming of ductility, deformation extent can further increase.Therefore, iff be merely with the negative material laminated layer of film like on collector body, the energy density as battery is descended, charge is worsened.

With respect to this, the described base material of cathode of this example has the structure of lamination metal film on organic membrane, composite membrane, the silica-based organic membrane that is had metal oxide film by overlay film or top layer, therefore since metal film carry out stress that expansion produces and obtain mitigation by organic membrane or composite membrane, silica-based cushioning effect separately along with the occlusion/release of lithium by overlay film, organic membrane and metal oxide film.So the stress that is produced in the time of can suppressing charge/discharge increases, the result can suppress base material of cathode or collector body produces distortion such as fold.And can suppress base material of cathode and produce be full of cracks or peel off from collector body.That is to say, utilize described base material of cathode lamination on collector body and the negative pole that forms can obtain to have high output voltage and high-energy-density, and the lithium secondary battery of excellent charge.

In addition, be not particularly limited, can adopt and the identical formation of well-known lithium secondary battery in the past for the formation beyond the negative pole.Particularly, mainly comprise the positive pole of reversibly occlusion/release lithium, and have the conductive electrolyte of lithium.Utilize barrier film to keep electrolyte as required, make electrolyte and negative pole and anodal the contact under the state in remaining in barrier film, thereby carry out the exchange of lithium.

As long as anodal reversibly occlusion/release lithium then is not particularly limited, can use normally used positive pole in the lithium secondary battery.Particularly, can use lamination positive electrode material layer on collector body and the positive pole that obtains.For example can form positive pole by following manner: positive electrode and conductive agent, adhesive are dispersed in make pulp-like in the dispersion solvent, this slurry is coated on the collector body, in addition dry then.Thickness for collector body, positive electrode material layer is not particularly limited, and can wait arbitrarily according to battery design electric capacity and set.

Also be not particularly limited for positive electrode, can use the well-known in the past positive electrodes such as oxide that comprise lithium and transition elements.Particularly, can use LiCoO ₂, LiNiO ₂, LiMnO ₂, LiMn ₂O ₄, LiCo _0.5Ni _0.5O ₂Deng.Conductive agent for example uses acetylene black, carbon black, powdered graphite etc. so long as have the material of conductivity and then be not particularly limited.As long as adhesive can form the shape that the back keeps positive electrode material layer at positive pole, be not particularly limited, can use rubber is resin system adhesives such as adhesive or fluororesin.

As long as barrier film can keep having the conductive electrolyte of lithium, and can get final product, its material or structure etc. is not particularly limited remaining electric insulation between negative pole and the positive pole.For example, can use porous resin films such as cellular polypropylene film, cellular polyethylene film, perhaps by adhesive-bonded fabric of the resin manufacture that comprises polyolefin etc. etc.

As long as electrolyte has the lithium conductibility, be not particularly limited.For example, can use the non-aqueous electrolytic solution of electrolyte dissolution gained in nonaqueous solvents that will comprise lithium.The electrolyte that comprises lithium for example uses LiPF ₆, LiBF ₄, LiClO ₄, LiAsF ₆, LiCF ₃SO ₃Deng lithium salts.Nonaqueous solvents for example uses propene carbonate, ethylene carbonate, dimethyl carbonate, methyl ethyl carbonate, diethyl carbonate, gamma-butyrolacton, 1,2-dimethoxy-ethane, 1, the mixed solvent of 2-diethoxyethane, ethyoxyl methoxy base ethane etc. or these nonaqueous solventss.Concentration for non-aqueous electrolytic solution is not particularly limited, and also can use so-called polymer dielectric or solid electrolyte etc.

The lithium secondary battery that utilizes the described base material of cathode of this example to be used as negative pole can form various shapes such as coin shape, cylindrical shape, square or plate shaped battery.In addition, also be not particularly limited for the electric capacity of this lithium secondary battery, employed compact battery employed large-sized battery in hybrid vehicle etc. all can be suitable for from precision equipment etc.

(second example)

＜base material of cathode 〉

Fig. 2 represents the schematic diagram of the base material of cathode 20 of this example.As shown in Figure 2, the base material of cathode 20 of this example comprises: organic membrane 22 and metal film 24 that supporter 21, top layer are covered by metal oxide film 23.More specifically, the base material of cathode 20 of present embodiment is characterised in that: by implementing platings by the supporter 21 of the organic membrane 22 of metal oxide film 23 lining and handle possessing the top layer, and form metal film 24.

＜supporter 〉

The supporter 21 that uses in the base material of cathode 20 of this example is supporters identical with first example.

＜organic membrane 〉

Organic membrane 22 in the base material of cathode 20 of this example is to be formed by organic compound or organic resin, is not particularly limited.Preferably form by organic compound with hydrophilic group or organic resin with hydrophilic group.If have hydrophilic group on the surface of organic membrane 22, form the interaction of material so by this hydrophilic group and aftermentioned metal oxide film, can form the metal oxide film 23 that adheres to securely with organic membrane 22.

The organic membrane 22 that described organic membrane 22 is preferably formed by aftermentioned photoresistance composition more preferably are patterned to the photoresistance pattern of regulation shape by pattern exposure.When on the photoresistance pattern, forming metal oxide film 23, if have hydrophilic group on the surface of photoresistance pattern, form the interaction of material so by this hydrophilic group and aftermentioned metal oxide film, can form the metal oxide film 23 that adheres to securely with the photoresistance pattern.That is to say, can obtain high density and have the pattern of high mechanical properties.

[photoresistance composition, photoresistance pattern]

When forming the base material of cathode 20 of this example, use photoresistance composition, the photoresistance pattern identical with first example.

＜metal oxide film 〉

The metal oxide film 23 so long as formed by metal oxide on top layer of described organic membrane 22 of being covered gets final product, and is not particularly limited.Preferred silica-based by overlay film.Metal oxide film 23 forms material by following metal oxide film and forms.

[metal oxide film formation material]

The metal oxide film of this example forms material and is characterised in that: contain the metallic compound that can generate hydroxyl by hydrolysis, and dissolve this metallic compound and do not have the functional group's of metallic compound reaction solvent therewith.

[metallic compound]

As mentioned above, metallic compound is the compound that can generate hydroxyl by hydrolysis.The metal oxide film that will contain this metallic compound forms material and is coated on the described organic membrane 22, perhaps as required after further being coated with water distribution (preferred deionized water) after the coating, even under the low temperature about room temperature, metallic compound also can react with moisture in the atmosphere or the water that is coated with, and generates hydroxyl by hydrolysis.And the hydroxyl that is generated is dehydrating condensation each other, and a plurality of metallic compound molecules are bonding each other, forms the metal oxide film 23 of the higher densification of film density thus.In addition, when having reactive group such as carboxyl, hydroxyl when described organic membrane 22, the reactive group of organic membrane 22 reacts (dehydrating condensation, absorption etc.) with the hydroxyl that is generated by metallic compound, forms the metal oxide film 23 that sticks to organic membrane 22 surfaces securely.

Metallic compound for example uses has the metallic compound that can generate the functional group of hydroxyl by hydrolysis, the metallic compound of preferred functional group and metallic atom Direct Bonding.As for functional group's number, be more than 2 preferably with respect to 1 metallic atom functional group, more preferably 2～4, more preferably 4.If have the metallic compound of the functional group more than 2 with respect to 1 metallic atom, the hydroxyl that is generated by hydrolysis so is dehydrating condensation each other, and a plurality of metallic compound molecules are bonding continuously each other, forms firm metal oxide film 23 thus.

Can enumerate by the functional group that hydrolysis generates hydroxyl: alkoxyl, NCO, carbonyl etc.In addition, halogen atom also has same function, and therefore in this example, halogen is also included among the described functional group.It is 1～5 straight chain shape or the lower alkoxy that props up chain that alkoxyl can be enumerated carbon number, particularly, (O-Me), (O-Et), (O-nPr), (O-iPr), n-butoxy (O-nBu) etc. for isopropoxy for positive propoxy for ethyoxyl can to use methoxyl group.Halogen atom can be enumerated chlorine atom, fluorine atom, bromine atoms, iodine atom etc., especially preferably uses the chlorine atom.

When having reactive group such as carboxyl or hydroxyl when the surface of organic membrane 22, these reactive groups can carry out condensation reaction with alkoxyl or NCO, thereby can form the metal oxide film 23 that sticks to securely on the organic membrane 22, therefore preferred the use.In addition, carbonyl or halogen atom are adsorbed on the organic membrane 22 by the interaction with reactive groups such as the surperficial existing carboxyl of organic membrane 22 or hydroxyls, thereby can form the metal oxide film 23 that adheres to securely on the organic membrane 22, therefore preferred the use.Particularly NCO and halogen atom (particularly chlorine atom) is active higher, and needn't carry out heat treated especially and can form metal oxide film 23 easily, thereby preferred the use, most preferably uses NCO.

Constitute in the metal of metallic compound, except normally used metal, also comprise: boron, silicon, germanium, antimony, selenium, tellurium etc.The metal that constitutes metallic compound can be enumerated: titanium, zirconium, aluminium, niobium, silicon, boron, lanthanum, yttrium, barium, cobalt, iron, zirconium, tantalum etc.Among these, preferred titanium, silicon, preferred especially silicon.In addition, the number of the metallic atom in the metallic compound can be 1, also can be for more than 2, and preferred 1.

Metallic compound also can have the functional group's atom or organic group in addition that can generate hydroxyl by hydrolysis.For example can have hydrogen atom.Organic group for example can be enumerated alkyl (preferred carbon number is 1～5 low alkyl group) etc., preferred ethyl, methyl.

Metallic compound (below, be also referred to as " metal alkoxide class ") with alkoxyl can be enumerated: butanols titanium (Ti (O-nBu) ₄), propyl alcohol zirconium (Zr (O-nPr) ₄), aluminium butoxide (Al (O-nBu) ₃), butanols niobium (Nb (O-nBu) ₅), tetramethyl alcohol silicon (Si (O-Me) ₄), ethanol boron (B (O-Et) ₃) wait the metallic alkoxide compound beyond the rare earth metal; Lanthanum isopropoxide (Ln (O-iPr) ₃), yttrium isopropoxide (Y (O-iPr) ₃) wait the metallic alkoxide compound of rare earth metal; Alkanol barium titanium (BaTi (OR ⁶⁰) _x) wait two alkoxide cpds (" R wherein in addition, ⁶⁰" be that carbon number is 1～5 low alkyl group, X is 2～4 integer); Methyltrimethoxy silane (MESi (O-Me) ₃), diethyl diethoxy silane (Et ₂Si (O-Et) ₂) wait and have 2 above alkoxyls, and have the metallic alkoxide compound of the organic group beyond the alkoxyl; Have dentates such as acetylacetone based, and have metallic alkoxide compound of 2 above alkoxyls etc.

In addition, also can use in described metal alkoxide class and to add a spot of water, make partial hydrolysis of described metal alkoxide class and condensation and the alkoxide sol that obtains or the particulate of alkoxide gel.Further, butanols titanium tetramer (C ₄H ₉O[Ti (OC ₄H ₉) ₂O] ₄C ₄H ₉) wait two nuclear or the alkoxide cpds of bunch type with a plurality of or multiple metallic element, perhaps be also included within the described metal alkoxide class based on the macromolecule of the crosslinked metallic alkoxide compound of one dimension etc. via oxygen atom.

Metallic compound with NCO can be enumerated: with general formula [M (NCO) _x] the represented compound with 2 above NCOs (M is a metallic atom, and X is 2～4 integer).Particularly, can enumerate: four isocyanic acid silane (Si (NCO) ₄), four isocyanic acid titaniums (Ti (NCO) ₄), four isocyanic acid zirconiums (Zr (NCO) ₄), three isocyanic acid aluminium (Al (NCO) ₃) etc.

Metallic compound with halogen atom can be enumerated: with general formula [M (X ₁) _n] (M is a metallic atom, X ₁Be to be selected from a kind of in fluorine atom, chlorine atom, bromine atoms and the iodine atom, n is 2～4 integer) represented metal halide with (preferred 2～4) halogen atom more than 2.Particularly, can enumerate: titanium tetrachloride (TiCl ₄), tetrachloro silicane (SiCl ₄) etc.In addition, the metallic compound with halogen atom also can be a metal complex, also can use cobalt chloride (COCl ₂) etc.

Metallic compound with carbonyl can be enumerated: oxo acetoacetate titanium (TiO (CH ₃COCH ₂COO) ₂), iron pentacarbonyl (Fe (CO) ₅) wait the multinuclear nanocluster of metal carbonyl and these metal carbonyls.

Higher from activity, and needn't carry out heat treated can form metal oxide film 13 aspects easily and consider, in the described various metallic compound, preferred especially the silicon compound that uses with (preferred 2～4) NCO more than 2 and/or halogen atom.The number of the silicon in the silicon compound of 1 molecule can for 1 also can be for more than 2, preferred 1.Especially preferably with the represented compound of general formula [SiWa] (a represents 2～4 integer, and W represents NCO or halogen atom, a plurality of W can be mutually the same also can be different).Described a more preferably 4, halogen atom more preferably with the described chlorine atom that is similarly of preamble.Among these, especially preferably has the silicon compound of NCO.

In addition, metallic compound discussed above can be used alone, and also can be use mixing two or more simultaneously.

[solvent]

It is described metallic compound is dissolved in the solvent (S) and obtains that the metal oxide film of this example forms material.Solvent (S) is not so long as have the functional group of metallizing thing reaction, and can the solvent (S1) of employed metallic compound dissolving is promptly passable, can use well-known in the past organic solvent.The functional group of metallizing thing reaction can enumerate: vinyl etc. have the group, hydroxyl, carboxyl, halogen of carbon-to-carbon double bond etc.Therefore, so long as do not have these functional groups' solvent, metallic compound just can stably be present in the solvent.

Particularly, described solvent (S1) preferred fat compounds of group.Wherein, " aliphat " in this specification is the relative concept for aromatic series, is defined as group with armaticity, compound etc.That is to say that " aliphatic compound " is meant the compound with armaticity.Aliphatic compound can be the chain compound that does not have ring in the structure, also can be the cyclic compound that has ring in the structure in addition, preferred cyclic compound.Cyclic compound preferred hydrocarbons compound, more preferably saturated hydrocarbon compound.This cyclic compound can be enumerated: monocycle alkane, and polycyoalkanes such as dicyclo alkane, three cycloalkane, Fourth Ring alkane, bonding substituent compound such as alkyl etc. on these rings.

In addition, described solvent (S1) is preferably selected the solvent less to the influence of environment, for example, preferably uses the solvent of initiation material as natural materials.Initiation material is that the solvent of natural materials can be enumerated: the terpenic series solvent that obtains by the derived essential oil of plant etc. (for example, following to monocyclic monoterpene such as terpane, adjacent terpane, terpanes, perhaps dicyclic monoterpene such as pinane etc.).

In addition, the preferred use of described solvent (S1) can be with the solvent of organic membrane 22 dissolvings.If this solvent when so particularly forming metal oxide film 23 on the surface of photoresistance pattern, is not easy the shape of photoresistance pattern is caused damage.

Never can the metallizing thing reaction, less and aspects such as photoresistance pattern dissolved can not considered to the influence of environment, preferred especially the use with the represented compound of following general formula (1) as solvent (s-1).

[changing 32]

[in the formula (1), R ²¹～R ²³Independent respectively is the alkyl of hydrogen atom or a straight chain shape or a chain, R ²¹～R ²³In at least two be alkyl, this alkyl can with cyclohexane ring in this alkyl linked carbon atom beyond carbon atom bonding and form ring]

In the formula (1), R ²¹～R ²³In at least two be the alkyl of straight chain shape or chain.That is to say, can be R ²¹～R ²³In two be the alkyl of straight chain shape or chain, and another is hydrogen atom, also can be R ²¹～R ²³It all is the alkyl of a straight chain shape or a chain.Preferred R ²¹～R ²³In two be the alkyl of straight chain shape or chain.

R ²¹～R ²³The straight chain shape or the preferred carbon number of alkyl of chain be 1～5 low alkyl group, more preferably carbon number is 1～3 low alkyl group.Particularly, can enumerate: methyl, ethyl, propyl group, isopropyl, normal-butyl, isobutyl group, amyl group, isopentyl, neopentyl etc.Among these, special preferable methyl or isopropyl.

R ²¹～R ²³In at least two alkyl can distinguish identical also can be different.Preferred R ²¹～R ²³In at least one alkyl for chain, more preferably at least one is an isopropyl.Described solvent (s-1) especially preferably have isopropyl and methyl both.

R ²¹～R ²³Alkyl can with cyclohexane ring in this alkyl linked carbon atom beyond carbon atom bonding and form ring.Wherein, " with in the cyclohexane ring with this alkyl linked carbon atom beyond carbon atom bonding and form ring ", be meant and utilize the group (alkylene) of removing a hydrogen atom on the alkyl from then on, and at carbon atom on the cyclohexane ring and that this is alkyl linked, therewith form between the carbon atom beyond the carbon atom crosslinked.

For R ²¹～R ²³Bonding position be not particularly limited, preferred at least two alkyl be bonded in respectively in 1 of cyclohexane ring and 4 (contraposition) or 1 and 3 (position) on.

Particularly, can enumerate with the represented compound of described formula (1): terpane (boiling point is about 170 ℃), a terpane (boiling point is about 170 ℃), adjacent terpane (boiling point is about 170 ℃), pinane (boiling point is about 169 ℃) etc.The structure of these compounds is shown in following.Among these, especially preferably to terpane.

[changing 33]

To the adjacent terpane pinane of terpane between terpane

Described solvent (S1) can be used alone, and also can be use mixing two or more simultaneously.In the solvent (S), in the scope of preferred 50～100 quality % of ratio of solvent (S1), more preferably 80～100 quality %, more preferably 100 quality %.

Solvent (S) also can contain solvent (S1) solvent (S2) in addition in the scope of not damaging effect of the present invention.Solvent (S2) for example can be enumerated: methyl alcohol, ethanol, propyl alcohol, n-hexane, normal heptane, toluene, benzene, isopropylbenzene etc.Consider preferred normal heptane (boiling point is about 98 ℃), isopropylbenzene (boiling point is about 152 ℃) among these from forming fine and close film aspect.Solvent (S2) can be used alone, and also can be use mixing two or more simultaneously.

Content for solvent (S) is not particularly limited, be about 1～200mM preferably making metal oxide film form with the molar concentration in the composition (metallic compound with as required and the total concentration of the following organic compound of use), preferred 50～150mM more preferably uses in the scope of 50～100mM.If molar concentration in this scope, just can form more even metal oxidation film, thus preferred.

[composition arbitrarily]

Described metal oxide film formation material also can contain any composition except metallic compound and solvent (S).Composition for example can be enumerated organic compound arbitrarily.The metal oxide film that utilization includes organic compounds forms material, can form the composite membrane of metal oxide and organic compound.As long as organic compound can be dissolved in the described solvent (S) and then be not particularly limited.Here said dissolving is not limited in the situation that organic compound is separately a solubilized, also comprises the phenylazobenzoic acid as 4-, by with the compound situation about being dissolved in the chloroform equal solvent of metal alkoxide class.And there is no particular restriction to the molecular weight of organic compound.

From the viewpoint of film-strength or make metal oxide film and viewpoint that the adhesiveness of organic membrane 22 is more firm considers that described organic compound preferably has a plurality of reactive groups (preferred hydroxyl or carboxyl), and at room temperature (25 ℃) are the solid proterties.This organic compound for example preferably uses: polyacrylic acid, polyvinyl alcohol, polyethylene phenol, polymethylacrylic acid, polyglutamic acid etc. have the macromolecular compound of hydroxyl or carboxyl; Polysaccharides such as starch, glycogen, polysialic acids; Disaccharides such as glucose, mannose, monosaccharide; And terminal porphyrin compound with hydroxyl or carboxyl or dendritic (dendrimer) etc.

In addition, described organic compound also can preferably use the cationic macromolecular compound.Metal alkoxide class or metal oxide interact as anion with respect to the cation of cationic macromolecular compound, therefore can realize firm bonding.The concrete example of cationic macromolecular compound can be enumerated: PDDA (PDDA, dimethyldiallyl ammonium chloride), polymine, polylysine, shitosan, end have amino dendritic etc.

These organic compounds play a role as being used for forming the constituent of the higher film of mechanical strength.In addition, these organic compounds also can be used as and are used for the film that is obtained is given the functional position of function and played a role, perhaps also can bring into play the effect of following composition: behind the system film molecule of this organic compound is removed, thereby in film, formed and the corresponding hole of its molecular shape.Organic compound can be used alone, and also can be use mixing two or more simultaneously.With respect to metallic compound 100 mass parts, preferred 0.1～50 mass parts of the content of organic compound, preferred especially 1～20 mass parts.

[formation of metal oxide film]

Use described metal oxide film to form material, on described organic membrane 22, form metal oxide film 23.Particularly, metal oxide film formed the surface that material is coated on organic membrane 22 after, it is dry then to clean this surface with organic solvent.That is to say, behind the coating metal oxide film formation material, clean and unnecessary metallic compound (for example, attached to the metallic compound on the supporter 21) is removed.And during drying was finished, metallic compound utilized airborne moisture and slow hydrolysis generation hydroxyl afterwards, this hydroxyl dehydrating condensation, thus form metal oxide film 23 on the surface of organic membrane 22.When metal oxide film formation material comprises organic substance, be the metal oxide film that laminated film constituted 23 that forms by organic substance and metal oxide.

Wherein, in the past silica-based need be as spin-coating glass SOG (spin-coating glass by overlay film, spin-on-glass) method etc. is carried out high-temperature process like that, and therefore for example when using the photoresistance pattern to be used as described organic membrane 22, the photoresistance pattern is understood owing to high-temperature process overheats.With respect to this, the described metal oxide film of this example forms material can form metal oxide film 23 at low temperatures, so can not damage the shape of the photoresistance pattern that it is covered.In addition, consider, preferably under inert gas environment, form the operation of metal oxide film 23 from controlling reactive aspect.At this moment, do not utilize airborne moisture and handle.

The coating process that metal oxide film forms material can adopt well-known in the past method, is not particularly limited.For example, can enumerate following method: the supporter 21 that will possess organic membrane 22 is immersed in (dip coating) in the metal oxide membrane material; Perhaps utilizing spin-coating method that metal oxide film is formed material is coated on the organic membrane 22.In addition, also can utilize methods such as alternating adsorption method to form metal oxide film 23.

Temperature (coating temperature) when metal oxide film is formed material and is coated on the organic membrane 22 can not be decided according to the activity of employed metallic compound and different without exception, is generally in 0～100 ℃ the scope.In addition, be coated on the organic membrane 22 till drying from metal oxide film being formed material (comprise coating, cleaning, as required and the processing of carrying out such as absorption) time, be that metal oxide film forms material and the time of contact of organic membrane 12 and the temperature during this (contacting temperature) according to the activity of employed metallic compound and different before the hydrolysis, can not decide without exception, be generally several seconds to several hours, temperature is in the scope identical with described coating temperature.

The organic solvent that is used to clean can preferably use the identical solvent of illustrative solvent with the solvent (S) that forms material as metal oxide film.Can preferably adopt following method to clean: utilize spray-on process etc. with organic solvent supply to form the formed surface of filming of material by metal oxide film after, under reduced pressure aspirate unnecessary organic solvent and the method for cleaning; Perhaps be immersed in the method for cleaning in the organic solvent; By the method for spraying and cleaning; And utilize method that steam cleans etc.The temperature of temperature conditions during cleaning during with coating metal oxide film formation material is identical.

By after metal oxide film being formed the surface that material is coated on organic membrane 22, clean and the unnecessary metallic compound on the supporter 21 is removed, can form the very excellent metal oxide film 23 of uniformity of thickness.That is to say, by cleaning, the metallic compound that only will mainly utilize more weak physical absorption and be adsorbed on the supporter 21 is removed, the surface of organic membrane 22 is the metallic compound of residual chemisorbed equably only, thus can precision very good and reappearance how to form the uniform film of meter level higherly.Therefore, when having produced chemisorbed between the organic membrane 22 metallizing things, described cleaning operation is effective especially.

Wherein, " chemisorbed " in this specification, be meant between surperficial existing reactive group (preferred hydroxyl or carboxyl) the metallizing thing of organic membrane 22 to form chemical bond (covalent bond, hydrogen bond, coordinate bond etc.) or electrostatic bonding (ionic bond etc.), metallic compound or its metal ion are bonded in the state on the surface of organic membrane 22 thus.In addition, so-called " physical absorption ", be meant metallic compound or its metal ion utilize Van der Waals force (van der Waals force) to wait a little less than molecular separating force and be bonded in the state on the surface of organic membrane 22.

Be not particularly limited for carrying out dry method after cleaning, can adopt well-known in the past method.For example can use that nitrogen etc. is dry uses gas,, so just can directly utilize circulator to dry if utilize circulator to come coating metal oxide film formation material.

Behind the coating metal oxide film formation material up to carrying out between dry period, processing such as can place as required, with the chemisorbed and/or the physical absorption of the metallic compound in advancing organic membrane 22 and forming by metal oxide film that material is formed and film.

Clean the back up between dry period to formed formed the filming of material by metal oxide film, can add water treatment, making films contact with water, so that surperficial metallic compound hydrolysis and generate hydroxyl.Thus, the metal oxide film 23 of multilayer film that can easily form lamination, and can adjust the thickness of metal oxide film 23.That is to say, by metal oxide film form hydroxyl that the formed surface of filming of material generated, with the further metallic compound reaction in formed the filming of coating metal oxide film formation material and adhering to securely on this films, the metal oxide film 23 of multilayer film that obtained lamination.The method that adds water treatment can adopt well-known in the past method, is not particularly limited.For example, prevailing method is to make the sol-gal process of filming and contacting with water.More specifically, can enumerate: be coated with the method for water distribution in film coated surface, perhaps will film is immersed in method in the organic solvent that contains a spot of water.In addition, when the reactive higher metallic compound that comprises with water, being placed in the atmosphere can the hydrolysis with the vapor in the atmosphere reaction, so also can not add water treatment.In order to prevent to sneak into impurity etc., generate highly purified metal oxide, water preferably uses deionized water.In addition, add in the water treatment,, can significantly shorten the processing time by using catalyst such as acid or alkali.

Thickness for metal oxide film 23 is not particularly limited.More than the preferred 0.1nm, more preferably 0.5～50nm, more preferably 1～30nm.Can adjust the thickness of metal oxide film 23 by carrying out coating that metal oxide film forms material repeatedly, clean and adding water treatment.That is to say, can by carry out repeatedly with metal oxide film form material coating form film after, clean and place as required, be hydrolyzed then and handle this a series of operation, and form by the metal oxide film that uniform film constituted 23 with desired thickness.For example, can precision form several nm～tens nm well, and be the metal oxide film 23 of hundreds of nm according to the thickness of condition.

When use comprised metal oxide film that four isocyanic acid silicon, butanols titanium etc. contain a kind of metal alkoxide of metallic atom and forms material and be used as metallic compound, according to the difference of contact conditions, lamination thickness was the film of several dusts one by one.At this moment, per 1 thickness of being increased of circulation is corresponding with the lamination number of times of metal oxide film formation material.On the other hand, if use the particulate etc. of alkoxide gel to be used as metallic compound, so also can per 1 circulation lamination thickness be the film about 60nm.In addition, form when utilizing spin-coating method when forming by metal oxide film that material is formed films, concentration that can be by changing employed solvent or metallic compound, rotary speed etc., and be about several nm～200nm with film thickness monitoring at random.At this moment, also by changing the kind of per 1 employed metallic compound that circulates, and obtain the metal oxide film 23 that forms by the formed thin film lamination of different kinds of metals oxide.

In addition, be not particularly limited for the total film thickness of organic membrane 22, below the preferred 1 μ m, more preferably below the 0.7 μ m, more preferably below the 0.5 μ m with metal oxide film 23.Be not particularly limited for total lower limit, more than the preferred 0.01 μ m, more preferably more than the 0.05 μ m.

The plating of the base material of cathode of this example handles, and lithium rechargeable battery is handled with the plating of first example, to reach lithium rechargeable battery identical.

[the 3rd example]

＜base material of cathode 〉

Fig. 3 represents the schematic diagram of the base material of cathode 30 of this example.As shown in Figure 3, the base material of cathode 30 of this example comprises: supporter 31, composite membrane 32 and metal film 33.More specifically, the base material of cathode 30 of present embodiment is characterised in that: form metal film 33 on the supporter 30 that possesses composite membrane 32.

＜supporter 〉

Employed supporter 31 is supporters identical with first example in the base material of cathode 30 of this example.

＜composite membrane 〉

Composite membrane 32 in the base material of cathode 30 of this example is formed by the compound film formation material that includes organic principles such as organic compounds or organic resin and inorganic constituentss such as inorganic compound or inorganic resin, be not particularly limited for this compound film formation material, composite membrane 32 more preferably is patterned to the patterning composite membrane of regulation shape preferably by the formed composite membrane of following compound film formation material by pattern exposure.

[compound film formation material]

For the compound film formation material of the base material of cathode 30 that is used to form this example, if include organic principles such as organic compounds or organic resin, with inorganic constituentss such as inorganic compound or inorganic resin, then be not particularly limited.

Described inorganic constituents is not particularly limited as long as the exposure light when carrying out patterned exposure satisfies the required transparency, for example can enumerate: glass, pottery (cordierite etc.), metal etc.More specifically, can enumerate: PbO-SiO ₂System, PbO-B ₂O ₃-SiO ₂System, ZnO-SiO ₂System, ZnO-B ₂O ₃-SiO ₂System, BiO-SiO ₂System, BiO-B ₂O ₃-SiO ₂The glass powder of the lead borosilicate glass of system, zinc borosilicate glass, borosilicic acid bismuth glass etc.; Each oxide of Na, K, Mg, Ca, Ba, Ti, Zr, Al etc. such as cobalt oxide, iron oxide, chromium oxide, nickel oxide, cupric oxide, manganese oxide, neodymia, vanadium oxide, cerium oxide titan yellow, cadmium oxide, ruthenium-oxide, silicon dioxide, magnesium oxide, spinelle; ZnO:Zn, Zn ₃(PO ₄) ₂: Mn, Y ₂SiO ₅: Ce, CaWO ₄: Pb, BaMgAl ₁₄O ₂₃: Eu, ZnS:(Ag, Cd), Y ₂O ₃: Eu, Y ₂SiO ₅: Eu, Y ₃Al ₅O ₁₂: Eu, YBO ₃: Eu, (Y, Gd) BO ₃: Eu, GdBO ₃: Eu, ScBO ₃: Eu, LuBO ₃: Eu, Zn ₂SiO ₄: Mn, BaAl ₁₂O ₁₉: Mn, SrAl ₁₃O ₁₉: Mn, CaAl ₁₂O ₁₉: Mn, YBO ₃: Tb, BaMgAl ₁₄O ₂₃: Mn, LuBO ₃: Tb, GdBO:Tb, ScBO ₃: Tb, Sr ₆Si ₃O ₃Cl ₄: Eu, ZnS:(Cu, Al), ZnS:Ag, Y ₂O ₂S:Eu, ZnS:Zn, (Y, Cd) BO ₃: Eu, BaMgAl ₁₂O ₂₃: fluorophor powders such as Eu; The metal dust of iron, nickel, palladium, tungsten, copper, aluminium, silver, gold, platinum etc. etc.The transparency such as glass, pottery is excellent, so preferred.Wherein, when using glass powder (glass paste), show the most significant effect, thus preferred especially.

The pattern form of the composite membrane of the particle diameter of described inorganic constituents during according to patterning is and different, and preferred average grain diameter is 0.5～10 μ m, preferred 1～8 μ m.By making average grain diameter in described scope, when forming pattern with high precision, can not produce concave-convex surface, to such an extent as to and the exposure light diffusion light can not make patterning the time be difficult to arrive the bottom.The shape of described inorganic constituents can be enumerated: spherical, block, sheet, ingotism shape etc.These inorganic constituentss can be used separately, also can be used in combination of two or more simultaneously.

In addition, described inorganic constituents also can be the mixture of the different particulate of physics value.Particularly by using different glass powder or the ceramic powders of thermal softening point, the shrinkage in the time of can suppressing roasting.And, because the average grain diameter of described inorganic constituents is 0.5～10 μ m, so in order to prevent its secondary aggregation, in addition in order to improve dispersiveness, also can be in not damaging its scope as the character of inorganic constituents, utilizing organic acid, inorganic acid, silane coupler, titanate esters is that coupling agent, aluminium are that coupling agent and surfactant etc. carry out surface treatment in advance.The preferred following method of surface treatment method: after being dissolved in inorganic agent in organic solvent or the water etc., add inorganic constituents and stirring, distillation removes and desolvates, and carries out the heat treated more than 2 hours under about 50 ℃～200 ℃.In addition, also can when making compound film formation material gelatinization, add inorganic agent.

Described organic principle preferably contains (A3) water-soluble cellulose derivative, (B3) photopolymerization monomer with, and (C3) Photoepolymerizationinitiater initiater, more preferably contains the acrylic resin that (D3) has hydroxyl.

[(A3) water-soluble cellulose derivative]

Be not particularly limited for described (A3) water-soluble cellulose derivative, concrete example can be enumerated: carboxy methyl cellulose, hydroxy ethyl cellulose, hydroxy ethylmethylcellulose, hydroxy propyl cellulose, ethyl hydroxy ethyl cellulose, carboxy methyl ethyl cellulose, HYDROXY PROPYL METHYLCELLULOSE etc.These water-soluble cellulose derivatives can use separately, also can use two or more simultaneously.It is higher for the transmissivity of ultraviolet ray, excimer laser, X ray, electron beam isoreactivity light or radioactive ray as the compound film formation material of adhesive resin to contain this water-soluble cellulose derivative, so have excellent anti-development, can form the pattern with high precision composite membrane.

[(B3) photopolymerization monomer]

Be not particularly limited for described (B3) photopolymerization monomer, concrete example can be enumerated: glycol diacrylate, ethylene glycol dimethacrylate, triethylene glycol diacrylate, the triethylene glycol dimethylacrylate, trimethylolpropane triacrylate, trimethylol-propane trimethacrylate, the trimethylolethane trimethacrylate acrylate, the trimethylolethane trimethacrylate methacrylate, pentaerythritol diacrylate, dimethyl pentaerythritol acrylate, pentaerythritol triacrylate, pentaerythritol acrylate trimethyl, tetramethylol methane tetraacrylate, pentaerythrite tetramethyl acrylate, the dipentaerythritol tetraacrylate, dipentaerythritol tetramethyl acrylate, dipentaerythritol five acrylate, dipentaerythritol pentamethyl acrylate, dipentaerythritol acrylate, dipentaerythritol hexamethyl acrylate, the glycerol acrylate, the glycerol methacrylate, phenolphthalein basic ring oxygen diacrylate is replaced as (methyl) acrylate of these exemplary compounds the fumarate of fumarate, be replaced as the methylene-succinic acid ester of methylene-succinic acid ester, be replaced as the maleate of maleate etc.

[(C3) Photoepolymerizationinitiater initiater]

Be not particularly limited for described (C3) Photoepolymerizationinitiater initiater, for example can illustration: benzophenone, styrax class, styrax alkyl ether, acetophenones, aminoacetophenone class, benzil class, styrax alkyl ether, benzil alkyl ketal class, anthraquinone class, ketal class, thioxanthene ketone etc.More specifically; can enumerate: 2; 4-pair-trichloromethyl-6-(3-bromo-4-methoxyl group) phenyl-s-triazine; 2; 4-pair-trichloromethyl-6-(2-bromo-4-methoxyl group) phenyl-s-triazine; 2; 4-pair-trichloromethyl-6-(3-bromo-4-methoxyl group) styryl phenyl-s-triazine; 2; 4-pair-trichloromethyl-6-(2-bromo-4-methoxyl group) styryl phenyl-s-triazine; 2; 4; 6-trimethylbenzoyl diphenyl phosphine oxide; 1-[4-(2-hydroxyl-oxethyl) phenyl]-2-hydroxy-2-methyl-1-propane-1-ketone; 2; the 4-diethyl thioxanthone; 2; 4-dimethyl thioxanthones; the 2-clopenthixal ketone; 1-chloro-4-propoxyl group thioxanthones; 3; 3-dimethyl-4-methoxy benzophenone; benzophenone; 1-(4-isopropyl phenyl)-2-hydroxy-2-methyl propane-1-ketone; 1-(4-dodecylphenyl)-2-hydroxy-2-methyl propane-1-ketone; 4-benzoyl-4 '-methyl dimethoxy base sulfide; the 4-dimethylaminobenzoic acid; 4-dimethylaminobenzoic acid methyl esters; 4-dimethylaminobenzoic acid ethyl ester; 4-dimethylaminobenzoic acid butyl ester; 4-dimethylaminobenzoic acid-2-Octyl Nitrite; 4-dimethylaminobenzoic acid-2-isopentyl ester; 2; the 2-diethoxy acetophenone; the benzil dimethyl ketal; benzyl-'beta '-methoxy ethyl acetals; 1-phenyl-1; 2-propane diketone-2-(adjacent ethoxy carbonyl) oxime; o-benzoyl yl benzoic acid methyl esters; two (4-dimethylaminophenyl) ketone; 4; 4 '-two (diethylamino) benzophenone; benzil; styrax; benzoin methyl ether; benzoin ethyl ether; benzoin isopropyl ether; the styrax n-butyl ether; benzoin isobutyl ether; to the dimethylamino benzoylformaldoxime; to tert-butyl group trichloroacetophenone; to tert-butyl group dichloroacetophenone; thioxanthones; 2-methyl thioxanthones; the 2-isopropyl thioxanthone; Dibenzosuberone; α; α-Er Lv-4-Ben Yangjibenyitong; amyl group-4-dimethylaminobenzoic acid ester; 2-(Chloro-O-Phenyl)-4,5-diphenyl-imidazole base dimer etc.These Photoepolymerizationinitiater initiaters can use separately, also can be used in combination of two or more simultaneously.

With respect to (A3) water-soluble cellulose derivative and (B3) summation 100 mass parts of photopolymerization monomer, the preferred content of described (C3) Photoepolymerizationinitiater initiater is 0.1～10 mass parts, more preferably 0.2～5 mass parts.By making Photoepolymerizationinitiater initiater in described scope, can not make hardening descend the ground inhibition owing to the bottom sclerosis that the Photoepolymerizationinitiater initiater absorbing light causes is bad.

The acrylic resin of hydroxyl [(D3) have]

Can in described organic principle, allocate the acrylic resin that (D3) has hydroxyl as required.This acrylic resin with hydroxyl can be enumerated: with monomer with hydroxyl as main combined polymerization monomer, the further copolymer that obtains with carrying out polymerization as required with these other monomers with monomer copolymerizable of hydroxyl.

Described monomer with hydroxyl is suitable is acrylic or methacrylic acid and carbon number is the mono-esterification thing of single alcohol of 1～20.Particularly, can enumerate: acrylic acid hydroxy methyl, methacrylic acid hydroxyl methyl esters, 2-Hydroxy ethyl acrylate, methacrylic acid-2-hydroxy methacrylate, acrylic acid-2-hydroxy propyl ester, methacrylic acid-2-hydroxy propyl ester, acrylic acid-3-hydroxy propyl ester, methacrylic acid-3-hydroxy propyl ester, acrylic acid-2-hydroxyl butyl ester, methacrylic acid-2-hydroxyl butyl ester, acrylic acid-3-hydroxyl butyl ester, methacrylic acid-3-hydroxyl butyl ester, acrylic acid-4-hydroxyl butyl ester, methacrylic acid-4-hydroxyl butyl ester etc.In addition, can enumerate: acrylic or methacrylic acid and carbon number are the mono-esterification thing of 1～10 glycol, or glycerol acrylate, glycerol methacrylate, dipentaerythritol mono acrylic ester, dipentaerythritol monomethacrylates, 6-caprolactone modified acroleic acid hydroxy methacrylate, 6-caprolactone modified methacrylic acid hydroxy methacrylate, acrylic acid 2-hydroxyl-epoxy ester compounds such as 3-phenoxy group propyl ester.

Can for example can enumerate with described other monomers: α such as acrylic acid, methacrylic acid, methylene-succinic acid, citraconic acid, methylene-succinic acid, maleic acid, fumaric acid with monomer copolymerizable of hydroxyl, beta-unsaturated carboxylic acid, and these α, the acid anhydrides of beta-unsaturated carboxylic acid or half carboxylate; Methyl acrylate, ethyl acrylate, the acrylic acid n-propyl, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, sec-butyl acrylate, cyclohexyl acrylate, acrylic acid-2-ethyl caproite, the acrylic acid stearyl, methyl methacrylate, EMA, n propyl methacrylate, isopropyl methacrylate (isopropyl methacrylate), isopropyl methacrylate (sec-propylmethacrylate), n-BMA, isobutyl methacrylate, the secondary butyl ester of methacrylic acid, cyclohexyl methacrylate, methacrylic acid-2-Octyl Nitrite, the methacrylic acid stearyl, acrylic acid-2,2,2-trifluoro methyl esters, methacrylic acid-2,2, α such as 2-trifluoro methyl esters, the beta-unsaturated carboxylic acid ester; And styrene, AMS, to phenylethylenes such as vinyltoluene etc.In addition, also can use: acrylonitrile, methacrylonitrile, acrylamide, Methacrylamide, vinyl acetate, glycidyl acrylate, glycidyl methacrylate etc.These monomers can use separately, also can be used in combination of two or more simultaneously.

It is preferred below 20,000 that described (D3) has the molecular weight of acrylic resin of hydroxyl.More preferably 15,000～5,000, more preferably 12,000～8,000.If molecular weight surpasses 20,000, with respect to (A3) water-soluble cellulose derivative and summation 100 mass parts that (D3) have the acrylic resin of hydroxyl, (D3) have below preferred 50 mass parts of acrylic resin of hydroxyl so.

In addition, with respect to total resinous principle amount 100 mass parts in the compound film formation material, (D3) have preferred 50～90 mass parts of content of the acrylic resin of hydroxyl, more preferably 60～80 mass parts, most preferably 65～75 mass parts.Allotment amount by making (D) composition can make the performances such as generation of the formation precision of pattern, anti-development, developing performance, development residue all good in described scope, thereby preferred.

[other]

In addition, except described (A3)～(D3) composition, also can in organic principle, add following additive as required aptly: ultra-violet absorber, sensitizer, sensitization auxiliary agent, polymerization inhibitor, plasticizer, thickener, organic solvent, dispersant, defoamer, organic or inorganic antisettling agent etc.

Adding sensitizer is in order to improve sensitivity.Particularly; can enumerate: 2; the 4-diethyl thioxanthone; isopropyl thioxanthone; 2; two (the 4-diethylamino benzal) cyclopentanone of 3-; 2; two (the 4-dimethylamino benzal) cyclohexanone of 6-; 2; two (4-dimethylamino the benzal)-4-methyl cyclohexanones of 6-; michaelis ketone (Michler ' s ketone); 4; two (the diethylamino)-benzophenone of 4-; 4; two (dimethylamino) chalcones of 4-; 4; two (diethylamino) chalcones of 4-; to dimethylamino cinnamylidene indone; to dimethylamino benzal indone; 2-(to the dimethylaminophenyl ethenylidene)-different aphthothiazoles; 1; two (the 4-dimethylamino benzal) acetone of 3-; 1; 3-carbonyl-two (4-diethylamino benzal) acetone; 3,3-carbonyl-two (7-diethyl amino coumarin); N-phenyl-N-ehtylethanolamine; the N-phenylethanol amine; N-tolyl diethanol amine; the N-phenylethanol amine; the dimethylaminobenzoic acid isopentyl ester; the diethylamino isoamyl benzoate; 3-phenyl-5-benzoyl sulfo-tetrazolium; 1-phenyl-5-ethoxy carbonyl sulfo-tetrazolium etc.These sensitizers can use separately, also can use two or more simultaneously.

Add polymerization inhibitor and be in order to improve the thermal stability when preserving.Particularly, can enumerate: the mono-esterification thing of hydroquinones, hydroquinones, N-nitroso diphenylamine, phenthazine, p-tert-butyl catechol, N-nonox, 2,6-two-tert-butyl group-p-methyl phenol, tetrachloroquinone, pyrogallol etc.

Add plasticizer and be in order to improve the followability of composite membrane to substrate, plasticizer can use phthalate etc.More specifically, can enumerate: dibutyl phthalate (DBP), dioctyl phthalate (DOP), dicyclohexyl phthalate, polyethylene glycol, glycerol, dibutyl tartrate etc.

Adding defoamer is in order to reduce the bubble in compound film formation material or the composite membrane, the hole after the minimizing roasting.Particularly, can enumerate: polyethylene glycol alkane glycol system, silicone-based, higher alcohols such as (molecular weight are 400～800) are defoamer etc.

Described composite membrane can be formed material dissolves or be scattered in the solvent and be prepared.Solvent is preferably higher with the compatibility of inorganic constituents, the solvent of the favorable solubility of organic principle.In addition, so long as can give the viscosity of appropriateness to compound film formation material, and can easily evaporate the solvent of removing by drying, then be not particularly limited.Particularly, can enumerate: ketones such as metacetone, methyl butyl ketone, dipropyl ketone, cyclohexanone; Alcohols such as n-amyl alcohol, 4-methyl-2-amylalcohol, cyclohexanol, diacetone alcohol; Ethers such as glycol monoethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, dihydroxypropane single-ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether are alcohols; Representative examples of saturated aliphatic such as n-butyl acetate, pentyl acetate monocarboxylic acid alkyl esters; Lactic acid ester such as ethyl lactate, n-butyl lactate; Methylcellosolve acetate, ethyl cellosolve acetate, propylene glycol methyl ether acetate, propylene glycol monoethyl ether acetate, ethyl-3-ethoxy-c acid esters, acetate-2-methoxyl group butyl ester, acetate-3-methoxyl group butyl ester, acetate-4-methoxyl group butyl ester, acetate-2-methyl-3-methoxyl group butyl ester, acetate-3-methyl-3-methoxyl group butyl ester, acetate-3-ethyl-3-methoxyl group butyl ester, acetate-2-ethyoxyl butyl ester, acetate-4-ethyoxyl butyl ester, acetate-4-propoxyl group butyl ester, acetate-ethers such as 2-methoxyl group pentyl ester are ester class etc.These solvents can use separately, also can be used in combination of two or more simultaneously.

For the viscosity with compound film formation material maintains in the comparatively suitable scope, with respect to summation 100 mass parts of organic principle and inorganic constituents, below preferred 300 mass parts of the content of solvent.More preferably 10～70 mass parts, more preferably 25～35 mass parts.

Be used to form in the compound film formation material of base material of cathode 30 of this example, summation 100 mass parts with respect to compound film formation material, the ratio of described organic principle and described inorganic powder is preferred: organic principle is 5～35 mass parts, and inorganic constituents is 95～65 mass parts.More preferably organic principle is 10～30 mass parts, and inorganic constituents is 90～70 mass parts, and more preferably organic principle is 15～25 mass parts, and inorganic constituents is 85～75 mass parts.

[patterning composite membrane]

Compound film formation material can be suitable for it is coated on the described supporter 31, and perhaps silk screen printing is in supporter 31 first-class methods.When needs form more pattern with high precision, preferably will be coated with compound film formation material and in addition dry and dry film that form and attach and be transferred on the supporter 31.Can use applicator, rod coater, line rod coater, roll coater, episodic curtain coater etc. during coating.The film thickness uniformity excellence of roll coater particularly, and can form thicker film expeditiously, therefore preferred.

Be formed on composite membrane on the supporter 31 to aforesaid by coating or transfer printing, irradiation ultraviolet radiation, excimer laser, X ray, electron beam isoreactivity light or radioactive ray carry out image exposure via mask.Then, use alkaline-based developer or water to implement development treatment, the dissolving of irradiation portion is not removed, and as required the patterning composite membrane that forms on the supporter 31 is carried out roasting.Perhaps do not use mask and to the exposure of whole composite membrane, do not carry out development treatment and form the patterning composite membrane, carry out roasting as required.When forming more pattern with high precision, dry film is transferred on the supporter 31, carry out image exposure after, implement development treatment, form the patterning composite membrane thus.Perhaps do not carry out image exposure but to the exposure of whole composite membrane, do not carry out development treatment then and form sclerosis, carry out roasting as required by overlay film.Sintering temperature for example can be chosen in 400～600 ℃ of following roastings 10～90 minutes so long as the temperature of the organic principle burn off in the compound film formation material can be got final product.That is to say that " composite membrane " of this example reaches " patterning composite membrane " and comprise that also organic principle is by the film of burn off.In addition, during the transfer printing dry film, can utilize the hot-roll lamination machine to wait and carry out hot press.The employed radiation exposure device that exposes can use normally used ultraviolet lamp in the photolithography (photolithography), and employed exposure device etc. when making semiconductor and liquid crystal indicator.

The alkali composition that is used for the alkaline-based developer of development treatment can be enumerated: alkali-metal hydroxide such as lithium, sodium, potassium; Carbonate, heavy carbonate, phosphate, pyrophosphate; Primary amine such as benzylamine, butylamine; Secondary amine such as dimethylamine, dibenzylamine, diethanol amine; Tertiary amines such as trimethylamine, triethylamine, triethanolamine; Cyclic amine such as morpholine, piperazine, pyridine; Polyamines such as ethylenediamine, hexamethylene diamine; Ammonium hydroxide classes such as Tetramethylammonium hydroxide, tetraethyl ammonium hydroxide, trimethyl benzyl ammonium hydroxide, trimethylphenyl benzylic hydrogens amine-oxides; Trimethyl hydroxide sulfonium class; Sulfonium hydroxide classes such as trimethyl hydroxide sulfonium, diethylmethyl hydroxide sulfonium, dimethyl benzyl hydroxide sulfonium; Choline, contain the buffer solution of silicate etc.In addition, during development treatment, form properties of materials according to composite membrane, and select kind, composition, the concentration of developer solution aptly, developing time, development temperature, developing method (for example infusion process, suspension system, spray process, spray-on process, paddling process), developing apparatus etc.

In addition, the aspect ratio of the patterning composite membrane that obtains in this way is preferred more than 0.1.By the aspect ratio that makes the patterning composite membrane is more than 0.1, and the surface area of base material of cathode 30 is increased, and can make aftermentioned handle the metal film amount increase that forms by plating, thereby realizes higher output and higher energy density.

(the 4th example)

＜base material of cathode 〉

Fig. 4 represents the schematic diagram of the base material of cathode 40 of this example.As shown in Figure 4, the base material of cathode 40 of this example comprises: supporter 41, silica-based by overlay film 42 and metal film 43.More specifically, the base material of cathode 40 of this example more possesses metal film 43 having the silica-based by the surface of the supporter 41 of overlay film 42 of patterning.

Can utilize following mode and obtain the base material of cathode 40 of this example.At first, on supporter 41, form the photoresistance pattern.On formed photoresistance pattern, be coated with silica-based formation and use coating fluid by overlay film, form silica-based by overlay film.Then, unwanted photoresistance pattern is removed, on supporter 41, obtained the silica-based of patterning thus by overlay film 42.At last, silica-basedly form metal film 43 on by the supporter 41 of overlay film 42 what have a patterning.

＜supporter 〉

Can form photoresistance pattern or silica-based in its surface as long as be used for the supporter 41 of the base material of cathode 40 of this example, be not particularly limited by overlay film 42.For example, can use electronic component with well-known in the past supporters such as substrates.Particularly, can enumerate: silicon chip, be provided with organic system or inorganic be the silicon chip of anti-reflective film, formed the silicon chip of magnetic film, metal substrates such as copper, chromium, iron, aluminium, or glass substrate etc.In addition, these supporters also can comprise the material that is selected from least a element in copper, nickel, stainless steel, molybdenum, tungsten, titanium and the tantalum by double as, metal forming, and adhesive-bonded fabric, the collector bodies such as metal current collector with three-dimensional structure also can be formed on these collector bodies.

[photoresistance composition, photoresistance pattern]

The photoresistance composition, the photoresistance pattern that are used to form the base material of cathode 40 of this example are to use photoresistance composition, the photoresistance pattern identical with first example.

＜silica-based by overlay film

Silica-based by overlay film 42 in the base material of cathode 40 of this example formed by silica-based formation with coating fluid by overlay film.Particularly, be on formed photoresistance pattern on the base material of cathode 40, be coated with and silica-basedly formed with behind the coating fluid by overlay film, remain in silica-based on the supporter 41 when removing the removing photoresistance pattern by overlay film 42.Contain the silica-based by overlay film formation composition of siloxane polymer and solvent described silica-based being comprised with coating fluid by overlay film formation.

[siloxane polymer]

As siloxane polymer, preferably make at least a product that is hydrolyzed reaction and obtains that is selected from in the represented silane compound of following general formula (I).

[changing 34]

R _4-nSi(OR’) _n (I)

In the described general formula (I), R represents hydrogen atom, alkyl or phenyl, and R ' represents alkyl or phenyl, and n represents 2～4 integer.When a plurality of R and Si bonding, these a plurality of R can be the same or different.Can be the same or different with a plurality of (OR ') group of Si bonding.As the preferred carbon number of the alkyl of R is 1～20 straight chain shape or the alkyl that props up chain, and more preferably carbon number is 1～4 straight chain shape or the alkyl that props up chain.As the preferred carbon number of the alkyl of R ' is 1～5 straight chain shape or the alkyl that props up chain.Particularly considering from the hydrolysis rate aspect, is 1 or 2 as the preferred carbon number of the alkyl of R '.

When the n in the described general formula (I) was 4, silane compound (i) was represented with following general formula (II).

[changing 35]

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

In the described general formula (II), R ¹, R ², R ³And R ⁴The independent respectively expression alkyl or phenyl identical with described R '.A, b, c and d satisfy 0≤a≤4,0≤b≤4,0≤c≤4,0≤d≤4, and the integer of the condition of a+b+c+d=4.

When the n in the described general formula (I) was 3, silane compound was (ii) represented with following general formula (III).

[changing 36]

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

In the described general formula (III), R ⁵Expression hydrogen atom, the alkyl or phenyl identical with described R.R ⁶, R ⁷And R ⁸The independent respectively expression alkyl or phenyl identical with described R '.E, f and g satisfy 0≤e≤3,0≤f≤3,0≤g≤3, and the integer of the condition of e+f+g=3.

When the n in the described general formula (I) was 2, silane compound was (iii) represented with following general formula (IV).

[changing 37]

R ⁹R ¹⁰Si(OR ¹¹) _b(OR ¹²) _i (IV)

In the described general formula (IV), R ⁹And R ¹⁰Expression hydrogen atom, the alkyl or phenyl identical with described R.R ¹¹, and R ¹²The independent respectively expression alkyl or phenyl identical with described R '.H and i satisfy 0≤h≤2,0≤i≤2, and the integer of the condition of h+i=2.

The concrete example of described silane compound (i) can be enumerated: tetramethoxy-silicane, tetraethoxysilane, tetrapropoxysilane, four butoxy silanes, four amoxy silane, tetraphenoxy-silicane alkane, trimethoxy monosubstituted ethoxy silane, the dimethoxy diethoxy silane, triethoxy mono methoxy silane, trimethoxy list propoxyl group silane, mono methoxy three butoxy silanes, mono methoxy three amoxy silane, mono methoxy triple phenoxyl silane, dimethoxy dipropoxy silane, tripropoxy mono methoxy silane, trimethoxy only son TMOS, dimethoxy dibutoxy silane, triethoxy list propoxyl group silane, diethoxy dipropoxy silane, three butoxy list propoxyl group silane, dimethoxy monosubstituted ethoxy only son TMOS, diethoxy mono methoxy only son TMOS, diethoxy list propoxyl group only son TMOS, dipropoxy mono methoxy monosubstituted ethoxy silane, dipropoxy mono methoxy only son TMOS, dipropoxy monosubstituted ethoxy only son TMOS, dibutoxy mono methoxy monosubstituted ethoxy silane, dibutoxy monosubstituted ethoxy list propoxyl group silane, tetraalkoxysilanes such as mono methoxy monosubstituted ethoxy list propoxyl group only son TMOS, wherein, preferred tetramethoxy-silicane, tetraethoxysilane.

Described silane compound concrete example (ii) can be enumerated: trimethoxy silane, triethoxysilane, tripropoxy silane, three amoxy silane, triple phenoxyl silane, dimethoxy monosubstituted ethoxy silane, diethoxy mono methoxy silane, dipropoxy mono methoxy silane, dipropoxy monosubstituted ethoxy silane, two amoxy mono methoxy silane, two amoxy monosubstituted ethoxy silane, two amoxy list propoxyl group silane, two phenoxy group mono methoxy silane, two phenoxy group monosubstituted ethoxy silane, two phenoxy group list propoxyl group silane, methoxy ethoxy propoxyl group silane, single propoxyl group dimethoxy silane, single propoxyl group diethoxy silane, single butoxy dimethoxy silane, single amoxy diethoxy silane, single phenoxy group diethoxy silane, methyltrimethoxy silane, methyl triethoxysilane, methyl tripropoxy silane, methyl three amoxy silane, ethyl trimethoxy silane, ethyl tripropoxy silane, ethyl three amoxy silane, ethyl triple phenoxyl silane, propyl trimethoxy silicane, propyl-triethoxysilicane, propyl group three amoxy silane, propyl group triple phenoxyl silane, butyl trimethoxy silane, the butyl triethoxysilane, butyl tripropoxy silane, butyl three amoxy silane, butyl triple phenoxyl silane, methyl mono methoxy diethoxy silane, ethyl mono methoxy diethoxy silane, propyl group mono methoxy diethoxy silane, butyl mono methoxy diethoxy silane, methyl mono methoxy dipropoxy silane, methyl mono methoxy diamyl TMOS, methyl mono methoxy hexichol TMOS, ethyl mono methoxy dipropoxy silane, ethyl mono methoxy diamyl TMOS, ethyl mono methoxy hexichol TMOS, propyl group mono methoxy dipropoxy silane, propyl group mono methoxy diamyl TMOS, propyl group mono methoxy hexichol TMOS, butyl mono methoxy dipropoxy silane, butyl mono methoxy diamyl TMOS, butyl mono methoxy hexichol TMOS, methyl methoxy base oxethyl propoxyl group silane, propyl group methoxy ethoxy propoxyl group silane, butyl methoxy ethoxy propoxyl group silane, methyl mono methoxy monosubstituted ethoxy only son TMOS, ethyl mono methoxy monosubstituted ethoxy only son TMOS, propyl group mono methoxy monosubstituted ethoxy only son TMOS, butyl mono methoxy monosubstituted ethoxy only son TMOS etc., wherein, preferred trimethoxy silane, triethoxysilane, methyltrimethoxy silane.

Described silane compound concrete example (iii) can be enumerated: dimethoxy silane, diethoxy silane, dipropoxy silane, the diamyl TMOS, the hexichol TMOS, methoxy ethoxy silane, methoxy propoxy silane, methoxyl group amoxy silane, the methoxybenzene TMOS, the ethoxy-c TMOS, ethyoxyl amoxy silane, the phenoxy ethoxy base silane, methyl dimethoxysilane, methyl methoxy base oxethyl silane, methyldiethoxysilane, methyl methoxy base propoxyl group silane, methyl methoxy base amoxy silane, methyl methoxy phenoxyl silane, ethyl dipropoxy silane, ethyl methoxy propoxy silane, ethyl diamyl TMOS, ethyl hexichol TMOS, propyl group dimethoxy silane, propyl group methoxy ethoxy silane, propyl group ethoxy-c TMOS, the propyl group diethoxy silane, propyl group diamyl TMOS, propyl group hexichol TMOS, butyl dimethoxy silane, butyl methoxy ethoxy silane, the butyl diethoxy silane, butyl ethoxy-c TMOS, butyl dipropoxy silane, butyl methyl diamyl TMOS, butyl methyl hexichol TMOS, dimethyldimethoxysil,ne, dimethyl methoxy base oxethyl silane, dimethyldiethoxysilane, dimethyl diamyl TMOS, dimethyl hexichol TMOS, dimethyl ethoxy-c TMOS, dimethyl dipropoxy silane, diethyl dimethoxy silane, diethyl methoxy propoxy silane, the diethyl diethoxy silane, diethyl ethoxy-c TMOS, dipropyl dimethoxy silane, the dipropyl diethoxy silane, dipropyl diamyl TMOS, dipropyl hexichol TMOS, dibutyl dimethoxy silane, the dibutyl diethoxy silane, dibutyl dipropoxy silane, dibutyl methoxyl group amoxy silane, dibutyl methoxybenzene TMOS, Methylethyl dimethoxy silane, the Methylethyl diethoxy silane, Methylethyl dipropoxy silane, Methylethyl diamyl TMOS, Methylethyl hexichol TMOS, methyl-propyl dimethoxy silane, the methyl-propyl diethoxy silane, methyl butyl dimethoxy silane, the methyl butyl diethoxy silane, methyl butyl dipropoxy silane, Methylethyl ethoxy-c TMOS, ethyl propyl dimethoxy silane, ethyl propyl methoxy ethoxy silane, dipropyl dimethoxy silane, dipropyl methoxy ethoxy silane, propyl group butyl dimethoxy silane, propyl group butyl diethoxy silane, dibutyl methoxy ethoxy silane, dibutyl methoxy propoxy silane, dibutyl ethoxy-c TMOS etc., wherein, preferred dimethoxy silane, diethoxy silane, methyl dimethoxysilane, methyldiethoxysilane.

Among these silane compounds, the combination of preferable methyl trialkoxy silane and tetraalkoxysilane.Preferred 30: 70～90: 10 of the allotment mol ratio of methyl trialkoxysilane and tetraalkoxysilane.

In addition, described siloxane polymer preferable weight-average molecular weight is 1,000～10, in 000 the scope.This mainly is because guarantee the flatness of film forming or film easily, and etch-rate patience is also very excellent.If particularly molecular weight is low excessively, siloxane polymer can volatilize so, might can't form film.

[solvent]

Described solvent can be enumerated: monohydric alcohols such as methyl alcohol, ethanol, propyl alcohol, butanols; Polyalcohols such as ethylene glycol, diethylene glycol, propylene glycol, glycerol, trimethylolpropane, hexanetriol; The monoether class of polyalcohols such as glycol monoethyl ether, ethylene glycol monoethyl ether, ethylene glycol 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, dihydroxypropane single-ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether; Ester classes such as methyl acetate, ethyl acetate, butyl acetate; Ketones such as acetone, methyl ethyl ketone, naphthenic one, methyl isoamyl ketone; Glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol bisthioglycolate propyl ether, butyl cellosolve, Propylene Glycol Dimethyl Ether (PGDM), propylene glycol diethyl ether, propylene glycol butyl oxide, diethylene glycol dimethyl ether, diethylene glycol MEE, diethylene glycol diethyl ether etc. are with polyalcohol ethers of the whole alkyl etherificates of hydroxyl groups etc.Among these, more preferably naphthenic one or alkane glycol dialkyl ether.In addition, the preferred PGDM of alkane glycol dimethyl ether (Propylene Glycol Dimethyl Ether).These organic solvents can use separately, also can be used in combination of two or more.The allotment amount of described solvent preferably silica-based be the scope of 70～99 quality % in being formed with composition by overlay film.

[other]

Described silica-based formation with composition by overlay film also can contain other compositions except described siloxane polymer and solvent.For example, also can contain the ring-type alkali compounds.The preferred cyclic amine of this ring-type alkali compounds more specifically, can be used DBU (1,8-diazabicyclo (5.4.0) 11 carbon-7-alkene, 1,8-diazabicyclo (5.4.0) undec-7-ene) aptly.

With respect to the solid constituent amount of described siloxane polymer, the preferred 10ppm of the addition of described ring-type alkali compounds～1%.If the addition of described ring-type alkali compounds in this scope, just can promote that siloxane polymer carries out polymerization, reduce by the amount of moisture in the overlay film.And the silica-based stability of solution that is formed with composition by overlay film improves, and it is good that coating becomes.

In addition, described silica-basedly formed with also containing pore former in the composition by overlay film.So-called pore former is meant to being decomposed when carrying out roasting by silica-based formation with formed the filming of composition by overlay film, thereby makes finally formed silica-based by the material of formation hole on the overlay film 42.This pore former for example can be enumerated the end alkyl thing of poly-alkane glycol and poly-alkane glycol.

The carbon number of the alkylene of described poly-alkane glycol is preferred 1～5, and more preferably 1～3.The concrete example of poly-alkane glycol can be enumerated: lower alkyl glycol such as polyethylene glycol, polypropylene glycol.

The end alkyl thing of described poly-alkane glycol is meant that the single end of poly-alkane glycol or the hydroxyl of two ends utilize alkyl and alkoxylate.The alkyl that is used for making end alkoxy groupization can be the alkyl of a straight chain shape or a chain, and the carbon number of this alkyl is preferred 1～5, more preferably 1～3.The alkyl of straight chain shapes such as special preferable methyl, ethyl, propyl group.

The weight average molecular weight of this poly-alkane glycol (Mw) is preferred 100～10,000, and more preferably 200～5,000, more preferably 400～4,000.By making weight average molecular weight below the higher limit of described scope, can not damage described poly-alkane glycol in coating fluid compatibility and obtain good coating, and silica-based film thickness uniformity by overlay film 42 is good.By making weight average molecular weight more than the lower limit of described scope, can make silica-basedly to be formed cellular, thereby play bigger cushioning effect by overlay film 42, thereby preferred.

With respect to the silica-based solid constituent (SiO that uses composition that formed by overlay film ₂Reduced mass), preferred 25～100 quality % of the use amount of described pore former, more preferably 30～70 quality %.Use amount by making solvent composition can make silica-basedly to be formed cellulars by overlay film 42 more than the lower limit of described scope, and the use amount by making it is below the higher limit of described scope, and it is fully silica-based by overlay film 42 to obtain intensity.

Described silica-based be to obtain in the following manner by overlay film 42: on the supporter 41 that has formed the photoresistance pattern, be coated with silica-based formation and use coating fluid, carry out after heat drying and the roasting, except that the removing photoresistance pattern by overlay film.The silica-based coating process that is formed with coating fluid by overlay film is not particularly limited, for example can adopts coating process arbitrarily such as spray-on process, spin-coating method, dip coating, print roll coating method.

Heat drying preferably 80～300 ℃ of down dry 1～6 fen clock times, more preferably divided for 3 stages heated up to come up interimly.For example, in atmosphere or in the inert gas environment such as nitrogen, drying is 30 seconds～2 minutes under 70～120 ℃, as the 1st dried, afterwards, drying is 30 seconds～2 minutes under 130～220 ℃, as the 2nd dried, then, drying is 30 seconds～2 minutes under 150～300 ℃, as the 3rd dried.Like this, by carrying out more than 3 stages, the dried of the stage about preferred 3～6 stages can make the surface of filming become even.

In addition, preferably under the temperature about 300～400 ℃, carry out roasting in the nitrogen environment.

Silica-based by overlay film for the top that is formed on the photoresistance pattern can carry out etch processes (eat-backing) etc. by the whole face to supporter aptly and this is silica-basedly removed by overlay film.In addition, Ci Shi etch processes can adopt well-known engraving method to carry out.

Employed stripper is not particularly limited when removing the removing photoresistance pattern, can use well-known in the past photoresistance stripper.For example, also can use organic system stripper, water system stripper, O ₂In the ashing treatment any.

[embodiment]

Below, use embodiment to illustrate in greater detail the present invention.But the present invention is not limited to following examples.

＜pattern forms 〉

[embodiment 1]

With diphenyl [4-(thiophenyl) phenyl] the sulfonium hexafluorophosphate of the multifunctional bisphenol-A phenolic type epoxy resin of 100 mass parts " Epikote 157S70 (trade name; japan epoxy resin company makes) ", 5 mass parts and sulfo-two-to 1 of the mixture " UVI-6992 (trade name; Dow Chemical's manufacturing) " of penylene-two (diphenyl sulfonium)-two (hexafluorophosphates), 5 mass parts, the gamma-butyrolacton of 5-dihydroxy naphthlene and 43 mass parts mixes, preparation minus photoresistance composition 1.

[embodiment 1a]

After using the rotary coating machine to be coated on this minus photoresistance composition 1 on the silicon chip, in addition dry, obtain to have the photosensitive polymer combination layer of the thickness of 20 μ m.Utilize hot plate, to this minus photoresistance composition layer 1 60 ℃ of following prebake conditions 5 minutes and 90 ℃ of following prebake conditions 5 minutes.Then, use PLA-501F (contact aligner, Canon Inc. makes) to carry out pattern exposure (soft contact, GHI line), utilize hot plate under 90 ℃, to carry out exposure back heating (PEB) in 5 minutes, use PGMEA, utilize infusion process to carry out 4 minutes development treatment.Then, use baking oven, the resin pattern after developing is toasted after carrying out 1 hour under 200 ℃ together with substrate, obtaining width thus on silicon chip is the photoresistance pattern 1a of the column of 10 μ m (spacing is 20 μ m).

[embodiment 1b]

In addition, with 1 mass parts with the represented compound of following structural formula (z1) (K-1S (trade name), San-Apro company makes), 40 mass parts with the represented resin that increases owing to the effect of acid with respect to the dissolubility of alkali of following structural formula (z2), 60 mass parts in the presence of formaldehyde and acid catalyst, the phenolic resins that makes metacresol and paracresol addition condensation and obtain, and 1 mass parts 1, the 5-dihydroxy naphthlene, be dissolved in the propylene glycol methyl ether acetate equably, by the aperture is that the filter membrane of 1 μ m filters, preparation solid constituent mass concentration is the eurymeric photoresistance composition of 40 quality %, utilize and form identical method with the pattern of described minus photoresistance composition, obtaining width on silicon chip is the photoresistance pattern 1b of the column of 10 μ m (spacing is 20 μ m).

[changing 38]

[embodiment 1c]

Will be as use metacresol/paracresol/2 of (A) composition, 3, the mixing phenols of 5-pseudocuminol=40/35/25 (mol ratio), with the mixing aldehydes and utilize well-established law and synthetic Mw=5 of salicylide/formaldehyde=1/5 (mol ratio), 200 phenolic resins 13g, two (5-cyclohexyl-4-hydroxy-2-methyl phenyl)-3 of 1 mole as (B) composition, 4-dihydroxy benzenes methylmethane (B1) with 2 moles 1,2-naphthoquinones diazido-5-sulfonic acid chloride [below, abbreviate (5-NQD) as] esterification reaction product, 1 mole two (2, the 4-dihydroxy phenyl) esterification reaction product of methane (B2) and 2 moles 5-NQD, two (4-hydroxyls-2 with 1 mole, 3, the 5-trimethylphenyl)-the mixture 7.5g (mass mixing ratio=B1: B2: B3=4: 1: 1) of 2-hydroxy phenyl methane (B3) and the esterification reaction product of 2 moles 5-NQD, two (2-methyl-4-hydroxy phenyl)-phenylmethane 5.5g as (C) composition, and propylene glycol methyl ether acetate solvent 74g is mixed preparation eurymeric photoresistance composition.

This eurymeric photoresistance composition is coated on the silicon chip, carries out prebake conditions and handle, forming thickness is the organic membrane of 1.48 μ m.Use i line exposing device (ProductName " NSR-2005i10D ", Tokyo answers chemical industry company to make) optionally this organic membrane is exposed, then, utilizing concentration is the tetramethylammonium hydroxide aqueous solution (ProductName " NMD-3 " of 2.38 quality %, Tokyo answers chemical industry company to make) carry out 60 second development treatment, carry out flushing in 30 seconds with pure water and handle, pass through drying steps then, forming width is the patterning organic membrane 1c of the column of 5 μ m (spacing is 20 μ m).

[embodiment 2a]

Except not forming the metal oxide film, the same operation of utilization and embodiment 1a forms the photoresistance pattern.On the other hand, in the mode that reaches 100mM with four isocyanic acid silane (Si (NCO) ₄) be dissolved in the terpane, the preparation metal oxide film forms material.By spin coating (being coated with for 10 seconds) with 100rpm, after being coated on this metal oxide film formation material on the photoresistance pattern equably, with terpane being cleaned (cleaning for 10 seconds) with 500rpm, carry out drying for 10 seconds with 2000rpm then, carry out drying for 10 seconds with 3000rpm.As a result, acquisition has formed uniform coating (silicon oxide film (SiO on the surface of photoresistance pattern ₂)) photoresistance pattern 2a.This coating is the ultrathin membrane that thickness is about 1nm.

[embodiment 2b]

Except using photoresistance pattern 1b, utilize with the same method of embodiment 2a and form photoresistance pattern 2b.

[embodiment 3]

Utilize mixer, will be as hydroxy propyl cellulose 5 mass parts of water-soluble cellulose derivative, styrene/methacrylic acid hydroxy methacrylate=60/40 (quality %) copolymer (Mw=30000) 5 mass parts as acrylic resin with hydroxyl, acrylic acid-2-hydroxyl-3-phenoxy group propyl ester (trade name M-600A as photopolymerization monomer, chemistry limited company of common prosperity society makes) 15 mass parts, as 2 of Photoepolymerizationinitiater initiater, 2-dimethoxy-2-phenyl acetophenone (trade name IR-651, Ciba-Geigy company makes) 1.0 mass parts, dicyclohexyl phthalate 12 mass parts as plasticizer, and mixed preparation organic principle solution 3 hours as ethyl acetate 100 mass parts of solvent.Then, to this organic principle solution (solid constituent is 50 quality %) 35 mass parts with mix as glass paste 82.5 mass parts of inorganic constituents, prepare compound film formation material.

Then, above prepared compound film formation material is coated on the polyethylene terephthalate, to dried coating film 6 minutes, solvent is removed fully under 100 ℃, forming thickness is the composite membrane of 27 μ m.

Then, utilize the hot-roll lamination machine, under 105 ℃ the composite film of above manufacturing is being pressed onto on the silicon chip that is heated to 80 ℃ in advance.Air pressure is 3kg/cm ², laminate speed is 1.0m/min.Then, will peel off, utilize extra-high-pressure mercury vapour lamp as the polyethylene terephthalate of support membrane, via pattern mask with 500mJ/cm ²Exposure carry out ultraviolet exposure.Use liquid temperature is 30 ℃ a water, with 3kg/cm ²Expulsion pressure, a little 5 times the spray development of developing, forming width is the patterning composite membrane 3 of the column of 10 μ m (spacing is 20 μ m).Wherein, so-called development point is meant the time till unexposed complete obiteration when carrying out exposure-processed.

[embodiment 4]

Except that the solid constituent mass concentration is 20 quality %, with the method acquisition eurymeric photoresistance composition same with embodiment 2b.

After utilizing the rotary coating machine to be coated on this eurymeric photoresistance composition on the silicon chip, carry out drying, obtain to have the photosensitive polymer combination layer of 2 μ m thickness.Utilize hot plate under 130 ℃ to this eurymeric photoresistance composition layer prebake conditions 1 minute.Then, use PLA-501F (contact aligner, Canon Inc. makes) to carry out pattern exposure (soft contact, the GHI line), utilize hot plate under 75 ℃, to carry out exposure back heating (PEB) in 5 minutes, use the tetramethyl ammonium hydroxide of 3 quality %, utilize infusion process to carry out 2 minutes development treatment.Obtaining diameter thus on silicon chip is the photoresistance pattern of the hole shape of 1 μ m (spacing is 2 μ m).

On the other hand, 220.0g methyltrimethoxy silane, 246.0g tetramethoxy-silicane, 301.0g propylene glycol monopropyl ether are mixed, stir.In this mixture, add 60% nitric acid of 204.0g water, 52 μ L, stirred again 3 hours.Then, reacted 2 days down at 26 ℃.With the DBU of the described reactant of 8.0g, 11.8g propylene glycol monopropyl ether, 0.2g is that 0.1% propylene glycol monopropyl ether solution is mixed, and obtains silica-based formation by overlay film and uses composition.

By spin coating, the silica-based formation by overlay film that is obtained is coated on the described silicon chip that forms the photoresistance pattern with composition, 80 ℃, 150 ℃, and each hot plate of 200 ℃ on heated respectively 1 minute.Then, use and to peel off 104 (Tokyo answers chemical industry company to make), under 70 ℃, carry out 20 minutes impregnation process, then in nitrogen environment, 400 ℃ of following roastings 30 minutes, form thickness and be about the silica-based of 2 μ m by overlay film 4.

The making of＜base material of cathode 〉

This has been formed the silicon chip of silicon oxide film on photoresistance pattern 1a and 1b, photoresistance pattern 2a, 2b have perhaps been formed, patterning composite membrane 3, the silica-based silicon chip by overlay film 4 or patterning organic membrane 5 on the pattern flooded for 60 seconds in sodium radio-phosphate,P-32 solution, carried out clean.Then, will be through the silicon chip of described cleaning step at 0.05g/dm ³Stannic chloride (SnCl ₂) 60 seconds of dipping in the aqueous solution, afterwards at 0.05g/dm ³Palladium bichloride (PdCl ₂) 60 seconds of dipping in the aqueous solution, carry out catalysis thinner step with this.

Then, will be immersed in through the silicon chip of described catalysis thinner step in the nickel plating bath of carboxylic acids complexing agent of lead ion, 0.30M of sodium hypophosphite, the 0.30ppm of the nickelous sulfate that comprises 0.20M, 0.30M and carry out Nickel Plating Treatment.In addition, the temperature of the nickel plating bath of this moment is 70 ℃, and the pH value is adjusted into 5.5.

Then, will be immersed in through the silicon chip of described electroless plating nickel step in the zinc-plated bath of trisodium citrate of reducing agents such as titanium trichloride, 0.50M of the stannic chloride that comprises 0.20M, 0.08M and carry out zinc-plated processing.In addition, the temperature of the zinc-plated bath of this moment is 70 ℃, and the pH value is adjusted into 8.5.

Make: use the base material of cathode with the photoresistance pattern 1a that is obtained among the described embodiment 1 nonaqueous electrolytic solution secondary battery (below, be called battery embodiment 1a), use have the base material of cathode of photoresistance pattern 1b nonaqueous electrolytic solution secondary battery (below, be called battery embodiment 1b), use have the base material of cathode of photoresistance pattern 2a nonaqueous electrolytic solution secondary battery (below, be called battery embodiment 2a), use have the base material of cathode of photoresistance pattern 2b nonaqueous electrolytic solution secondary battery (below, be called battery embodiment 2b), use have the base material of cathode of patterning composite membrane 3 nonaqueous electrolytic solution secondary battery (below, be called battery embodiment 3), use have on the pattern silica-based by the nonaqueous electrolytic solution secondary battery of the base material of cathode of overlay film 4 (below, be called battery embodiment 4), use has the nonaqueous electrolytic solution secondary battery (below, be called battery embodiment 5) of the base material of cathode of patterning organic membrane 5.Utilize following method to measure the discharge capacity of these batteries after 1～3 circulation.The results are shown in following table 1.

Nonaqueous electrolytic solution secondary battery is to utilize following mode to make.Each base material of cathode of obtaining among the embodiment as work electrode, is used LiCoO ₂Be used as electrode (positive pole), make the two poles of the earth across barrier film and subtend.Use LiPF ₆The mixed liquor of/ethylene carbonate and dimethyl carbonate (capacity ratio is 1: 1) as nonaqueous electrolytic solution, utilizes well-established law to make nonaqueous electrolytic solution secondary battery.In this nonaqueous electrolytic solution secondary battery, anodal capacity ratio with negative pole is 1: 1.

Measure the discharge capacity (mAh/cm of 1～3 circulation back per unit volume ²), as the discharge capacity of each nonaqueous electrolytic solution secondary battery.The discharge capacity of per unit volume is that volume with negative pole is as benchmark.But the expansion of negative pole when not considering to charge.

[table 1]

In the described base material of cathode, the enforcement of embodiment the surface area of base material of cathode of zinc-plated processing, be with plane and implement about 190% of situation that plating handles.The base material of cathode that only has patterning organic membrane 5 is about 115%.

[utilizability on the industry]

Utilize base material of cathode of the present invention, can realize having high output voltage and high-energy-density, and the battery of excellent charge, can be applied in employed compact battery from portable equipment etc., in hybrid vehicle etc. in the various uses of any electric capacity of employed large-sized battery.

Claims

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

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

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

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

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

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

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

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

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

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

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

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

[changing 1]

[changing 2]

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

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

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

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

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

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

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

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

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

(i) step of formation organic membrane on supporter;

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

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