JP2007272087A - Positive radiation-sensitive resin composition, transfer film and method for producing plated/shaped body - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a positive radiation-sensitive resin composition which exhibits excellent sensitivity to an active radiation and is excellent in resolution, adhesion, and the like. <P>SOLUTION: The radiation-sensitive resin composition comprises (A) an acid-dissociating group-containing resin comprising structural units of formulae (1) and (2), (B) a resin comprising a structural unit of formula (3), and (C) a photoacid generator. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a positive-type radiation-sensitive resin composition, a transfer film, and a method for producing a plated model. More specifically, a radiation-sensitive resin composition that exhibits excellent sensitivity to actinic radiation and is suitable for the production of a plated model, a radiation-sensitive resin film formed from this composition, and a transfer film having this resin film Moreover, it is related with the manufacturing method of the plating molded article using this composition.

  In recent years, with the miniaturization of integrated circuit elements, a large scale integrated circuit (LSI) is highly integrated and a shift to an integrated circuit (Application Specific Integrated Circuit: ASIC) adapted to a specific application is rapidly progressing. For this reason, multi-pin thin film mounting for mounting LSIs on electronic devices is required, and bare chip mounting using a tape automated bonding (TAB) method or a flip chip method has been adopted. In such a multi-pin thin film mounting method, it is necessary that a protruding electrode called a bump having a height of 10 μm or more is disposed on the substrate with high accuracy as a connection terminal.

  Such bumps are currently processed in the following procedure. First, a barrier metal serving as a conductive layer is laminated on a wafer on which an LSI element is processed, and then a radiation-sensitive resin composition, so-called resist, is applied and dried. Next, radiation is irradiated through a mask (hereinafter also referred to as “exposure”) so that a portion where a bump is formed is opened, and then development is performed to form a pattern. Next, an electrode material such as gold or copper is deposited by electrolytic plating using this pattern as a mold. Next, after peeling off the resin portion, the barrier metal is removed by etching. Thereafter, the chip is cut out from the wafer into a square, and the process proceeds to a packaging process such as TAB or a mounting process such as flip chip.

In the series of bump processing steps described above, the following characteristics are required for the resist.
(1) A coating film having a uniform thickness of 20 μm or more can be formed.
(2) High resolution to cope with narrow pitch of bumps.
(3) The side wall of the pattern serving as a mold is nearly vertical, and the pattern is faithful to the mask dimensions.
(4) High sensitivity and excellent developability in order to increase production efficiency of the process.
(5) It has good wettability with respect to the plating solution.
(6) The resist component does not elute into the plating solution during plating and does not deteriorate the plating solution.
(7) High adhesion to the substrate so that the plating solution does not ooze out to the interface between the substrate and the resist during plating.
(8) After plating, it should be easily peeled off with a stripping solution.
Furthermore, the resulting plating deposit is
(9) It is also necessary that the shape of the pattern serving as a mold is faithfully transferred and that the mask dimensions are faithful.

Conventionally, as a resist for bump processing, a positive radiation sensitive resin composition containing a novolak resin and a naphthoquinonediazide group-containing compound as main components has been used (for example, see Patent Document 1).
However, there is a problem that even if a resist made of the above composition is developed, the pattern shape becomes an inclined shape (forward taper shape) tapered from the substrate surface toward the resist surface, and a pattern having a vertical side wall cannot be obtained. there were. In addition, since the sensitivity of the resist composed of the above composition is low, there is a problem that the exposure time is long and the production efficiency is low. Furthermore, the resolution and the fidelity to the mask dimension of the thick plating deposits were not sufficient.

On the other hand, as a radiation sensitive resin composition suitable for various types of radiation, a component having an acidic functional group protected with an acid dissociable group, and a radiation sensitive acid generator that generates an acid upon exposure (hereinafter referred to as “acid generator”). Many compositions (chemically amplified radiation-sensitive compositions) that utilize the chemical amplification effect between them have been proposed.
For example, Patent Document 2 discloses a composition containing a polymer in which a carboxylic acid is protected with a t-butoxycarbonyl group or a polymer in which a phenolic hydroxyl group is protected with a t-butoxycarbonyl group, and an acid generator. ing. In the composition, the t-butoxycarbonyl group in the polymer is dissociated by the action of an acid generated by exposure to have an acidic group composed of a carboxyl group or a phenolic hydroxyl group. As a result, the exposed area of the resist film becomes easily soluble in an alkali developer, so that the exposure time is shortened and the production efficiency can be improved.

Further, for further improvement in production efficiency, shortening of the exposure time is required, and accordingly, development of a radiation sensitive resin composition exhibiting superior sensitivity has been strongly demanded.
Patent Document 3 contains a polymer in which a phenolic hydroxyl group is protected with a t-butoxycarbonyl group or an ethoxyethyl group and a resin containing an alkali-soluble group as a resin whose solubility in alkali is increased by the action of an acid. A chemically amplified positive photoresist containing an acrylic resin or a vinyl resin is disclosed. In particular, the composition contains an acrylic resin as the alkali-soluble group-containing resin, whereby adhesion to the substrate during development and plating solution resistance are improved.

JP-A-10-207057 JP 59-45439 A JP 2004-309776 A

  An object of the present invention is to provide a positive-type radiation-sensitive resin composition that exhibits excellent sensitivity to actinic radiation and is excellent in resolution, adhesion, and the like, and a thick film such as a bump or a wiring using the resin composition A method for producing a plated shaped article capable of forming a well-shaped plated shaped article excellent in adhesion to a substrate sputtered with a metal such as gold and the accuracy of plating dimensions when forming a plated shaped article, and An object is to provide a positive-type radiation-sensitive resin film formed from this resin composition and a transfer film having this resin film.

〔一般式（１）において、Ｒ^１は水素原子又はメチル基を示し、Ｒ^２はメチル基又はエチル基を示し、Ｒ^３は炭素数１〜６の直鎖状、分岐状若しくは環状のアルキル基を示す。尚、Ｒ^２及びＲ^３が相互に結合して環状構造を形成してもよい。〕

〔一般式（２）において、Ｒ^４は水素原子又はメチル基を示し、Ｒ^５は一価の有機基を示す。また、ｍは０〜４の整数であり、ｎは１〜４の整数である。〕

〔一般式（３）において、Ｒ^６は水素原子又はメチル基を示し、Ｒ^７、Ｒ^８は、相互に独立に、水素原子、炭素数１〜６の直鎖状、分岐状若しくは環状のアルキル基を示す。尚、Ｒ^７及びＲ^８が相互に結合して環状構造を形成してもよい。また、ｐは１〜４の整数である。〕
As a result of intensive studies, the present inventors have found that the above problems can be solved by a resin composition having the following constitution, and have completed the present invention.
As means for achieving the above object, the invention of claim 1
(A) an acid dissociable group-containing resin containing a structural unit represented by the following general formula (1) and a structural unit represented by the following general formula (2):
(B) contains a resin containing a structural unit represented by the following general formula (3), and (C) a component that generates an acid upon irradiation with radiation, and is used for producing a plated model. A positive-type radiation-sensitive resin composition (hereinafter, also simply referred to as “radiation-sensitive resin composition”).

[In General Formula (1), R ¹ represents a hydrogen atom or a methyl group, R ² represents a methyl group or an ethyl group, and R ³ represents a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms. Indicates. R ² and R ³ may be bonded to each other to form a cyclic structure. ]

[In General Formula (2), R ⁴ represents a hydrogen atom or a methyl group, and R ⁵ represents a monovalent organic group. Moreover, m is an integer of 0-4, n is an integer of 1-4. ]

[In General Formula (3), R ⁶ represents a hydrogen atom or a methyl group, and R ⁷ and R ⁸ are each independently a hydrogen atom, a linear, branched or cyclic alkyl having 1 to 6 carbon atoms. Indicates a group. R ⁷ and R ⁸ may be bonded to each other to form a cyclic structure. Moreover, p is an integer of 1-4. ]

〔一般式（４）において、Ｒ^９及びＲ^１０は、それぞれ同一でも異なっていてもよく、水素原子、炭素数１〜６の置換若しくは非置換のアルキル基、炭素数３〜２０の置換若しくは非置換の脂肪族基、置換若しくは非置換のアリール基、水酸基、又はカルボキシル基を示す。また、Ｒ^１１は炭素数１〜４のアルキル基であり、ｑは１〜１００の整数である。〕
The invention of claim 2 further contains a vinyl alkyl ether resin represented by the following general formula (4), and the content of the vinyl alkyl ether resin is 2 to 100 parts by mass of the resin component. It is a radiation sensitive resin composition of Claim 1 which is 60 mass parts.

[In General Formula (4), R ⁹ and R ¹⁰ may be the same or different, and each represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, a substituted or non-substituted group having 3 to 20 carbon atoms. A substituted aliphatic group, a substituted or unsubstituted aryl group, a hydroxyl group, or a carboxyl group is shown. R ¹¹ is an alkyl group having 1 to 4 carbon atoms, and q is an integer of 1 to 100. ]

  The invention according to claim 3 is the radiation sensitive resin composition according to claim 1 or 2, wherein the content of the component (C) is 0.1 to 20 parts by mass with respect to 100 parts by mass of the resin component. is there.

  The invention according to claim 4 is the radiation-sensitive material according to any one of claims 1 to 3, wherein the component (C) is at least one compound selected from the group consisting of an onium salt compound, a sulfonimide compound and a diazomethane compound. It is an adhesive resin composition.

  Invention of Claim 5 is a radiation sensitive resin composition in any one of Claim 1 thru | or 4 which further contains an acid diffusion controlling agent.

  The invention according to claim 6 is the radiation-sensitive resin composition according to any one of claims 1 to 5, wherein the plated model is a bump.

  The invention of claim 7 is a positive radiation sensitive resin film formed from the radiation sensitive resin composition according to any one of claims 1 to 6 (hereinafter simply referred to as “radiation sensitive”). Also called “resin film”).

  The invention according to claim 8 is a transfer film comprising the radiation-sensitive resin film according to claim 7.

The invention of claim 9
(A) A step of forming a resin film on a substrate by applying the radiation-sensitive resin composition according to any one of claims 1 to 6 onto a substrate having a conductive layer on the surface and drying the composition;
(B) irradiating the resin film with radiation through a mask having a predetermined pattern;
(C) heating the substrate having the resin film, and developing to form a pattern;
(D) using the pattern as a mold and forming a plated object by electrolytic plating;
(E) a method for producing a plated model, comprising: a step of peeling a resin film remaining on a substrate; and (f) a step of removing a conductive layer other than a region where the plated model is formed. .

The invention of claim 10
(A) forming the resin film on the substrate by laminating the radiation-sensitive resin film according to claim 7 on the substrate having a conductive layer on the surface;
(B) irradiating the resin film with radiation through a mask having a predetermined pattern;
(C) heating the substrate having the resin film, and developing to form a pattern;
(D) using the pattern as a mold and forming a plated object by electrolytic plating;
(E) a method for producing a plated model, comprising: a step of peeling a resin film remaining on a substrate; and (f) a step of removing a conductive layer other than a region where the plated model is formed. .

  The invention of claim 11 is the method for producing a plated article according to claim 9 or 10, wherein the resin film formed on the substrate has a thickness of 20 to 100 μm.

If the radiation sensitive resin composition of this invention is used, the sensitivity which was excellent with respect to actinic radiation will be shown, and the pattern used as the template of electrolytic plating can be formed faithfully to a mask dimension.
In addition, the resin composition of the present invention can accurately transfer the shape of a pattern to be a mold even in the electrolytic plating stage, and can form a plated model that is faithful to the mask dimensions, and also has sensitivity, resolution, and adhesion. Etc. are also excellent.
Therefore, the radiation-sensitive resin composition of the present invention can be used very suitably for the production of thick-film plated objects such as bumps or wirings in integrated circuit elements.

  Hereinafter, the positive-type radiation-sensitive resin composition, the positive-type radiation-sensitive resin film, the transfer film, and the method for producing a plated model according to the present invention will be described in detail.

[Positive radiation sensitive resin composition]
In the radiation-sensitive resin composition of the present invention, when an acid is generated by exposure, a chemical reaction (for example, change in polarity) occurs in a resin film (that is, a resist film) formed from the resin composition by the catalytic action of the acid. , Chemical bond decomposition, etc.) occur, and the solubility in the developer changes in the exposed area. The radiation-sensitive resin composition of the present invention is a resin composition for producing a plated molded article that uses this phenomenon to form a pattern that serves as a template for electrolytic plating.

The pattern forming mechanism will be further described as follows. First, an acid is generated by exposure to an acid generator. By the catalytic action of this acid, the acid dissociable functional group contained in the positive radiation sensitive resin composition reacts to become an acidic functional group, and an acid dissociable substance is generated. As a result, the solubility of the exposed portion of the polymer in an alkaline developer increases. The reaction of the acid-dissociable functional group is promoted by heating after exposure (post exposure bake: hereinafter also referred to as “PEB”).
The acid newly generated by the reaction of the acid-dissociable functional group acts as a catalyst for the reaction of another acid-dissociable functional group, and the reaction of the acid-dissociable functional group and the generation of the acid are “amplified” one after another. It will be. By utilizing such a chemical amplification action, a predetermined pattern is formed with high sensitivity (that is, low exposure) and high resolution.

[(A) Acid-dissociable group-containing resin]
The (A) acid-dissociable group-containing resin (hereinafter simply referred to as “resin (A)”) used in the radiation-sensitive resin composition of the present invention is a structural unit represented by the following general formula (1) ( Hereinafter referred to as “structural unit (1)”) and a structural unit represented by the following general formula (2) (hereinafter referred to as “structural unit (2)”).
This resin is an alkali-insoluble or alkali-insoluble resin in which the acidic functional group in the resin is protected with a functional group called an acetal group, and the resin becomes alkali-soluble when the acetal group is dissociated by the action of an acid. Note that group -OCH the following general formula ^{(1) (R 2) (} OR 3) , together with the benzene ring in the formula, forms an acetal structure.
Here, “alkali insoluble or hardly soluble in alkali” means an alkali development condition employed when a resist pattern is formed from a resist film formed using a radiation-sensitive resin composition containing an acid-dissociable group-containing resin. Below, when a film using only an acid-dissociable group-containing resin instead of the resist film is developed, it means that 50% or more of the initial film thickness of the film remains after development.

〔一般式（１）において、Ｒ^１は水素原子又はメチル基を示し、Ｒ^２はメチル基又はエチル基を示し、Ｒ^３は炭素数１〜６の直鎖状、分岐状若しくは環状のアルキル基を示す。尚、Ｒ^２及びＲ^３が相互に結合して環状構造を形成してもよい。〕

[In General Formula (1), R ¹ represents a hydrogen atom or a methyl group, R ² represents a methyl group or an ethyl group, and R ³ represents a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms. Indicates. R ² and R ³ may be bonded to each other to form a cyclic structure. ]

R ² in the general formula (1) is preferably a methyl group or an ethyl group.
In the above formula (1), examples of the linear, branched or cyclic alkyl group having 1 to 6 carbon atoms of R ³ include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, Examples include n-butyl group, i-butyl group, sec-butyl group, t-butyl group, n-pentyl group, neopentyl group, n-hexyl group, cyclopentyl group, cyclohexyl group and the like. Among these, a methyl group, an ethyl group, a butyl group, a cyclohexyl group, and the like are preferable.
Also, R ² and R ³ are bonded to each other, as the groups which form a cyclic structure together with the carbon to which R ² and R ³ are attached, tetrahydrofuranyl group, tetrahydropyranyl group.

  Specific examples of the structural unit (1) include p- (1-methoxyethoxy) styrene, p- (1-ethoxyethoxy) styrene, p- (1-n-propoxyethoxy) styrene, p- (1-i-). Propoxyethoxy) styrene, p- (1-n-butoxyethoxy) styrene, p- (1-t-butoxyethoxy) styrene, p- (1-n-pentyloxyethoxy) styrene, p- (1-neopentyloxy) Ethoxy) styrene, p- (1-n-hexyloxyethoxy) styrene, p- (1-cyclopentyloxyethoxy) styrene, p- (1-cyclohexyloxyethoxy) styrene, p- (1-methoxypropoxy) styrene, p -(1-ethoxypropoxy) styrene, p- (1-n-propoxypropoxy) styrene, p- (1-i-propyl) Poxypropoxy) styrene, p- (1-n-butoxypropoxy) styrene, p- (1-t-butoxypropoxy) styrene, p- (1-n-pentyloxypropoxy) styrene, p- (1-neopentyloxy) Propoxy) styrene, p- (1-n-hexyloxypropoxy) styrene, p- (1-cyclopentyloxypropoxy) styrene, p- (1-cyclohexyloxypropoxy) styrene, p- (2-tetrahydrofuranyloxy) styrene, Mention may be made of units in which a polymerizable unsaturated bond such as p- (2-tetrahydropyranyloxy) styrene is cleaved.

Of these structural units (1), p- (1-methoxyethoxy) styrene, p- (1-ethoxyethoxy) styrene, p- (1-butoxyethoxy) styrene, p- (1-methoxypropoxy) styrene, Polymerizable unsaturated bonds such as p- (1-ethoxypropoxy) styrene, p- (1-cyclohexyloxyethoxy) styrene, p- (2-tetrahydrofuranyloxy) styrene, p- (2-tetrahydropyranyloxy) styrene Is a cleaved unit.
In the resin (A), only one type of structural unit (1) may be present, or two or more types may be present.

〔一般式（２）において、Ｒ^４は水素原子又はメチル基を示し、Ｒ^５は一価の有機基を示す。また、ｍは０〜４の整数であり、ｎは１〜４の整数である。〕

[In General Formula (2), R ⁴ represents a hydrogen atom or a methyl group, and R ⁵ represents a monovalent organic group. Moreover, m is an integer of 0-4, n is an integer of 1-4. ]

Specific examples of the structural unit (2) include, for example, p-hydroxystyrene, m-hydroxystyrene, o-hydroxystyrene, α-methyl-4-hydroxystyrene, 3-methyl-4-hydroxystyrene, 2-methyl- Such as 4-hydroxystyrene, 2-methyl-3-hydroxystyrene, 4-methyl-3-hydroxystyrene, 5-methyl-3-hydroxystyrene, 3,4-dihydroxystyrene, 2,4,6-trihydroxystyrene, etc. Examples include units in which a non-aromatic double bond is cleaved in a monomer.
Among these, a unit in which a non-aromatic double bond of p-hydroxystyrene, m-hydroxystyrene, o-hydroxystyrene, and α-methyl-4-hydroxystyrene is cleaved is preferable. By including such a structural unit, the solubility during development can be appropriately controlled.

The resin (A) may contain “other structural units”. Furthermore, it may have a structure partially crosslinked with an appropriate crosslinking group (for example, a crosslinking group having a diethylene glycol skeleton).
As said other structural unit, the structural unit represented by following General formula (5) is mentioned, for example.

In General formula (5), R < ¹² > is a hydrogen atom or a methyl group, R < ¹³ > -R < ¹⁵ > is a C1-C4 alkyl group, a C4-C20 alicyclic hydrocarbon group, and an aromatic group. Or a substituted hydrocarbon group in which at least one hydrogen atom of these hydrocarbon groups is substituted with a polar group other than a hydrocarbon group, and R ^{13 to} R ¹⁵ may be the same as or different from each other. In addition, when any two of R ^{13 to} R ¹⁵ are an alkyl group or a substituted alkyl group, the alkyl chains are bonded to each other to form an alicyclic hydrocarbon group having 4 to 20 carbon atoms or a substituted alicyclic group. A hydrocarbon group may be formed.

Examples of the alkyl group having 1 to 4 carbon atoms include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, 2-methylpropyl group, 1-methylpropyl group, and t-butyl. Groups and the like.
Examples of the alicyclic hydrocarbon group having 4 to 20 carbon atoms include cycloalkyl groups such as a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group; adamantane, bicyclo [2.2.1] Heptane, tetracyclo [6.2.1.1 ^3,6 . And groups derived from bridged hydrocarbons such as 0 ^2,7 ] dodecane and tricyclo [5.2.1.0 ^2,6 ] decane.

Moreover, when any two of R < ¹³ > -R < ¹⁵ > are alkyl groups, the alkyl chain may couple | bond together and the C4-C20 alicyclic hydrocarbon group may be formed. As this alicyclic hydrocarbon group, the same thing as the said alicyclic hydrocarbon group can be mentioned.

Examples of the aromatic group include a phenyl group, an o-tolyl group, an m-tolyl group, a p-tolyl group, a 4-t-butylphenyl group, a 1-naphthyl group, and a benzyl group.
Examples of the polar group other than the hydrocarbon group that can be substituted with a hydrogen atom in the substituted hydrocarbon group include, for example, chloro group; hydroxyl group; carboxyl group; oxo group (that is, ═O group); hydroxymethyl group, 1 -Hydroxyalkyl such as hydroxyethyl group, 2-hydroxyethyl group, 1-hydroxypropyl group, 2-hydroxypropyl group, 3-hydroxypropyl group, 2-hydroxybutyl group, 3-hydroxybutyl group, 4-hydroxybutyl group Groups; alkoxy groups having 1 to 6 carbon atoms such as methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, 2-methylpropoxy group, 1-methylpropoxy group, t-butoxy group; Cyano group; cyanomethyl group, 2-cyanoethyl group, 3-cyanopropyl group, 4-cyanobutyl group, etc. Cyanoalkyl groups such primes 2-6 thereof.

  The structure of the general formula (5) can be obtained by polymerization using a monomer represented by the following general formula (5 ′) (hereinafter also referred to as “monomer (5 ′)”). it can.

In the above formula (5 ^'), R 12 ^{to R 15} have the same meanings as ^R 12 ^{to R 15} in the formula (5).
Examples of such a monomer (5 ′) include t-butyl (meth) acrylate, 1,1-dimethyl-propyl (meth) acrylate, 1,1-dimethyl-butyl (meth) acrylate, and 2-cyclohexyl. Propyl (meth) acrylate, 1,1-dimethyl-phenyl (meth) acrylate, tetrahydropyranyl (meth) acrylate, 2-t-butoxycarbonylmethyl (meth) acrylate, 2-benzyloxycarbonylethyl (meth) acrylate, 2 -Methyladamantyl (meth) acrylate, 1,1-dimethyl-3-oxobutyl (meth) acrylate, 2-benzyl-2-propyl (meth) acrylate and the like.

Furthermore, as “other structural units”, structural units represented by the following general formulas (6) and (7) (hereinafter also referred to as “structural units (6)” and “structural units (7)”, respectively). Can be mentioned.
When the structural unit (6) and / or (7) is contained in the acid-dissociable group-containing resin (A), the adhesion of the resist to the substrate is enhanced, and the plating solution serves as an interface between the substrate and the resist during plating. There is an effect to prevent the protrusion. Furthermore, since the acidity of the phenolic hydroxyl group can be changed by adjusting the type and number of substituents contained in the structural unit, the radiation-sensitive resin composition according to the present invention with respect to the alkaline developer. Solubility can be adjusted.

In the general formulas (6) and (7), R ¹⁶ is a hydrogen atom or a methyl group, R ¹⁷ is — (CH ₂ ) _n —, and R ¹⁸ is an alkyl group having 1 to 4 carbon atoms. Here, m is an integer of 0 to 4, and n is an integer of 0 to 3.

  Examples of the alkyl group having 1 to 4 carbon atoms include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, 2-methylpropyl group, 1-methylpropyl group, and t-butyl. Groups and the like.

  Examples of the monomer that can be the structural unit (6) include a monomer represented by the following general formula (6 ′) (hereinafter also referred to as “monomer (6 ′)”). Moreover, as a monomer which can become said structural unit (7), the monomer (henceforth "monomer (7 ')") represented by the following general formula (7') is mentioned, for example. It is done.

In the formula (6 ') and ^{(7'), R 16 ~R} 18, m, n have the same meanings as ^R 16 ^~R 18, m, n in the formula (6) and (7) in.

  Examples of the monomer (6 ′) include p-hydroxyphenyl acrylamide, p-hydroxyphenyl methacrylamide, o-hydroxyphenyl acrylamide, o-hydroxyphenyl methacrylamide, m-hydroxyphenyl acrylamide, m-hydroxyphenyl methacrylamide, p-hydroxybenzylacrylamide, p-hydroxybenzylmethacrylamide, 3,5-dimethyl-4-hydroxybenzylacrylamide, 3,5-dimethyl-4-hydroxybenzylmethacrylamide, 3,5-tertbutyl-4-hydroxybenzylacrylamide Amides such as 3,5-tertbutyl-4-hydroxybenzylmethacrylamide, o-hydroxybenzylacrylamide, o-hydroxybenzylmethacrylamide Containing vinyl compounds.

As said monomer (7 '), p-hydroxyphenyl (meth) acrylate, o-hydroxyphenyl (meth) acrylate, m-hydroxyphenyl (meth) acrylate, p-hydroxybenzyl (meth) acrylate, 3,5 -(Meth) acrylic acid esters such as dimethyl-4-hydroxybenzyl (meth) acrylate, 3,5-tertbutyl-4-hydroxybenzyl (meth) acrylate, o-hydroxybenzyl (meth) acrylate and the like.
Among these monomers (6 ′) and (7 ′), p-hydroxyphenylacrylamide, p-hydroxyphenylmethacrylamide, 3,5-dimethyl-4-hydroxybenzylacrylamide, 3,5-dimethyl- 4-hydroxybenzylmethacrylamide is preferred.
The monomers (6 ′) and (7 ′) can be used alone or in admixture of two or more. Further, the monomer (6 ′) and the monomer (7 ′) may be used in combination.

Further, the resin (A) may contain “another structural unit”. Examples of other structural units include styrene, α-methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 2-methoxystyrene, 3-methoxystyrene, 4-methoxystyrene, 4- t-butoxystyrene, 4-t-butoxycarbonyloxystyrene, 4-t-butoxycarbonylmethyloxystyrene, 4- (2′-t-butoxycarbonylethyloxy) styrene, 4-tetrahydrofuranyloxystyrene, 4-tetrahydropyrani Vinyl aromatic compounds such as ruoxystyrene;
Methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, sec-butyl (meth) Acrylate, t-butyl (meth) acrylate, n-pentyl (meth) acrylate, neopentyl (meth) acrylate, n-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2 -Hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, norbornyl (meth) acrylate, isobornyl (meth) acrylate Tricyclodecanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, adamantyl (meth) acrylate, 2-methyladamantyl (meth) acrylate, tetrahydrofuranyl (meth) acrylate, tetrahydropyranyl (meth) acrylate, phenyl (meth) ) (Meth) acrylic acid esters such as acrylate, benzyl (meth) acrylate, phenethyl (meth) acrylate, monomers represented by the following general formulas (8) to (10);
Unsaturated carboxylic acids such as (meth) acrylic acid, crotonic acid, maleic acid, fumaric acid, cinnamic acid;
Carboxyalkyl esters of unsaturated carboxylic acids such as 2-carboxyethyl (meth) acrylate, 2-carboxypropyl (meth) acrylate, 3-carboxypropyl (meth) acrylate;
Unsaturated nitrile compounds such as (meth) acrylonitrile, α-chloroacrylonitrile, crotonnitrile, maleinnitrile, fumaronitrile;
Unsaturated amide compounds such as (meth) acrylamide, N, N-dimethyl (meth) acrylamide, crotonamide, maleinamide, fumaramide;
Unsaturated imide compounds such as maleimide, N-phenylmaleimide, N-cyclohexylmaleimide;
N-vinyl-ε-caprolactam, N-vinyl pyrrolidone, 2-vinyl pyridine, 3-vinyl pyridine, 4-vinyl pyridine, 2-vinyl imidazole, other nitrogen-containing vinyl compounds such as 4-vinyl imidazole, etc. Examples include units in which a saturated bond is cleaved.

〔式（８）〜（１０）において、ｎは、それぞれ、１〜６の自然数を示す。〕

[In Formula (8)-(10), n shows the natural number of 1-6, respectively. ]

  Among the above structural units, styrene, α-methylstyrene, 4-t-butoxystyrene, 4-t-butoxycarbonyloxystyrene, 4-t-butoxycarbonylmethyloxystyrene, 4- (2′-t- Butoxycarbonylethyloxy) styrene, t-butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, isobornyl (meth) acrylate, tricyclodecanyl (meth) acrylate, 2-methyladamantyl (meth) acrylate, the above formula A unit in which a polymerizable unsaturated bond such as the monomer represented by (8) or (9) is cleaved is preferable.

In the resin (A), only one type of other structural unit may be present, or two or more types may be present.
In resin (A), the ratio of the number of structural units (1) to the total number of structural units (1) and structural units (2) is the acetal structure in structural unit (1), other structural units or It varies depending on the type and content of the cross-linking group and cannot be defined unconditionally, but is preferably 5 to 90%, more preferably 10 to 80%.
Furthermore, the content of other structural units is usually 50 mol% or less, preferably 30 mol% or less, assuming that all the structural units are 100 mol%.
Moreover, the content rate of a crosslinking group is 15 mol% or less normally, when it makes all the structural units 100 mol%, Preferably it is 10 mol% or less.

The weight average molecular weight (hereinafter referred to as “Mw”) in terms of polystyrene measured by gel permeation chromatography of the resin (A) is preferably 1,000 to 500,000, more preferably 3,000 to 300,000. is there.
The ratio (Mw / Mn) of Mw of the resin (A) and polystyrene-reduced number average molecular weight (hereinafter referred to as “Mn”) measured by gel permeation chromatography is usually 1 to 5, preferably 1. ~ 3.

In the resin (A) in the present invention, for example, (a) a part of the phenolic hydroxyl group in the (co) polymer of p-hydroxystyrene is subjected to ethyl vinyl ether, n-butyl vinyl ether, cyclohexane under weakly acidic conditions. (B) A vinyl ether such as ethyl vinyl ether, n-butyl vinyl ether, cyclohexyl vinyl ether, etc., under a weakly acidic condition, by subjecting an addition reaction with a vinyl ether compound such as xyl vinyl ether; A monomer corresponding to the structural unit (1) is synthesized by addition reaction with the compound, and this monomer can be produced by a method of copolymerizing with p-hydroxystyrene by a conventional method.
In addition, the structure partially crosslinked by the crosslinking group having a diethylene glycol skeleton in the resin (A) can be obtained by, for example, reacting an appropriate amount of diethylene glycol divinyl ether at the same time in the addition reaction with the vinyl ether compound in the method (a). Can be introduced.

[Other resins containing acid-dissociable groups]
In the positive radiation sensitive resin composition of the present invention, the acid dissociable group-containing resin (A) and an acid dissociable group-containing resin other than the resin (A) (hereinafter referred to as “other acid dissociable groups”). "Containing resin")). Hereinafter, other acid-dissociable group-containing resins will be described.
The other acid-dissociable group-containing resin is an alkali-insoluble or alkali-insoluble resin in which an acidic functional group is protected with an acid-dissociable group and becomes alkali-soluble when this acid-dissociable group is dissociated. Consists of.

The acidic functional group is not particularly limited as long as it exhibits acidity, and examples thereof include a phenolic hydroxyl group, a carboxyl group, and a sulfonic acid group. These may exist independently and may exist 2 or more types.
Examples of the acid dissociable group include a substituted methyl group, 1-substituted ethyl group, 1-substituted-n-propyl group, 1-branched alkyl group, silyl group, germyl group, alkoxycarbonyl group, acyl group, And a cyclic acid dissociable group. These may exist independently and may exist 2 or more types.

  Examples of the substituted methyl group include methoxymethyl group, methylthiomethyl group, ethoxymethyl group, ethylthiomethyl group, methoxyethoxymethyl group, benzyloxymethyl group, benzylthiomethyl group, phenacyl group, 4-bromophenacyl group, 4 -Methoxyphenacyl group, 4-methylthiophenacyl group, α-methylphenacyl group, cyclopropylmethyl group, benzyl group, diphenylmethyl group, triphenylmethyl group, 4-bromobenzyl group, 4-nitrobenzyl group, 4 -Methoxybenzyl group, 4-methylthiobenzyl group, 4-ethoxybenzyl group, 4-ethylthiobenzyl group, piperonyl group, methoxycarbonylmethyl group, ethoxycarbonylmethyl group, n-propoxycarbonylmethyl group, i-propoxycarbonylmethyl group , N-but Aryloxycarbonyl methyl group, and a t- butoxycarbonyl methyl group.

  Examples of the 1-substituted ethyl group include 1-methoxyethyl group, 1-methylthioethyl group, 1,1-dimethoxyethyl group, 1-ethoxyethyl group, 1-ethylthioethyl group, 1,1-diethoxy. Ethyl group, 1-phenoxyethyl group, 1-phenylthioethyl group, 1,1-diphenoxyethyl group, 1-benzyloxyethyl group, 1-benzylthioethyl group, 1-cyclopropyloxyethyl group, 1-cyclohexyl Oxyethyl group, 1-phenylethyl group, 1,1-diphenylethyl group, 1-methoxycarbonylethyl group, 1-ethoxycarbonylethyl group, 1-n-propoxycarbonylethyl group, 1-i-propoxycarbonylethyl group, Examples include 1-n-butoxycarbonylethyl group, 1-t-butoxycarbonylethyl group, and the like. That.

Examples of the 1-substituted-n-propyl group include 1-methoxy-n-propyl group and 1-ethoxy-n-propyl group.
Examples of the 1-branched alkyl group include i-propyl group, sec-butyl group, t-butyl group, 1,1-dimethylpropyl group, 1-methylbutyl group, 1,1-dimethylbutyl group and the like. Can do.

Examples of the silyl group include trimethylsilyl group, ethyldimethylsilyl group, methyldiethylsilyl group, triethylsilyl group, i-propyldimethylsilyl group, methyldi-i-propylsilyl group, tri-i-propylsilyl group, t- Examples thereof include a butyldimethylsilyl group, a methyldi-t-butylsilyl group, a tri-t-butylsilyl group, a phenyldimethylsilyl group, a methyldiphenylsilyl group, and a triphenylsilyl group.
Examples of the germyl group include trimethylgermyl group, ethyldimethylgermyl group, methyldiethylgermyl group, triethylgermyl group, i-propyldimethylgermyl group, methyldi-i-propylgermyl group, tri-i. -Propylgermyl group, t-butyldimethylgermyl group, methyldi-t-butylgermyl group, tri-t-butylgermyl group, phenyldimethylgermyl group, methyldiphenylgermyl group, triphenylgermyl group, etc. it can.
As said alkoxycarbonyl group, a methoxycarbonyl group, an ethoxycarbonyl group, i-propoxycarbonyl group, t-butoxycarbonyl group etc. can be mentioned, for example.

  Examples of the acyl group include acetyl group, propionyl group, butyryl group, heptanoyl group, hexanoyl group, valeryl group, pivaloyl group, isovaleryl group, laurylyl group, myristoyl group, palmitoyl group, stearoyl group, oxalyl group, malonyl group, Succinyl group, glutaryl group, adipoyl group, piperoyl group, suberoyl group, azelaoil group, sebacoyl group, acryloyl group, propioyl group, methacryloyl group, crotonoyl group, oleoyl group, maleoyl group, fumaroyl group, mesaconoyl group, canphoroyl group, benzoyl Group, phthaloyl group, isophthaloyl group, terephthaloyl group, naphthoyl group, toluoyl group, hydroatropoyl group, atropoyl group, cinnamoyl group, furoyl group, thenoyl group, nicotinoyl group, iso Kochinoiru group, p- toluenesulfonyl group, and mesyl group.

  Examples of the cyclic acid dissociable group include a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cyclohexenyl group, a 4-methoxycyclohexyl group, a tetrahydropyranyl group, a tetrahydrofuranyl group, a tetrahydrothiopyranyl group, and a tetrahydrothiofuran group. Nyl group, 3-bromotetrahydropyranyl group, 4-methoxytetrahydropyranyl group, 4-methoxytetrahydrothiopyranyl group, 3-tetrahydrothiophene-1,1-dioxide group and the like can be mentioned.

  Among these acid dissociable groups, benzyl group, 2-benzyl-2-propyl group, t-butoxycarbonylmethyl group, 1-methoxyethyl group, 1-ethoxyethyl group, 1-cyclohexyloxyethyl group, 1-ethoxy -N-propyl group, t-butyl group, 1,1-dimethylpropyl group, trimethylsilyl group, t-butoxycarbonyl group, tetrahydropyranyl group, tetrahydrofuranyl group, tetrahydrothiopyranyl group, tetrahydrothiofuranyl group are preferred. .

  In the present invention, the other acid-dissociable group-containing resin may contain “other structural units” such as units represented by the general formulas (5), (6), and (7). . Furthermore, the above “further structural unit” may be included.

The rate of introduction of acid dissociable groups in the other acid dissociable group-containing resins (the ratio of the number of acid dissociable groups to the total number of acidic functional groups and acid dissociable groups in the other acid dissociable group-containing resins) is: Although it can be in various ranges depending on the acid dissociable group and the type of resin into which the group is introduced, it is preferably 5 to 100%, more preferably 10 to 100%.
A branched structure can be introduced into the other acid-dissociable group-containing resin by a polyfunctional monomer and / or an acetal crosslinking group in the resin. By introducing such a structure, the heat resistance of the resin can be improved.
The introduction rate of the branched structure due to the polyfunctional monomer and / or the acetal crosslinking group in the other acid-dissociable group-containing resin is the same as that of the branched structure and the other acid-dissociable group-containing resin into which the branched structure is introduced. Depending on the type, it can be in various ranges, but is preferably 10 mol% or less with respect to the total structural units.

The molecular weight range of the other acid-dissociable group-containing resins is not particularly limited, and may be various molecular weight ranges as necessary. Usually, polystyrene measured by gel permeation chromatography (GPC). The converted weight average molecular weight (hereinafter referred to as “Mw”) is 1,000 to 500,000, preferably 2,000 to 400,000, and more preferably 3,000 to 300,000.
In the case of the other acid-dissociable group-containing resin having no branched structure, it is more preferably 1,000 to 150,000, particularly preferably 3,000 to 100,000. In the case of an acid-dissociable group-containing resin, it is more preferably 5,000 to 500,000, particularly preferably 8,000 to 300,000. When the Mw of other acid-dissociable group-containing resins is in the above range, the resin film has sufficient strength and plating resistance, has excellent alkali solubility after exposure of the polymer, and can easily form a fine pattern. Excellent development characteristics of resist.

Further, the ratio (Mw / Mn) of Mw of the other acid-dissociable group-containing resin and polystyrene-reduced number molecular weight (hereinafter referred to as “Mn”) measured by GPC is not particularly limited. Although it can be set as the range of various molecular weights, it is 1-10 normally, Preferably it is 1-8. By being in such a range, the obtained resist has excellent resolution performance.
There is no limitation in particular about the manufacturing method of said other acid dissociable group containing resin. For example, a method of introducing one or more acid dissociable groups into the acid functional group in an alkali-soluble group-containing resin produced in advance, one or more polymerizations having an acid functional group protected by the acid dissociable group A method for polymerizing a polymerizable unsaturated monomer, a method for polymerizing the one or more polymerizable unsaturated monomers and one or more other polymerizable unsaturated monomers, and protecting with the acid dissociable group Produced by a method of polycondensing one or more polycondensation components having an acidic functional group, or a method of polycondensing the one or more polycondensation components with one or more other polycondensation components. be able to.

  Here, a method of polymerizing one or more polymerizable unsaturated monomers having an acidic functional group protected by the acid dissociable group, or the one or more polymerizable unsaturated monomers and one type In the method of polymerizing with the other polymerizable unsaturated monomer, the radical polymerization initiator, the anion polymerization catalyst, the coordination anion polymerization catalyst, and the cation polymerization catalyst are selected depending on the type of the monomer and the reaction medium. A polymerization method such as bulk polymerization, solution polymerization, precipitation polymerization, emulsion polymerization, suspension polymerization, or bulk-suspension polymerization can be suitably employed by appropriately selecting a polymerization initiator such as a polymerization catalyst. Also, a method of polycondensing one or more polycondensation components having an acidic functional group protected by the acid dissociable group, or one or more polycondensation components and one or more other polycondensation components In the method of polycondensation, (co) polycondensation can be carried out in an aqueous medium or a mixed medium of water and a hydrophilic solvent in the presence of an acidic catalyst.

  Examples of the radical polymerization initiator include azo compounds such as 2,2′-azobisisobutyronitrile (AIBN) and 2,2′-azobis- (2,4-dimethylvaleronitrile), benzoyl peroxide, and lauryl peroxide. And organic peroxides such as t-butyl peroxide.

The solvent used in the solution polymerization method is not particularly limited as long as it does not react with the monomer component used and dissolves the polymer to be produced. For example, methanol, ethanol, n-hexane, toluene, tetrahydrofuran, 1,4-dioxane, ethyl acetate, n-butyl acetate, acetone, methyl ethyl ketone, methyl isobutyl ketone, 2-heptanone, cyclohexanone, ethylene glycol monomethyl ether, propylene glycol monomethyl Examples include ether, propylene glycol monomethyl ether acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, ethyl lactate, and γ-butyrolactone. These solvents can be used alone or in admixture of two or more.
When other acid-dissociable group-containing resins are produced by a solution polymerization method, the resulting polymer solution may be used for the preparation of a positive radiation-sensitive resin composition as it is, or another polymer solution may be used. The acid-dissociable group-containing resin may be separated and used for the preparation of a positive radiation-sensitive resin composition.
In the polymerization, a molecular weight regulator such as a mercaptan compound or a halogen hydrocarbon can be used as necessary.
In the present invention, other acid-dissociable group-containing resins can be used alone or in admixture of two or more.

[(B) Imido group-containing resin]
For the radiation-sensitive resin composition of the present invention, a resin (B) containing a structural unit represented by the following general formula (3) (hereinafter referred to as “imide group-containing resin (B)”) is used.
By combining this imide group-containing resin (B), adhesion to a metal sputter substrate such as gold can be improved.

〔一般式（３）において、Ｒ^６は水素原子又はメチル基を示し、Ｒ^７、Ｒ^８は、相互に独立に、水素原子、炭素数１〜６の直鎖状、分岐状若しくは環状のアルキル基を示す。尚、Ｒ^７及びＲ^８が相互に結合して環状構造を形成してもよい。また、ｐは１〜４の整数である。〕

[In General Formula (3), R ⁶ represents a hydrogen atom or a methyl group, and R ⁷ and R ⁸ are each independently a hydrogen atom, a linear, branched or cyclic alkyl having 1 to 6 carbon atoms. Indicates a group. R ⁷ and R ⁸ may be bonded to each other to form a cyclic structure. Moreover, p is an integer of 1-4. ]

In the above formula (3), examples of the linear, branched or cyclic alkyl group having 1 to 6 carbon atoms of R ⁷ and R ⁸ include a methyl group, an ethyl group, an n-propyl group, and an i-propyl group. , N-butyl group, i-butyl group, sec-butyl group, t-butyl group, n-pentyl group, neopentyl group, n-hexyl group, cyclopentyl group, cyclohexyl group and the like. Among these, a methyl group, an ethyl group, a butyl group, a cyclohexyl group, and the like are preferable.
Moreover, when R < ⁷ > and R < ⁸ > couple | bond together and form a cyclic structure, it is preferable to form a cyclohexane ring, a benzene ring, etc.

  Specific examples of the structural unit (3) include, for example, N-acryloyloxymethyl succinimide, N-methacryloyloxymethyl succinimide, N-acryloyloxymethyl-4,5-dimethylsuccinimide, N -Methacryloyloxymethyl-4,5-dimethylsuccinimide, N-acryloyloxymethyl-4,5-dimethylsuccinimide, N-methacryloyloxymethyl-4,5-diethylsuccinimide, N-acrylic Leuoxymethyl phthalimide, N-methacryloyloxymethyl phthalimide, N-acryloyloxymethyl hexahydrophthalimide, N-methacryloyloxymethyl hexahydrophthalimide, N-acryloyloxyethyl succinimide N-methacryloyloxyethyl succinimide, N-acryloyl Xylethyl-4,5-dimethylsuccinimide, N-methacryloyloxyethyl-4,5-dimethylsuccinimide, N-acryloyloxyethyl-4,5-dimethylsuccinimide, N-methacryloyloxyethyl- 4,5-diethylsuccinimide, N-acryloyloxyethyl phthalimide, N-methacryloyloxyethyl phthalimide, N-acryloyloxyethyl hexahydrophthalimide, N-methacryloyloxyethyl hexahydrophthal Acid imide, N-acryloyloxypropyl succinimide, N-methacryloyloxypropyl succinimide, N-acryloyloxypropyl-4,5-dimethylsuccinimide, N-methacryloyloxypropyl-4,5- Dimethyl succinimide, N-acryloyloxypro 4,5-dimethyl succinimide, N-methacryloyloxypropyl-4,5-diethyl succinimide, N-acryloyloxypropyl phthalimide, N-methacryloyloxypropyl phthalimide, N-acryl Leuoxypropylhexahydrophthalimide, N-methacryloyloxypropylhexahydrophthalimide, N-acryloyloxybutyl succinimide, N-methacryloyloxybutyl succinimide, N-acryloyloxybutyl-4, 5-dimethylsuccinimide, N-methacryloyloxybutyl-4,5-dimethylsuccinimide, N-acryloyloxybutyl-4,5-dimethylsuccinimide, N-methacryloyloxybutyl-4,5- Diethyl succinimide, N-acryloyloxybutyl phthalate List units in which polymerizable unsaturated bonds such as acid imide, N-methacryloyloxybutyl phthalimide, N-acryloyloxybutyl hexahydrophthalimide, N-methacryloyloxybutyl hexahydrophthalimide are cleaved Can do.

  Among these, N-acryloyloxymethyl succinimide, N-acryloyloxyethyl succinimide, N-acryloyloxymethyl phthalimide, N-acryloyloxyethyl phthalimide, N-acryloyloxy Methyl hexahydrophthalimide and N-acryloyloxyethyl hexahydrophthalimide are preferred.

In addition, the said imide group containing resin (B) may be used individually by 1 type, and may use 2 or more types together.
Moreover, although the said imide group containing resin (B) may be comprised only from the structural unit represented by the said General formula (3), it contains the said structural unit (6) and / or (7). May be. Furthermore, other structural units may be contained.

  Examples of the other structural units include p-hydroxystyrene, m-hydroxystyrene, o-hydroxystyrene, α-methyl-4-hydroxystyrene, 3-methyl-4-hydroxystyrene, 2-methyl-4-hydroxy. Styrene, 2-methyl-3-hydroxystyrene, 4-methyl-3-hydroxystyrene, 5-methyl-3-hydroxystyrene, 3,4-dihydroxystyrene, 2,4,6-trihydroxystyrene, styrene, α- Methyl styrene, maleic anhydride, (meth) acrylonitrile, crotonnitrile, maleinonitrile, fumaronitrile, mesaconitrile, citraconitrile, itacon nitrile, (meth) acrylamide, crotonamide, maleinamide, fumaramide, mesaconamide, citraconic acid A polymerizable double bond moiety in a monomer having a polymerizable double bond, such as C, itaconamide, vinyl aniline, vinyl pyridine, vinyl-ε-caprolactam, vinyl pyrrolidone, vinyl imidazole, etc., is generated by participating in addition polymerization. Examples include units.

  The imide group-containing resin (B) may be, for example, one or more monomers corresponding to the structural unit represented by the general formula (3), and if necessary, a single amount corresponding to the other structural unit. It can be produced by (co) polymerizing with the body. In these (co) polymerization reactions, a polymerization initiator or polymerization catalyst such as a radical polymerization initiator, an anionic polymerization catalyst, a coordination anionic polymerization catalyst, or a cationic polymerization catalyst is appropriately used depending on the type of monomer and reaction medium. And a conventionally known polymerization method such as bulk polymerization, solution polymerization, precipitation polymerization, emulsion polymerization, suspension polymerization, bulk-suspension polymerization or the like can be appropriately employed.

There is no limitation in particular about the content rate of the structural unit represented by General formula (3) in the said imide group containing resin (B), Although it can be set as various ranges as needed, Preferably it is 10-100. It is mol%, More preferably, it is 20-100 mol%.
Further, the molecular weight of the imide group-containing resin (B) is not particularly limited, and can be set in various ranges according to the characteristics of the radiation-sensitive resin composition of the present invention. It is 000-150,000, More preferably, it is 3,000-100,000, Mw / Mn is 1-13 normally, Preferably it is 1-10.

[Alkali-soluble group-containing resin]
If necessary, the positive radiation sensitive resin composition of the present invention contains an acid-dissociable group-containing resin such as resin (A) and an alkali-soluble group-containing resin other than the imide group-containing resin (B). can do.
The alkali-soluble group-containing resin has at least one functional group having an affinity with an alkali developer, for example, an acidic functional group such as a phenolic hydroxyl group, a carboxyl group, and a sulfonyl group. The resin may be soluble or insoluble in an alkali developer.

  The alkali-soluble group-containing resin is not particularly limited as long as it has the above properties. For example, an addition polymerization resin having one or more structural units represented by the following general formulas (11-1) to (11-3), And a polycondensation resin having at least one structural unit represented by the following general formula (11-4).

In the above formulas (11-1) to (11-4), R ¹⁹ and R ²² represent a hydrogen atom or a methyl group, and R ²⁰ represents —OH, —COOH, —R ²¹ —COOH, —OR ²¹ —COOH or OCOR ²¹ -COOH (provided ^{that, R 21} is - _{(CH 2) g} -. are shown, g is an integer from 1 to 4) ^indicates, R 23 ^{to R 27} number hydrogen atom or a carbon independently 1-4 Represents an alkyl group.

As the alkali-soluble group-containing resin, in particular, poly (p-hydroxystyrene), p-hydroxystyrene / α-methyl-4-hydroxystyrene copolymer, p-hydroxystyrene / styrene copolymer and the like are the main components. The resin to be used is preferable from the viewpoint of solubility control during development.
The alkali-soluble group-containing resin may contain the structural unit (6) and / or (7). In addition, the said alkali-soluble group containing resin may be used individually by 1 type, and may use 2 or more types together.

  When the alkali-soluble group-containing resin is an addition polymerization resin, the resin may be composed of only one or more of the structural units represented by the formulas (11-1) to (11-3). It can also have other structural units.

  The addition polymerization resin is, for example, one kind of each monomer corresponding to the structural units represented by the general formulas (11-1) to (11-3) like the imide group-containing resin (B). The above can be manufactured by (co) polymerizing with the monomer corresponding to said other structural unit as needed.

  Further, when the alkali-soluble group-containing resin is a polycondensation resin, it may be composed only of the structural unit represented by the general formula (11-4), but may further have other structural units. Good. Such a polycondensation resin includes one or more phenols and one or more aldehydes corresponding to the structural unit represented by the general formula (11-4), as necessary, other structural units. Can be produced by (co) polycondensation in the presence of an acidic catalyst in a water medium or in a mixed medium of water and a hydrophilic solvent.

  Examples of the phenols include o-cresol, m-cresol, p-cresol, 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 3,4-xylenol, 3,5-xylenol, Examples include 2,3,5-trimethylphenol and 3,4,5-trimethylphenol.

  Examples of the aldehydes include formaldehyde, trioxane, paraformaldehyde, benzaldehyde, acetaldehyde, propyl aldehyde, and phenylacetaldehyde.

When the alkali-soluble group-containing resin is a resin including structural units represented by general formulas (11-1) to (11-4), the general formulas (11-1) to (11) in the alkali-soluble group-containing resin are used. There is no limitation in particular about the content rate of the structural unit represented by (11-4), Although it can be made into various ranges as needed, Preferably it is 10-100 mol%, More preferably, it is 20-100 mol %.
The molecular weight of the alkali-soluble group-containing resin is not particularly limited, and can be set in various ranges depending on the characteristics of the radiation-sensitive resin composition of the present invention. Mw is preferably 1,000 to 150, It is 000, More preferably, it is 3,000-100,000, Mw / Mn is 1-10 normally, Preferably it is 1-5.

  When the alkali-soluble group-containing resin has a structural unit containing a carbon-carbon unsaturated bond represented by the general formulas (11-1) and (11-4), these hydrogenated products are also used. You can also. In this case, the hydrogenation rate is usually 70% or less, preferably 50% or less of the carbon-carbon unsaturated bonds contained in the structural units represented by the general formulas (11-1) and (11-4). More preferably, it is 40% or less. When the hydrogenation rate is in the above range, it is preferable because the development characteristics of the alkali-soluble group-containing resin with an alkali developer can be improved.

[(C) Component that generates acid upon irradiation]
The component that generates an acid upon irradiation with radiation (hereinafter, also referred to as “acid generator (C)”) used in the present invention is a compound that generates an acid upon exposure (irradiation with radiation). Due to the action of the generated acid, in the acid-dissociable group-containing resin, the existing acid-dissociable functional group is dissociated to generate an acidic functional group such as a carboxyl group or a phenolic hydroxyl group. As a result, the exposed portion of the resin film formed from the radiation-sensitive resin composition becomes readily soluble in an alkali developer, and a positive pattern can be formed.

  Examples of the acid generator (C) include onium salt compounds (including thiophenium salt compounds), halogen-containing compounds, diazoketone compounds, sulfone compounds, sulfonic acid compounds, sulfonimide compounds, diazomethane compounds, and the like. . Examples of these compounds are shown below.

Examples of the onium salt compounds include iodonium salts, sulfonium salts, phosphonium salts, diazonium salts, pyridinium salts, and the like.
Suitable examples of such onium salt compounds include diphenyliodonium trifluoromethanesulfonate, diphenyliodonium p-toluenesulfonate, diphenyliodonium hexafluoroantimonate, diphenyliodonium hexafluorophosphate, diphenyliodonium tetrafluoroborate, triphenylsulfonium trifluoromethane. Sulfonate, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium hexafluorophosphate, 4-t-butylphenyl diphenylsulfonium trifluoromethanesulfonate, 4-t-butylphenyl diphenylsulfonium perfluoro-n-octane sulfonate, 4-t -Butylphenyl diphenylsulfoniu Pyrenesulfonate, 4-t-butylphenyl diphenylsulfonium n-dodecylbenzenesulfonate, 4-t-butylphenyl diphenylsulfonium p-toluenesulfonate, 4-t-butylphenyl diphenylsulfonium benzenesulfonate, 4,7-di- Examples include n-butoxynaphthyl tetrahydrothiophenium trifluoromethanesulfonate.

Examples of the halogen-containing compound include haloalkyl group-containing hydrocarbon compounds and haloalkyl group-containing heterocyclic compounds.
Preferred examples of such halogen-containing compounds include 1,10-dibromo-n-decane, 1,1-bis (4-chlorophenyl) -2,2,2-trichloroethane, and phenyl-bis (trichloromethyl). (Trichloromethyl)-such as -s-triazine, 4-methoxyphenyl-bis (trichloromethyl) -s-triazine, styryl-bis (trichloromethyl) -s-triazine, naphthyl-bis (trichloromethyl) -s-triazine Examples thereof include s-triazine derivatives.

Examples of the diazoketone compound include 1,3-diketo-2-diazo compounds, diazobenzoquinone compounds, diazonaphthoquinone compounds, and the like.
Preferable examples of such a diazoketone compound include 1,2-naphthoquinone diazide-4-sulfonic acid ester of phenols and 1,2-naphthoquinone diazide-5-sulfonic acid ester of phenols.

Examples of the sulfonated product include β-ketosulfone, β-sulfonylsulfone, α-diazo compounds of these compounds, and the like.
Preferable examples of such a sulfone compound include 4-trisphenacylsulfone, mesitylphenacylsulfone, and bis (phenylsulfonyl) methane.

Examples of the sulfonic acid compound include alkyl sulfonic acid esters, haloalkyl sulfonic acid esters, aryl sulfonic acid esters, and imino sulfonates.
Preferable examples of such sulfonic acid compounds include benzoin tosylate, pyrogallol tris trifluoromethane sulfonate, o-nitrobenzyl trifluoromethane sulfonate, and o-nitrobenzyl-p-toluene sulfonate.

  Examples of the sulfonimide compound include N- (trifluoromethylsulfonyloxy) succinimide, N- (trifluoromethylsulfonyloxy) phthalimide, N- (trifluoromethylsulfonyloxy) diphenylmaleimide, N- (trifluoromethylsulfonyloxy). ) Bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (trifluoromethylsulfonyloxy) -7-oxabicyclo [2.2.1] hept-5-ene- 2,3-dicarboximide, N- (trifluoromethylsulfonyloxy) bicyclo [2.2.1] heptane-5,6-oxy-2,3-dicarboximide, N- (trifluoromethylsulfonyloxy) Naphthylimide, N- (4-methylphenylsulfonyloxy) Xinimide, N- (4-methylphenylsulfonyloxy) phthalimide, N- (4-methylphenylsulfonyloxy) diphenylmaleimide, N- (4-methylphenylsulfonyloxy) bicyclo [2.2.1] hept-5-ene -2,3-dicarboximide, N- (4-methylphenylsulfonyloxy) -7-oxabicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (4- Methylphenylsulfonyloxy) bicyclo [2.2.1] heptane-5,6-oxy-2,3-dicarboximide, N- (4-methylphenylsulfonyloxy) naphthylimide, N- (2-trifluoromethyl) Phenylsulfonyloxy) succinimide, N- (2-trifluoromethylphenylsulfonyloxy) Phthalimide, N- (2-trifluoromethylphenylsulfonyloxy) diphenylmaleimide, N- (2-trifluoromethylphenylsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide N- (2-trifluoromethylphenylsulfonyloxy) -7-oxabicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (2-trifluoromethylphenylsulfonyloxy) ) Bicyclo [2.2.1] heptane-5,6-oxy-2,3-dicarboximide, N- (2-trifluoromethylphenylsulfonyloxy) naphthylimide, N- (4-fluorophenylsulfonyloxy) Succinimide, N- (4-fluorophenylsulfonyloxy) -7-oxabici Chlo [2.1.1] hept-5-ene-2,3-dicarboximide, N- (4-fluorophenylsulfonyloxy) bicyclo [2.1.1] heptane-5,6-oxy-2, Examples include 3-dicarboximide, N- (4-fluorophenylsulfonyloxy) naphthylimide, N- (10-camphor-sulfonyloxy) naphthylimide, and the like.

  Examples of the diazomethane compound include bis (trifluoromethylsulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, bis (phenylsulfonyl) diazomethane, bis (p-toluenesulfonyl) diazomethane, methylsulfonyl-p-toluenesulfonyldiazomethane, and cyclohexylsulfonyl. Examples include -1,1-dimethylethylsulfonyldiazomethane and bis (1,1-dimethylethylsulfonyl) diazomethane.

  Of these acid generators (C), onium salt compounds, sulfonimide compounds, and diazomethane compounds are preferred.

In the radiation-sensitive resin composition of the present invention, the acid generator (C) can be used alone or in admixture of two or more.
The compounding amount of the acid generator (C) is usually 0.1 to 20 parts by mass, preferably 0.3 to 15 parts by mass, more preferably 100 parts by mass of the resin component in the radiation sensitive resin composition. Is 0.5 to 10 parts by mass. When the blending amount of the acid generator (C) is within the above range, a resist having excellent sensitivity, resolution, and transparency to radiation can be obtained, and a pattern having an excellent shape can be obtained.

[Vinyl alkyl ether resin]
In addition, the radiation-sensitive resin composition in the present invention may further contain a vinyl alkyl ether resin represented by the following general formula (4). This vinyl alkyl ether resin is a terminal-modified vinyl alkyl ether resin (polymer or oligomer), and the radiation-sensitive resin composition can form a pattern with a good shape by containing such a resin. In addition, the occurrence of cracks in the coating film can be reduced.

In the general formula (4), R ⁹ and R ¹⁰ may be the same or different and each represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, or a substituted or unsubstituted group having 3 to 20 carbon atoms. An aliphatic group, a substituted or unsubstituted aryl group, a hydroxyl group, or a carboxyl group. Among these, a hydrogen atom, a hydroxyl group, or a carboxyl group is preferable.
R ¹¹ is an alkyl group having 1 to 4 carbon atoms, and specific examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, etc., preferably methyl Group and ethyl group.

  The vinyl alkyl ether resins may be selected from resins that are fluid at room temperature to flexible resins depending on the degree of polymerization. Therefore, although it does not specifically limit as q in General formula (4), Usually, it is an integer greater than or equal to 1, Preferably it is 1-100, More preferably, it is 10-50.

  When the vinyl alkyl ether resin is contained, it is contained in the radiation-sensitive resin composition of the present invention in an amount of 2 to 60 parts by mass, preferably 5 to 50 parts by mass with respect to 100 parts by mass of the resin component. The When this content is lower than the above range, cracks may occur in the coating film during electrolytic plating, or after washing or drying after plating. When the content exceeds the above range, exposure is performed during development. The contrast between the area and the unexposed area may not be obtained, and the pattern shape may deteriorate.

[Additive]
In the radiation-sensitive resin composition of the present invention, one or more additives such as an acid diffusion controller, a surfactant, and a sensitizer are added as necessary within the range not impairing the object of the present invention. It may be added.

<Acid diffusion control agent>
The acid diffusion control agent that can be added to the radiation-sensitive resin composition of the present invention controls the diffusion phenomenon in the resist film of the acid generated from the acid generator (C) and the like by exposure, and in an unexposed region. It has the effect of suppressing undesirable chemical reactions. Therefore, the storage stability of the radiation sensitive resin composition can be improved by blending the acid diffusion controller.
In addition, by adding the acid diffusion control agent, it is possible to improve the resolution as a resist, and to suppress a change in the line width of the resist pattern due to a change in the holding time (PED) from exposure to development processing. Thus, it is preferable to add an acid diffusion controller because a radiation-sensitive resin composition having extremely excellent process stability can be obtained.

  The acid diffusion controller is preferably a nitrogen-containing organic compound whose basicity does not change by exposure or heat treatment during the resist pattern formation step. Examples of such a nitrogen-containing organic compound include a compound represented by the following general formula (12) (hereinafter referred to as “nitrogen-containing compound (I)”) and a diamino compound having two nitrogen atoms in the same molecule. (Hereinafter referred to as “nitrogen-containing compound (II)”), a polyamino compound or polymer having three or more nitrogen atoms (hereinafter referred to as “nitrogen-containing compound (III)”), an amide group-containing compound, a urea compound, And nitrogen-containing heterocyclic compounds. Among these nitrogen-containing organic compounds, nitrogen-containing compounds (I), nitrogen-containing compounds (II) and nitrogen-containing heterocyclic compounds are preferable. The acid diffusion controller may be used alone or in combination of two or more.

In the general formula (12), R ²⁸ , R ²⁹ and R ³⁰ may be the same or different from each other, and are a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or An unsubstituted aralkyl group is shown.
The substituted or unsubstituted alkyl group may be linear, branched or cyclic, and examples thereof include those having 1 to 15 carbon atoms, preferably 1 to 10 carbon atoms, specifically, methyl group, ethyl group N-propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group, t-butyl group, n-pentyl group, neopentyl group, n-hexyl group, texyl group, n-to Examples include a butyl group, an n-octyl group, an n-ethylhexyl group, an n-nonyl group, and an n-decyl group.
As said substituted or unsubstituted aryl group, a C6-C12 thing is mentioned, Specifically, a phenyl group, a tolyl group, a xylyl group, a cumenyl group, 1-naphthyl group etc. are mentioned.
Examples of the substituted or unsubstituted aralkyl group include those having 7 to 19 carbon atoms, preferably 7 to 13 carbon atoms, such as benzyl group, α-methylbenzyl group, phenethyl group, and naphthylmethyl group. Can be mentioned.

Examples of the nitrogen-containing compound (I) include monoalkylamines such as n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, n-decylamine;
Dialkylamines such as di-n-butylamine, di-n-pentylamine, di-n-hexylamine, di-n-heptylamine, di-n-octylamine, di-n-nonylamine, di-n-decylamine ;
Triethylamine, tri-n-propylamine, tri-n-butylamine, tri-n-pentylamine, tri-n-hexylamine, tri-n-heptylamine, tri-n-octylamine, tri-n-nonylamine, tri -Trialkylamines such as n-decylamine;
Aromatic amines such as aniline, N-methylaniline, N, N-dimethylaniline, 2-methylaniline, 3-methylaniline, 4-methylaniline, 4-nitroaniline, diphenylamine, triphenylamine, 1-naphthylamine;
Examples include alkanolamines such as ethanolamine, diethanolamine, and triethanolamine.

  Examples of the nitrogen-containing compound (II) include ethylenediamine, N, N, N ′, N′-tetramethylethylenediamine, tetramethylenediamine, hexamethylenediamine, N, N, N ′, N′-tetrakis (2- Hydroxyethyl) ethylenediamine, N, N, N ′, N′-tetrakis (2-hydroxypropyl) ethylenediamine, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenyl ether, 4,4′-diaminobenzophenone, 4, 4'-diaminodiphenylamine, 2,2'-bis (4-aminophenyl) propane, 2- (3-aminophenyl) -2- (4-aminophenyl) propane, 2- (4-aminophenyl) -2- (3-hydroxyphenyl) propane, 2- (4-aminophenyl) -2- (4- Loxyphenyl) propane, 1,4-bis [1- (4-aminophenyl) -1-methylethyl] benzene, 1,3-bis [1- (4-aminophenyl) -1-methylethyl] benzene and the like. Can be mentioned.

  Examples of the nitrogen-containing compound (III) include polymers of polyethyleneimine, polyallylamine, dimethylaminoethylacrylamide, and the like.

  Examples of the amide group-containing compound include formamide, N-methylformamide, N, N-dimethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, propionamide, benzamide, pyrrolidone, N-methylpyrrolidone and the like. Can be mentioned.

  Examples of the urea compound include urea, methylurea, 1,1-dimethylurea, 1,3-dimethylurea, 1,1,3,3-tetramethylurea, 1,3-diphenylurea, tributylthiourea and the like. be able to.

  Examples of the nitrogen-containing heterocyclic compound include imidazole, benzimidazole, 2-phenylbenzimidazole, 2-methylimidazole, 4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, and 4-methyl-2-phenyl. Imidazoles such as imidazole, pyridine, 2-methylpyridine, 4-methylpyridine, 2-ethylpyridine, 4-ethylpyridine, 2-phenylpyridine, 4-phenylpyridine, N-methyl-4-phenylpyridine, nicotine, nicotine In addition to pyridines such as acid, nicotinamide, quinoline, 8-oxyquinoline and acridine, pyrazine, pyrazole, pyridazine, quinosaline, purine, pyrrolidine, piperidine, 1-piperidineethanol, 2-piperidineethanol, mole Phosphorus, 4-methylmorpholine, piperazine, 1,4-dimethylpiperazine, 1,4-diazabicyclo [2.2.2] octane, triazine, 2,4,6-tri (2-pyridyl) -1,3,5 -A triazine etc. can be mentioned.

  Moreover, the nitrogen-containing compound which has an acid dissociable group can also be used as said nitrogen-containing organic compound. Examples of the nitrogen-containing compound having an acid dissociable group include N- (t-butoxycarbonyl) piperidine, N- (t-butoxycarbonyl) imidazole, N- (t-butoxycarbonyl) benzimidazole, N— (T-butoxycarbonyl) 2-phenylbenzimidazole, N- (t-butoxycarbonyl) dioctylamine, N- (t-butoxycarbonyl) diethanolamine, N- (t-butoxycarbonyl) dicyclohexylamine, N- (t-butoxycarbonyl ) Diphenylamine and the like.

The acid diffusion controller may be used alone or in combination of two or more.
The compounding amount of the acid diffusion control agent is usually 15 parts by mass or less, preferably 0.001 to 10 parts by mass, more preferably 0.005 with respect to 100 parts by mass of the total resin components in the radiation-sensitive resin composition. -5 parts by mass. By making the compounding amount of the acid diffusion controller within the above range, it is possible to improve the sensitivity as a resist and the developability of the exposed portion, and it is preferable because it can suppress a decrease in pattern shape and dimensional fidelity as a resist. .

<Surfactant>
The surfactant that can be added to the radiation-sensitive resin composition of the present invention exhibits the action of improving the coating property, striation, developability, and the like of the radiation-sensitive resin composition.
As such a surfactant, any of anionic, cationic, nonionic or amphoteric surfactants can be used, but nonionic surfactants are preferred.

Examples of the nonionic surfactant include polyoxyethylene higher alkyl ethers, polyoxyethylene higher alkyl phenyl ethers, higher fatty acid diesters of polyethylene glycol, and the like. Specifically, polyoxyethylene lauryl ether , Polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene n-octylphenol ether, polyoxyethylene n-nonylphenol ether, polyethylene glycol dilaurate, polyethylene glycol distearate and the like.
Commercially available products include “KP” (manufactured by Shin-Etsu Chemical Co., Ltd.), “Polyflow” (manufactured by Kyoeisha Yushi Chemical Co., Ltd.), “F Top” (manufactured by Tochem Products), and “MegaFuck” (manufactured by Dainippon Ink and Chemicals, Inc. ), "Florard" (manufactured by Sumitomo 3M), "Asahi Guard" and "Surflon" (manufactured by Asahi Glass).

These surfactants can be used alone or in admixture of two or more.
The compounding quantity of this surfactant is 2 mass parts or less normally as an active ingredient of surfactant with respect to 100 mass parts of all the resin components in a radiation sensitive resin composition.

<Sensitizer>
The sensitizer that can be added to the radiation-sensitive resin composition of the present invention absorbs the energy of radiation and transmits the energy to the acid generator (C) and other acid generators. It has the effect of increasing the production amount and thereby improving the apparent sensitivity of the radiation-sensitive resin composition.
Examples of such sensitizers include acetophenones, benzophenones, naphthalene, biacetyl, eosin, rose bengal, pyrenes, anthracenes, phenothiazines and the like. These sensitizers can be used alone or in admixture of two or more.

[Other additives]
The radiation sensitive resin composition of the present invention may further contain one or more other additives. Examples of other additives include ultraviolet absorbers, dispersants, plasticizers, thermal polymerization inhibitors for improving storage stability, and antioxidants.
Among these, the ultraviolet absorber is useful because it has a function of preventing a photoreaction caused by wraparound of scattered light during exposure to an unexposed portion. As such an ultraviolet absorber, a compound having a high extinction coefficient in the wavelength region of ultraviolet rays used for exposure is preferable. Organic pigments can also be used for the same purpose.

[Organic solvent]
In the present invention, the radiation-sensitive resin composition can be diluted with an organic solvent for the purpose of uniformly mixing.
Examples of the organic solvent include ethers, esters, ether esters, ketones, ketone esters, amides, amide esters, lactams, lactones, and (halogenated) hydrocarbons. it can.
Specifically, ethylene glycol monoalkyl ethers, diethylene glycol dialkyl ethers, propylene glycol monoalkyl ethers, propylene glycol dialkyl ethers, ethylene glycol monoalkyl ether acetates, propylene glycol monoalkyl ether acetates, acetate esters, Hydroxyacetic acid esters, lactic acid esters, alkoxyacetic acid esters, (non) cyclic ketones, acetoacetic acid esters, pyruvate esters, propionate esters, N, N-dialkylformamides, N, N-dialkyl Acetamides, N-alkylpyrrolidones, γ-lactones, (halogenated) aliphatic hydrocarbons, (halogenated) aromatic hydrocarbons and the like can be mentioned.

  More specifically, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol di-n-propyl ether, diethylene glycol Di-n-butyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol mono-n-propyl ether acetate, isopropenyl acetate, isopropenyl propio Nate, toluene Xylene, methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone, 4-heptanone, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, 2-hydroxy-3- Methyl methylbutyrate, methyl lactate, ethyl lactate, n-propyl lactate, i-propyl lactate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutylpropionate, 3- Methyl-3-methoxybutyl butyrate, ethyl acetate, n-propyl acetate, n-butyl acetate, methyl acetoacetate, ethyl acetoacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate , 3-etoki Ethyl propionate, N- methylpyrrolidone, N, N- dimethylformamide, N, may be mentioned N- dimethylacetamide.

Among these, propylene glycol monoalkyl ether acetates, 2-heptanone, lactic acid esters, propionic acid esters (specifically, 2-hydroxypropionic acid esters such as ethyl 2-hydroxypropionate, 3-methoxy It is preferable to use 3-alkoxypropionic acid esters such as methyl propionate, etc., since the uniformity in the film surface during coating becomes good.
These organic solvents may be used individually by 1 type, and may mix and use 2 or more types.

In addition, the organic solvent may contain a solvent other than the organic solvent (hereinafter referred to as “other solvent”) as necessary.
Examples of the other solvent include benzyl ethyl ether, di-n-hexyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, acetonyl acetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, and benzyl. Examples thereof include high-boiling solvents such as alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, and ethylene glycol monophenyl ether acetate.
These other solvents may be used alone or in combination of two or more.

  The amount of the organic solvent used is not particularly limited as long as the resin composition can be mixed uniformly, and is adjusted in consideration of the application method of the radiation sensitive resin composition, the use of the composition for producing a plated model, and the like. be able to. Generally, it is preferable that 20-80 mass parts of organic solvents are contained with respect to the total mass (100 mass parts) of a radiation sensitive resin composition, and it is more preferable that 30-70 mass parts is contained. . When the organic solvent is within the above range, the thickness of the resin film formed by applying the resin composition can be made uniform, and the shape of the desired high bump can be made uniform.

[Radiation-sensitive resin film and transfer film]
The radiation sensitive resin film in this invention is formed from the said radiation sensitive resin composition, It is characterized by the above-mentioned. The radiation-sensitive resin film can be formed by directly applying the resin composition on a predetermined molded plate and drying it. Moreover, the transfer film of this invention which has a radiation sensitive resin film can be obtained by apply | coating the said resin composition on a support film, and drying.
The film thickness of the radiation sensitive resin film is preferably 10 to 100 μm, more preferably 15 to 80 μm, and still more preferably 20 to 60 μm.
Examples of the method for applying the radiation-sensitive resin composition include spin coating, roll coating, screen printing, and applicator methods.
The drying conditions vary depending on the type of each component in the resin composition, the blending ratio, the coating film thickness, etc., but are usually from 70 to 140 ° C. for about 5 to 20 minutes, preferably from 80 to 130 ° C. About 10 minutes.
The material of the support film is not particularly limited as long as it has a strength that can withstand the production and use of the transfer film.

[Method of manufacturing plated model]
The method for producing a plated model according to the present invention is as follows.
(A) The above-mentioned radiation sensitive resin composition is coated on a substrate having a conductive layer on the surface (for example, a wafer having a barrier metal layer) and dried, whereby a sensitivity comprising the above resin composition on the substrate. Forming a radiation resin film;
(B) irradiating (exposing) radiation to the resin film through a mask having a predetermined pattern;
(C) heating the resin film after exposure and then developing to form a pattern;
(D) a step of forming a plated shaped article (for example, electrode material) by electrolytic plating using the pattern as a mold,
(E) a step of removing the resin film remaining on the substrate, and (f) a step of removing the conductive layer other than the region where the plated model is formed, for example, by a wet etching method or the like.

Examples of the substrate include soda glass, quartz glass, silicon carbide, titanium carbide, zirconium carbide, boron nitride, aluminum nitride, silicon nitride, silicon, germanium, gallium-arsenic, and gallium-phosphorus.
Examples of the conductive material used for forming the conductive layer on the surface of the substrate include aluminum, copper, silver, gold, palladium, and two or more alloys thereof (for example, palladium-gold). Can do. The conductive layer on the substrate surface can be formed by processing the conductive material by, for example, sputtering. The thickness of the conductive layer is not particularly limited, but is usually about 200 to 10,000 mm, preferably about 500 to 2,000 mm.
Examples of the method for applying the radiation-sensitive resin composition of the present invention on a substrate include spin coating, roll coating, screen printing, and applicator methods.
The transfer film of the present invention is not limited to the method in which the radiation-sensitive resin film formed on the substrate in the step (a) is formed by applying the radiation-sensitive resin composition onto the substrate and drying it. Alternatively, the radiation sensitive resin film may be formed by transferring and laminating on the substrate.

The radiation used for the exposure in the above step (b) is represented by ultraviolet light from a low-pressure mercury lamp, high-pressure mercury lamp, ultrahigh-pressure mercury lamp, metal halide lamp, g-line stepper, i-line stepper, etc .; KrF excimer laser or ArF excimer laser In addition to far-ultraviolet rays, charged particle beams such as electron beams, X-rays such as synchrotron radiation, and the like, and radiation having a wavelength in the range of 150 to 500 μm are particularly preferable.
The amount of exposure varies depending on the type of radiation, the composition of the composition, the thickness of the resin film, etc., but is usually about 1,000 to 20,000 J / m ^{2 in} the case of ultraviolet rays from a high-pressure mercury lamp, for example.

The development treatment in the above step (c) can be performed, for example, using an alkaline developer by a shower development method, a spray development method, an immersion development method, a paddle development method, or the like.
This development time is usually about 1 to 30 minutes at room temperature.
In addition, after developing with an alkaline developer, it is usually washed with water and dried.

  Examples of the alkaline developer include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, aqueous ammonia, ethylamine, n-propylamine, diethylamine, triethylamine, monoethanolamine, diethanolamine, triethanolamine, and tetramethyl. Examples include an alkaline aqueous solution in which one or two or more alkaline compounds such as ammonium hydroxide, tetraethylammonium hydroxide, choline, pyrrole, piperidine and the like are dissolved in water so that the concentration becomes, for example, 1 to 10% by mass. it can. For example, an appropriate amount of an organic solvent such as methanol or ethanol, a surfactant, or the like can be added to the alkaline aqueous solution.

In the electrolytic plating in the above step (d), in order to increase the affinity between the pattern surface and the plating solution, the pattern formed from the resin film may be subjected to a hydrophilic treatment such as an ashing treatment using oxygen plasma, for example. preferable.
Examples of the plating solution used for electrolytic plating include those containing the same components as the metals and alloys exemplified for the conductive layer. The conditions for electrolytic plating vary depending on the composition of the plating solution, etc. For example, in the case of gold plating, the temperature is usually 40 to 70 ° C., preferably about 55 to 70 ° C., and the current density is usually 0.1. ˜1 A / dm ² , preferably about 0.2 to 0.8 A / dm ² . After plating, after washing and drying, the state of the pattern, the thickness and state of the plated model are observed, and electrolytic plating is performed again as necessary.

  Although the thickness of the plated model varies depending on the application, for example, in the case of a bump, it is usually 5 to 50 μm, preferably 10 to 30 μm, and more preferably 15 to 25 μm. Moreover, in the case of wiring, it is 1-30 micrometers normally, Preferably it is 3-20 micrometers, More preferably, it is 5-15 micrometers.

As a peeling method of the resin film part which remains in the said process (e), the method etc. which immerse a board | substrate in the peeling liquid stirred at 20-80 degreeC, for example for about 1-10 minutes, etc. can be mentioned, for example. .
As the stripping solution, for example, a mixed solution of dimethyl sulfoxide and N, N-dimethylformamide can be used.

  EXAMPLES Hereinafter, although this invention is demonstrated more concretely based on an Example, this invention is not limited to these Examples at all. In the following, parts and% are based on mass unless otherwise specified.

<Synthesis of acid-dissociable group-containing resin (A)>
[Synthesis Example 1]
25 g of poly (p-hydroxystyrene) was dissolved in 100 g of propylene glycol monomethyl ether acetate, and bubbled with nitrogen gas for 30 minutes. Next, 3.5 g of ethyl vinyl ether was added to this solution, 1 g of p-toluenesulfonic acid pyridinium salt was added as a catalyst, and the mixture was allowed to react at room temperature for 12 hours. Thereafter, the reaction solution was dropped into a 1% by mass aqueous ammonia solution to precipitate the resin, filtered, and dried overnight in a vacuum dryer at 50 ° C. The obtained resin had Mw of 13000 and Mw / Mn of 1.7. Moreover, as a result of ¹ H-NMR analysis, it had a structure in which 24 mol% of the hydrogen atoms of the phenolic hydroxyl group in poly (p-hydroxystyrene) were substituted with ethoxyxyethyl groups. This resin is referred to as “resin (A-1)”.

[Synthesis Example 2]
25 g of a p-hydroxystyrene / pt-butoxycarbonyloxystyrene copolymer having a molar ratio of 92: 8 was dissolved in 100 g of propylene glycol monomethyl acetate and bubbled with nitrogen gas for 30 minutes. Next, 3.3 g of ethyl vinyl ether was added to this solution, 1 g of p-toluenesulfonic acid pyridinium salt was added as a catalyst, and the mixture was allowed to react at room temperature for 12 hours. Thereafter, the reaction solution was dropped into a 1% by mass aqueous ammonia solution to precipitate the resin, filtered, and dried overnight in a vacuum dryer at 50 ° C. The obtained resin had Mw of 13000 and Mw / Mn of 1.8. As a result of ¹³ C-NMR analysis, 23 mol% of the hydrogen atoms of the phenolic hydroxyl group in poly (p-hydroxystyrene) were substituted with ethoxyxyethyl groups and 8 mol% with t-butoxycarbonyloxy groups. It had a structure. This resin is referred to as “resin (A-2)”.

<Synthesis of other acid-dissociable group-containing resin (a)>
[Synthesis Example 3]
After 97 g of p-acetoxystyrene, 51 g of pt-butoxystyrene, 6 g of AIBN and 1 g of t-dodecyl mercaptan were dissolved in 160 g of propylene glycol monomethyl ether, polymerization was carried out for 16 hours while maintaining the reaction temperature at 70 ° C. in a nitrogen atmosphere. It was. After polymerization, the reaction solution was dropped into a large amount of hexane, and the resulting resin was coagulated and purified. Next, 150 g of propylene glycol monomethyl ether was added to the purified resin again, and then 300 g of methanol, 80 g of triethylamine and 15 g of water were further added, and a hydrolysis reaction was performed for 8 hours while refluxing at the boiling point. After the reaction, the solvent and triethylamine were distilled off under reduced pressure, the resulting resin was dissolved in acetone, then dripped into a large amount of water to solidify, and the resulting white powder was filtered and dried overnight at 50 ° C. under reduced pressure. did. The obtained resin had Mw of 16500 and Mw / Mn of 1.7. As a result of ¹³ C-NMR analysis, the copolymerization molar ratio of p-hydroxystyrene and pt-butoxystyrene was 67:33. there were. This resin is referred to as “resin (a-1)”.

<Synthesis of comparative polymer>
[Synthesis Example 4]
30 g of α-methyl-4-hydroxystyrene, 20 g of 2-hydroxyethyl acrylate and 31 g of t-butyl acrylate were mixed with 150 g of ethyl lactate and stirred at 50 ° C. to obtain a uniform solution. After bubbling this solution with nitrogen gas for 30 minutes, 4 g of AIBN was added, and polymerization was carried out for 7 hours while maintaining the reaction temperature at 70 ° C. while keeping the inside of the reaction system in a nitrogen atmosphere. After completion of the polymerization, the reaction solution was mixed with a large amount of hexane to solidify the produced polymer. Then, after redissolving the polymer in tetrahydrofuran, the operation of coagulating with hexane again was repeated several times to remove the unreacted monomer and dried at 50 ° C. under reduced pressure to obtain a white polymer (R-1). .

<Synthesis of imide group-containing resin (B)>
[Synthesis Example 5]
α-Methyl-4-hydroxystyrene (40 g) and N-acryloyloxyethyl hexahydrophthalimide (160 g) were mixed with propylene glycol monomethyl ether (300 g) to obtain a uniform solution. After bubbling this solution with nitrogen gas for 30 minutes, 6 g of AIBN was added, and while maintaining the reaction system in a nitrogen atmosphere, the reaction temperature was maintained at 70 ° C. for 3 hours to polymerize, and 3 g of AIBN was further added to react. The temperature was maintained at 80 ° C., and polymerization was further performed for 3 hours. After completion of the polymerization, the reaction solution was mixed with a large amount of hexane to solidify the produced polymer. Subsequently, after the polymer was redissolved in tetrahydrofuran, the operation of coagulation with hexane was repeated several times to remove unreacted monomers and dried at 50 ° C. under reduced pressure to obtain a white polymer. The obtained resin contains the following structural units, and Mw was 12000 and Mw / Mn was 6.5. This resin is referred to as “resin (B-1)”.

[Example 1]
(Preparation of positive radiation sensitive resin composition)
As shown in Table 1, 100 parts by mass of the acid dissociable group-containing resin (A-1) obtained in Synthesis Example 1, 5 parts by mass of the imide group-containing resin (B-1) obtained in Synthesis Example 5, and acid Generator [4,7-di-n-butoxynaphthyltetrahydrothiophenium trifluoromethanesulfonate (C-1)] 1 part by mass, terminal-modified vinyl alkyl ether resin (D-1) 5 parts by mass, and acid diffusion controller 0.34 parts by mass of [2,4,6-tri (2-pyridyl) -1,3,5-triazine (E-1)], 40 parts by mass of an organic solvent [ethyl lactate (F-1) and propylene glycol After dissolving in 90 parts by mass of monomethyl ether acetate (F-2)], the mixture was filtered through a Teflon (registered trademark) membrane filter having a pore diameter of 3 μm to prepare a radiation sensitive resin composition.

(Preparation of gold sputter substrate)
Sputtering was performed on a silicon wafer substrate having a diameter of 4 inches so that the thickness was about 500 mm, and then gold was sputtered so that the thickness was 1,000 mm, thereby forming a conductive layer. Hereinafter, the substrate on which the conductive layer is formed is referred to as a “gold sputter substrate”.

(Pattern formation)
The resin composition was applied to a gold sputter substrate using a spin coater, and then heated on a hot plate at 120 ° C. for 5 minutes to form a resin film having a thickness of 25 μm. Next, ultraviolet light (g, h, i mixed line) of 200 to 1500 mJ / cm ² was irradiated using an ultrahigh pressure mercury lamp (manufactured by OSRAM, “HBO”, output 1,000 W) through a pattern mask. The exposure amount was confirmed by an illuminometer (manufactured by Oak Manufacturing Co., Ltd., “UV-M10” (illuminance meter) connected to “probe UV-35” (light receiver)).
After the exposure, PEB was performed on a hot plate at 70 ° C. for 5 minutes. Subsequently, using a 2.38 mass% tetramethylammonium hydroxide aqueous solution, the film was immersed for 3 minutes at room temperature for development, washed with running water, and blown with nitrogen to form a pattern. Hereinafter, the substrate on which this pattern is formed is referred to as a “patterning substrate”.

(Formation of plated objects)
The patterning substrate was subjected to an ashing treatment (output 100 W, oxygen flow rate 100 ml, treatment time 1 minute) by oxygen plasma as a pretreatment for electroplating to perform a hydrophilic treatment. Next, this substrate is immersed in 1 liter of a non-cyanide gold plating solution (trade name “ECF-88K” manufactured by N.E. Chemcat Co., Ltd.), and the plating bath temperature is set to 70 ° C. and the current density is set to 0.8 A / dm ^2. Electrolytic plating was performed for about 30 minutes to form a plated shaped product having a thickness of 20 to 25 μm. Next, it was washed with running water, dried by blowing with nitrogen gas, and then immersed in a mixed solution of dimethyl sulfoxide and N, N-dimethylformamide (mass ratio = 50: 50) at room temperature for 5 minutes. The board | substrate which has a plating modeling thing was obtained by peeling the resin film part to perform, and also removing conductive layers other than the area | region which formed the plating modeling article on a board | substrate by wet etching. Hereinafter, the substrate having the plated model is referred to as a “plated substrate”.

(Evaluation)
The following evaluations are performed, and the evaluation results are shown in Table 2.
(1) Sensitivity When a 40 μm pitch pattern (30 μm wide blanked pattern / 10 μm wide left pattern) is formed on a gold sputtered substrate as the mask design dimension, the exposure amount at which the bottom dimension of the blank pattern is 30 μm is the optimum exposure dose. Evaluation was made based on the optimum exposure amount.

(2) Resolution Two patterning substrates on which two types of patterns (30 μm width removed pattern / 10 μm width remaining pattern, 32 μm width removed pattern / 8 mm width remaining pattern) with a mask design dimension of 40 μm pitch are separately formed are optical microscopes. Were observed with a scanning electron microscope and evaluated according to the following criteria.
A: 32 μm width removal pattern / 8 μm width remaining pattern can be resolved.
Δ: The 30 μm width removed pattern / 10 μm width remaining pattern can be resolved, but the 32 μm width removed pattern / 8 μm width remaining pattern cannot be resolved.
X: A pattern with a pitch of 40 μm cannot be resolved or cannot be resolved with good reproducibility.

(3) Adhesiveness Evaluation of adhesiveness with a substrate was evaluated by observing a cross section of a cured resist film after development at a magnification of 1500 using a scanning electron microscope, and by the following criteria.
◯: Resist lift is not observed around the opening and at the edge of the wafer.
X: Resist floating and resist peeling are observed.

(4) Crack resistance Substrate that has been formed on the patterning substrate in the same manner as described above, washed with running water, blown with nitrogen gas, and dried (the substrate on which the resin film portion has not been peeled off) Was allowed to stand in a clean room maintained at a room temperature of 23 ° C. and a humidity of about 45%. After 3 hours and 24 hours, the substrate surface was observed with an optical microscope and evaluated according to the following criteria. Here, the “remaining pattern” corresponds to a resist pattern.
○: No cracks appear in the remaining pattern even after 24 hours.
Δ: Cracks do not occur in the remaining pattern after 3 hours, but cracks occur in the remaining pattern after 24 hours.
X: Cracks occur in the remaining pattern after 3 hours.

(5) Plating shape (A)
The plated substrate on which the plated model is formed on the patterning substrate on which the pattern of the mask size is 40 μm pitch (30 μm wide pattern / 10 μm width remaining pattern) is observed with an optical microscope and a scanning electron microscope. evaluated.
A: The shape of the plating faithfully transfers the pattern shape formed from the resin film, and no knurled abnormal protrusion is observed.
X: The shape of the plating does not faithfully transfer the pattern shape formed from the resin film, and a knurled abnormal protrusion is recognized.

(6) Plating shape (B)
The plated substrate on which the plated model is formed on the patterning substrate on which the pattern of the mask size is 40 μm pitch (30 μm wide pattern / 10 μm width remaining pattern) is observed with an optical microscope and a scanning electron microscope. evaluated.
A: The shape of the plating bottom portion faithfully transfers the pattern shape formed from the resin film, and no trace of plating exuding on the pattern bottom portion is seen.
X: The shape of the plating bottom portion does not faithfully transfer the pattern shape formed from the resin film, and a trace of plating exuding at the pattern bottom portion is seen.

[Examples 2 to 4 and Comparative Examples 1 to 2]
A radiation sensitive resin composition having the composition shown in Table 1 was prepared in the same manner as in Example 1. Then, in the same manner as in Example 1, a pattern and a plated model were formed and evaluated. The evaluation results are also shown in Table 2.

In addition, each component in Table 1 is as follows.
<Acid generator (C)>
C-1: 4,7-di-n-butoxynaphthyltetrahydrothiophenium trifluoromethanesulfonate
<Vinyl alkyl ether resin (D)>
D-1: Terminal-OH-modified vinyl alkyl ether resin (manufactured by Kyowa Hakko Chemical Co., Ltd., “TOE-2000H”)
D-2: Polyvinyl methyl ether (Mw = 50,000: manufactured by Tokyo Chemical Industry Co., Ltd.) with an ethanol solution having a concentration of 50% by mass replaced with ethyl lactate using a rotary evaporator, and the concentration was 50% by mass. A solution of
<Acid diffusion control agent>
E-1: 2,4,6-tri (2-pyridyl) -1,3,5-triazine E-2: 2-phenylimidazole
<Organic solvent>
F-1: Ethyl lactate F-2: Propylene glycol monomethyl ether acetate

Claims (11)

(A) an acid dissociable group-containing resin containing a structural unit represented by the following general formula (1) and a structural unit represented by the following general formula (2):
(B) a resin containing a structural unit represented by the following general formula (3), and (C) a component that generates an acid upon irradiation with radiation,
And a positive-type radiation-sensitive resin composition characterized in that it is for producing a plated model.

[In General Formula (1), R ¹ represents a hydrogen atom or a methyl group, R ² represents a methyl group or an ethyl group, and R ³ represents a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms. Indicates. R ² and R ³ may be bonded to each other to form a cyclic structure. ]

[In General Formula (2), R ⁴ represents a hydrogen atom or a methyl group, and R ⁵ represents a monovalent organic group. Moreover, m is an integer of 0-4, n is an integer of 1-4. ]

[In General Formula (3), R ⁶ represents a hydrogen atom or a methyl group, and R ⁷ and R ⁸ are each independently a hydrogen atom, a linear, branched or cyclic alkyl having 1 to 6 carbon atoms. Indicates a group. R ⁷ and R ⁸ may be bonded to each other to form a cyclic structure. Moreover, p is an integer of 1-4. ]
A vinyl alkyl ether resin represented by the following general formula (4) is further contained, and the content of the vinyl alkyl ether resin is 2 to 60 parts by mass with respect to 100 parts by mass of the resin component. 1. The positive radiation sensitive resin composition according to 1.

[In General Formula (4), R ⁹ and R ¹⁰ may be the same or different, and each represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, a substituted or non-substituted group having 3 to 20 carbon atoms. A substituted aliphatic group, a substituted or unsubstituted aryl group, a hydroxyl group, or a carboxyl group is shown. R ¹¹ is an alkyl group having 1 to 4 carbon atoms, and q is an integer of 1 to 100. ]
  The positive radiation-sensitive resin composition according to claim 1, wherein the content of the component (C) is 0.1 to 20 parts by mass with respect to 100 parts by mass of the resin component.   The positive radiation sensitive resin composition according to any one of claims 1 to 3, wherein the component (C) is at least one compound selected from the group consisting of an onium salt compound, a sulfonimide compound and a diazomethane compound.   The positive radiation-sensitive resin composition according to any one of claims 1 to 4, further comprising an acid diffusion controller.   6. The positive radiation sensitive resin composition according to claim 1, wherein the plated model is a bump.   A positive radiation-sensitive resin film, which is formed from the positive radiation-sensitive resin composition according to claim 1.   A transfer film comprising the positive radiation-sensitive resin film according to claim 7. (A) The positive radiation sensitive resin composition according to any one of claims 1 to 6 is applied on a substrate having a conductive layer on the surface and dried to form a resin film on the substrate. Process,
(B) irradiating the resin film with radiation through a mask having a predetermined pattern;
(C) heating the substrate having the resin film, and developing to form a pattern;
(D) using the pattern as a mold and forming a plated object by electrolytic plating;
(E) A process for peeling a resin film remaining on a substrate, and (f) a process for removing a conductive layer other than a region where the plated model is formed. (A) forming the resin film on the substrate by laminating the positive radiation sensitive resin film according to claim 7 on the substrate having a conductive layer on the surface;
(B) irradiating the resin film with radiation through a mask having a predetermined pattern;
(C) heating the substrate having the resin film, and developing to form a pattern;
(D) using the pattern as a mold and forming a plated object by electrolytic plating;
(E) A process for peeling a resin film remaining on a substrate, and (f) a process for removing a conductive layer other than a region where the plated model is formed.   The method for manufacturing a plated article according to claim 9 or 10, wherein the resin film formed on the substrate has a thickness of 20 to 100 µm.