JP6791176B2 - Negative resist film laminate and pattern formation method - Google Patents

Description

The present invention relates to a negative resist film laminate and a pattern forming method.

Normally, in a semiconductor manufacturing process, a resist film is formed on a support such as a film, a sheet, a metal substrate, or a ceramic substrate by using a resist material, but a step is formed on the surface of the support as a circuit is formed. Therefore, the resist material used in the latter half of the semiconductor manufacturing process is required to have uniform coating properties on a surface having steps and no defects such as voids. When a liquid resist material is applied to the surface of such a non-uniform step support, it is difficult to obtain a uniform coating film thickness, and voids are likely to occur in the vicinity of the step. It is difficult to meet the above-mentioned requirements with a resist material, and a resist film is suitable.

Regarding a negative resist film satisfying such a requirement, Patent Document 1 describes a film material that retains flexibility by using an organosiloxane-based resin, but an organic solvent is used for development. Since the development is different from the usual alkaline aqueous solution development, there is a problem that it is necessary to change the equipment at the time of development. Further, Patent Document 2 describes a negative resist film using an alkali-soluble resin, but the adhesion is emphasized, and sufficient measures are taken against the generation of voids on the stepped substrate. Therefore, there has been a long-awaited need for a negative resist film obtained by improving these materials, which can be rolled and has good storage stability.

Japanese Unexamined Patent Publication No. 2011-145664 International Publication No. 2005-363678

The present invention has been made in view of the above circumstances, and is a negative resist film laminate capable of transferring a negative resist film to a support having a step without generating voids and can be stored in a roll state, and pattern formation. The purpose is to provide a method.

As a result of diligent studies to achieve the above object, the present inventors have found that a negative resist film laminate including a thermoplastic film and a predetermined negative resist film is useful, and the present inventors have found that the present invention I came to make a film.

Therefore, the present invention provides the following negative resist film laminate and pattern forming method.
1. 1. A negative resist film laminate comprising a thermoplastic film as a first support and a negative resist film.
The negative resist film
(A) Alkali-soluble resin having a phenolic hydroxy group,
(B) Plasticizer containing polyester,
(C) Photoacid generator,
A negative resist film laminate containing (D) a cross-linking agent and (E) 2 to 30% by mass of an organic solvent.
2. 2. (B) A laminate of 1 in which the polyester is a polyvalent carboxylic acid-based polyester having 2 to 6 carboxy groups.
3. 3. (1) A step of transferring a negative resist film of 1 or 2 laminates onto a second support.
(2) Step of exposing the resist film,
(3) A pattern forming method including a step of developing the resist film with an alkaline aqueous solution.
4. 3. The pattern forming method of 3 in which heat treatment is performed after transfer in the step (1).
5. A pattern forming method of 3 or 4 in which heat treatment is performed after exposure in step (2).
6. The pattern forming method according to any one of 3 to 5, which comprises (4) forming a metal plating layer on a second support by electrolytic plating or electroless plating after step (3).

According to the negative resist film laminate of the present invention, even if the support has a step, the negative resist film can be transferred onto the support without the generation of voids.

It is explanatory drawing of the crack confirmation part on the resist pattern in Example 10.

[Negative resist film laminate]
The negative resist film laminate of the present invention includes a thermoplastic film which is a first support and a negative resist film which can be transferred onto the second support.

[Thermoplastic film]
The thermoplastic film as the first support is a release base material, and is not particularly limited as long as it can be peeled off from the negative resist film without impairing the form of the negative resist film. As such a film, a single-layer film composed of a single polymer film or a multilayer film in which a plurality of polymer films are laminated can be used. Specifically, nylon film, polyethylene (PE) film, polyethylene terephthalate (PET) film, polyethylene naphthalate film, polyphenylene sulfide (PPS) film, polypropylene (PP) film, polystyrene film, polymethylpentene (TPX) film, Examples thereof include a polycarbonate film, a fluorine-containing film, a special polyvinyl alcohol (PVA) film, and a plastic film such as a release-treated polyester film.

Of these, as the first support, a PET film or PP film having appropriate flexibility, mechanical strength and heat resistance is preferable. Further, these films may be subjected to various treatments such as corona treatment or coating with a release agent. Commercially available products can be used as the thermoplastic film, for example, Therapy (registered trademark) WZ (RX), BX8 (R) (manufactured by Toray Film Processing Co., Ltd.), E7302, E7304 (manufactured by Toyobo Co., Ltd.). ), Purex (registered trademark) G31, G71T1 (manufactured by Teijin Film Solutions Co., Ltd.), PET38 × 1-A3, PET38 × 1-V8, PET38 × 1-X08 (manufactured by Nipper Co., Ltd.), etc. In the present invention, the term "flexibility" means the property that the film exhibits flexibility under normal temperature and pressure and does not generate cracks when deformed.

[Negative resist film]
The negative resist film contains (A) an alkali-soluble resin having a phenolic hydroxy group, (B) polyester, (C) a photoacid generator, (D) a cross-linking agent, and (E) 2 to 30% by mass of an organic solvent. Is included.

[(A) Alkali-soluble resin having a phenolic hydroxy group]
Examples of the alkali-soluble resin having a phenolic hydroxy group used as the base resin of the negative resist film include novolak resin, polyhydroxystyrene resin, hydroxystyrene and other radicals in which phenols and aldehydes are polycondensed in the presence of an acid catalyst. Examples thereof include a resin obtained by copolymerizing a polymerizable monomer (acrylic monomer such as methyl acrylate and methyl methacrylate, styrene). Of these, novolak resin is preferable.

Examples of the phenols include phenol; m-cresol, o-cresol, p-cresol, 2,3-xylenol, 2,5-xylenol, 3,5-xylenol, 3,4-xylenol and other xylenols, m-. Ethylphenol, p-ethylphenol, o-ethylphenol, 2,3,5-trimethylphenol, 2,3,5-triethylphenol, 4-tert-butylphenol, 3-tert-butylphenol, 2-tert-butylphenol, 2 Alkylphenols such as -tert-butyl-4-methylphenol, 2-tert-butyl-5-methylphenol, 6-tert-butyl-3-methylphenol; p-methoxyphenol, m-methoxyphenol, p-ethoxyphenol , M-ethoxyphenol, p-propoxyphenol, m-propoxyphenol and other alkoxyphenols; o-isopropenylphenol, p-isopropenylphenol, 2-methyl-4-isopropenylphenol, 2-ethyl-4-iso Isopropenylphenols such as propenylphenol; polyhydroxyphenols such as 4,4'-dihydroxybiphenyl, bisphenol A, phenylphenol, resorcinol, hydroquinone, pyrogallol; hydroxynaphthalene such as α-naphthol, β-naphthol, dihydroxynaphthalene And so on. Of these, phenol, o-cresol, m-cresol, p-cresol, 2,3-xylenol, 2,5-xylenol and / or 3,5-xylenol are preferably used as raw materials, and m-cresol and / Or it is more preferable to use p-cresol as a raw material.

Examples of the aldehydes include formaldehyde, paraformaldehyde, trioxane, acetaldehyde, propionaldehyde, butylaldehyde, trimethylacetaldehyde, achlorein, crotonaldehyde, cyclohexanealdehyde, furfural, frill achlorein, benzaldehyde, terephthalaldehyde, phenylacetaldehyde and α-phenylpropylaldehyde. , Β-phenylpropyl aldehyde, o-hydroxybenzaldehyde, m-hydroxybenzaldehyde, p-hydroxybenzaldehyde, o-methylbenzaldehyde, m-methylbenzaldehyde, p-methylbenzaldehyde, o-chlorobenzaldehyde, m-chlorobenzaldehyde, p-chloro Benzaldehyde and the like can be mentioned. These may be used individually by 1 type, and may be used in combination of 2 or more type. Of these aldehydes, formaldehyde is preferable because of its availability.

The novolak resin is preferably obtained by using 40 mol% or more of p-cresol as the raw material phenols, and more preferably 45 mol% or more of the phenols. In this case, the upper limit of the amount of p-cresol used is 100 mol% of the phenols, but when other phenols are used in addition to p-cresol, the upper limit of the amount of p-cresol used is 80. It is preferably mol%, more preferably 70 mol%. As the other phenols, m-cresol, 2,5-xylenol, and 3,5-xylenol are preferable, and m-cresol is more preferable.

The weight average molecular weight (Mw) of the resin of the component (A) is preferably 3,000 to 50,000, more preferably 5,000 to 30,000. In the present invention, Mw is a polystyrene-equivalent measured value obtained by gel permeation chromatography using tetrahydrofuran as a solvent.

[(B) Plasticizer]
The plasticizer of the component (B) contains polyester. The polyester is a condensate of a polyvalent carboxylic acid and a polyhydric alcohol, or a condensate of a polyvalent carboxylic acid anhydride and a polyhydric alcohol.

The polyvalent carboxylic acid preferably has 2 to 6 carboxy groups, and specifically, oxalic acid, succinic acid, malonic acid, glutaric acid, adipic acid, pimeric acid, speric acid, azelaic acid, and sebacine. Acids, Brasic acid, Methylmalonic acid, Citraconic acid, Fumaric acid, Maleic acid, Methylmaleic acid, Mesaconic acid, Glutaconic acid, Itaconic acid, Allylmalonic acid, Terraconic acid, Muconic acid, 2-Butindioic acid, Aconitic acid, Apple Acids, tartaric acid, grape acid, citric acid, oxomalonic acid, oxosuccinic acid, thioapple acid, glutamic acid, ethylenediamine tetraacetic acid, 1,2-cyclopropandicarboxylic acid, tolxic acid, gypsum acid, phthalic acid, isophthalic acid, terephthalic acid, phenyl Examples thereof include succinic acid, 2- (3-carboxyphenyl) -2-oxoacetic acid, meconic acid, cyclobutanedicarboxylic acid and the like. Furthermore, these acid anhydrides can be used. Of these, a divalent carboxylic acid is preferable. The polyvalent carboxylic acid may be used alone or in combination of two or more.

As polyvalent alcohols, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 3-methyl-1,3-butanediol, 1,4 -Butanediol, 1,4-cyclohexanemethanediol, 1,2-pentanediol, 1,3-pentanediol, 1,5-pentanediol, 1,6-hexanediol, 2-methyl-2,4-pentanediol , 3-Methyl-1,5-pentanediol, ethylene glycol, propylene glycol, neopentyl glycol, glycerin, pentaglycerol and the like. Of these, dihydric alcohols are preferred. The polyhydric alcohol may be used alone or in combination of two or more.

Polyester can be obtained by performing condensation polymerization according to a known method using the above raw materials. The amount of the raw material used may be appropriately adjusted according to the molecular weight of the obtained polymer, but usually, the amount of the polyhydric alcohol is about 0.5 to 3 mol with respect to 1 mol of the polyvalent carboxylic acid. Further, esterification may be carried out by a known method, using an acidic catalyst such as sulfuric acid, a metal such as a titanium compound, a tin compound, a zinc compound, a germanium compound or an antimony compound, and heating at about 150 to 300 ° C. as necessary for a condensation reaction. Just let me do it.

Commercially available products may be used as the polyester, for example, Polysizer (registered trademark) W-2050, W-2310, W-230-H, W-1020-EL, W-1410-EL, W-705. (Manufactured by DIC Co., Ltd.), ADEKA CORPORATION (registered trademark) PN-150, PN-170, PN-230, PN-280, PN-7230, PN-1010, PN-1020, PN-1030, P-200, PN-260, PN-650, PN-7650, PN-1430, HPN-3130, PN-446, PN-7310 (manufactured by ADEKA Corporation), D620, D621, D623, D643, D64, D633, D620N, D623N , D643D, D640A (manufactured by J-Plus Co., Ltd.), etc.

The Mw of the polyester is preferably 700 to 50,000, more preferably 1,500 to 45,000. When Mw is in the above range, the development speed is good, which is preferable.

Since the component (B) is a constituent component of the negative resist film, it is preferably alkali-soluble, and particularly preferably dissolved in an aqueous solution of tetramethylammonium hydroxide (TMAH).

The plasticizer of the component (B) may contain only the polyester, but may also contain a plasticizer other than the polyester. As the other plasticizer, conventionally known ones can be used. The content of the other plasticizer is not particularly limited as long as the effect of the present invention is not impaired.

The content of the component (B) is preferably 5 to 100 parts by mass, more preferably 10 to 60 parts by mass, still more preferably 15 to 50 parts by mass with respect to 100 parts by mass of the resin of the component (A). When the content is within the above range, there is no possibility that voids will be generated when the negative resist film is transferred onto the second support. The polyester component (B) may be used alone or in combination of two or more.

[(C) Photoacid generator]
The photoacid generator of the component (C) is not particularly limited as long as it is a compound that generates an acid by irradiation with high energy rays. Examples of the high-energy rays include ultraviolet rays, far ultraviolet rays, electron beams (EB), and specifically, g-rays, h-rays, i-rays, KrF excimer lasers, ArF excimer lasers, EBs, and synchrotron radiation. And so on.

Suitable photoacid generators include sulfonium salt, iodonium salt, sulfonyldiazomethane, N-sulfonyloxyimide type photoacid generator, benzoin sulfonate type photoacid generator, pyrogallol trisulfonate type photoacid generator, nitrobenzyl sulfonate type. Examples thereof include a photoacid generator, a sulfone-type photoacid generator, an O-arylsulfonyl oxime compound or an O-alkylsulfonyl oxime compound (oxime sulfonate) type photoacid generator.

The sulfonium salt is a salt of a sulfonium cation and a sulfonate anion. Examples of the sulfonium cation include triphenylsulfonium, (4-tert-butoxyphenyl) diphenylsulfonium, bis (4-tert-butoxyphenyl) phenylsulfonium, tris (4-tert-butoxyphenyl) sulfonium, and (3-tert-butoxyphenyl). Phenyl) diphenyl sulfonium, bis (3-tert-butoxyphenyl) phenyl sulfonium, tris (3-tert-butoxyphenyl) sulfonium, (3,4-di tert-butoxyphenyl) diphenyl sulfonium, bis (3,4-di tert) -Butoxyphenyl) phenyl sulfonium, tris (3,4-ditert-butoxyphenyl) sulfonium, diphenyl (4-thiophenoxyphenyl) sulfonium, (4-tert-butoxycarbonylmethyloxyphenyl) diphenyl sulfonium, tris (4-tert) -Butoxycarbonylmethyloxyphenyl) sulfonium, (4-tert-butoxyphenyl) bis (4-dimethylaminophenyl) sulfonium, tris (4-dimethylaminophenyl) sulfonium, 2-naphthyldiphenylsulfonium, dimethyl2-naphthylsulfonium, 4 Examples thereof include −hydroxyphenyldimethylsulfonium, 4-methoxyphenyldimethylsulfonium, trimethylsulfonium, 2-oxocyclohexylcyclohexylmethylsulfonium, trinaphthylsulfonium, tribenzylsulfonium and the like. Examples of the sulfonate anion include trifluoromethane sulfonate, nonaflate butane sulfonate, heptadecafluorooctane sulfonate, 2,2,2-trifluoroethane sulfonate, pentafluorobenzene sulfonate, 4-trifluoromethylbenzene sulfonate, and 4-fluorobenzene sulfonate. , Toluene sulfonate, benzene sulfonate, 4- (4-toluenesulfonyloxy) benzene sulfonate, naphthalene sulfonate, camphor sulfonate, octane sulfonate, dodecylbenzene sulfonate, butane sulfonate, methane sulfonate and the like. The sulfonium salt is preferably a combination of these.

The iodonium salt is a salt of an iodonium cation and a sulfonate anion. Examples of the iodonium cation include aryl iodonium cations such as diphenyl iodonium, bis (4-tert-butylphenyl) iodonium, 4-tert-butoxyphenylphenyl iodonium, and 4-methoxyphenylphenyl iodonium. Examples of the sulfonate anion include trifluoromethane sulfonate, nonaflate butane sulfonate, heptadecafluorooctane sulfonate, 2,2,2-trifluoroethane sulfonate, pentafluorobenzene sulfonate, 4-trifluoromethylbenzene sulfonate, and 4-fluorobenzene sulfonate. , Toluene sulfonate, benzene sulfonate, 4- (4-toluenesulfonyloxy) benzene sulfonate, naphthalene sulfonate, camphor sulfonate, octane sulfonate, dodecylbenzene sulfonate, butane sulfonate, methane sulfonate and the like. The iodonium salt is preferably a combination of these.

Examples of the sulfonyl diazomethane include bis (ethylsulfonyl) diazomethane, bis (1-methylpropylsulfonyl) diazomethane, bis (2-methylpropylsulfonyl) diazomethane, bis (1,1-dimethylethylsulfonyl) diazomethane, and bis (cyclohexylsulfonyl). Diazomethane, bis (perfluoroisopropylsulfonyl) diazomethane, bis (phenylsulfonyl) diazomethane, bis (4-methylphenylsulfonyl) diazomethane, bis (2,4-dimethylphenylsulfonyl) diazomethane, bis (2-naphthylsulfonyl) diazomethane, 4 -Methylphenylsulfonylbenzoyldiazomethane, tert-butylcarbonyl-4-methylphenylsulfonyldiazomethane, 2-naphthylsulfonylbenzoyldiazomethane, 4-methylphenylsulfonyl-2-naphthoyldiazomethane, methylsulfonylbenzoyldiazomethane, tert-butoxycarbonyl-4- Examples thereof include bissulfonyldiazomethane such as methylphenylsulfonyldiazomethane and sulfonylcarbonyldiazomethane.

Examples of the N-sulfonyloxyimide type photoacid generator include succinimide, naphthalenedicarboxylic acid imide, phthalimide, cyclohexyldicarboxylic acid imide, 5-norbornene-2,3-dicarboxylic acid imide, and 7-oxabicyclo [2.2.1]. ] -The hydrogen atom bonded to the nitrogen atom of an imide such as 5-heptene-2,3-dicarboxylic acid imide is a trifluoromethanesulfonyloxy group, a nonafluorobutane sulfonyloxy group, a heptadecafolooctanesulfonyloxy group, 2,2. , 2-Trifluoroethanesulfonyloxy group, pentafluorobenzenesulfonyloxy group, 4-trifluoromethylbenzenesulfonyloxy group, 4-fluorobenzenesulfonyloxy group, toluenesulfonyloxy group, benzenesulfonyloxy group, naphthalenesulfonyloxy group, Examples thereof include compounds substituted with a sulfonyloxy group such as a camphorsulfonyloxy group, an octanesulfonyloxy group, a dodecylbenzenesulfonyloxy group, a butanesulfonyloxy group, and a methanesulfonyloxy group.

Examples of the benzoin sulfonate type photoacid generator include benzointosylate, benzoinmesylate, benzoinbutane sulfonate and the like.

As the pyrogallol trisulfonate type photoacid generator, all of the hydroxy groups of pyrogallol, fluoroglycine, catechol, resorcinol or hydroquinone are trifluoromethanesulfonyloxy group, nonafluorobutanesulfonyloxy group, heptadecafluorooctanesulfonyloxy group, 2 , 2,2-Trifluoroethanesulfonyloxy group, pentafluorobenzenesulfonyloxy group, 4-trifluoromethylbenzenesulfonyloxy group, 4-fluorobenzenesulfonyloxy group, toluenesulfonyloxy group, benzenesulfonyloxy group, naphthalenesulfonyloxy Examples thereof include compounds substituted with a sulfonyloxy group such as a group, a camphor sulfonyloxy group, an octane sulfonyloxy group, a dodecylbenzenesulfonyloxy group, a butanesulfonyloxy group, and a methanesulfonyloxy group.

Examples of the nitrobenzyl sulfonate type photoacid generator include nitrobenzyl alcohols such as 2,4-dinitrobenzyl sulfonate, 2-nitrobenzyl sulfonate, 2,6-dinitrobenzyl sulfonate, trifluoromethane sulfonate, nonafluorobutane sulfonate, and heptadeca. Fluorooctane sulphonate, 2,2,2-trifluoroethane sulphonate, pentafluorobenzene sulphonate, 4-trifluoromethylbenzene sulphonate, 4-fluorobenzene sulphonate, toluene sulphonate, benzene sulphonate, naphthalene sulphonate, camphor sulphonate, octane sulphonate, dodecyl Examples thereof include esters with sulfonic acids such as benzenesulfonate, butanesulfonate, and methanesulfonate. A compound in which a nitro group is replaced with a trifluoromethyl group can also be used as a photoacid generator.

Examples of the sulfone-type photoacid generator include bis (phenylsulfonyl) methane, bis (4-methylphenylsulfonyl) methane, bis (2-naphthylsulfonyl) methane, and 2,2-bis (phenylsulfonyl) propane, 2,2-. Bis (4-methylphenylsulfonyl) propane, 2,2-bis (2-naphthylsulfonyl) propane, 2-methyl-2- (p-toluenesulfonyl) propiophenone, 2- (cyclohexylcarbonyl) -2- (p) -Toluenesulfonyl) propane, 2,4-dimethyl-2- (p-toluenesulfonyl) pentane-3-one and the like.

Examples of the O-arylsulfonyl oxime compound or the O-alkylsulfonyl oxime compound (oxime sulfonate) type photoacid generator include a glyoxime derivative type, a long oxime sulfonate type conjugated via thiophene or cyclohexadiene, and a trifluoromethyl group. Examples thereof include an oxime sulfonate type in which the stability of the compound is increased by an electron-withdrawing group, an oxime sulfonate type using a substituted acetonitrile derivative such as phenyl acetonitrile, and a bisoxime sulfonate type.

Examples of the glyoxime derivative type photoacid generator include bis-O- (p-toluenesulfonyl) -α-dimethylglyoxime, bis-O- (p-toluenesulfonyl) -α-diphenylglyoxime, and bis-O- (p). -Toluenesulfonyl) -α-dicyclohexylglyoxime, bis-O- (p-toluenesulfonyl) -2,3-pentandione-dioxime, bis-O- (n-butanesulfonyl) -α-dimethylglyoxime, bis- O- (n-butanesulfonyl) -α-diphenylglyoxime, bis-O- (n-butanesulfonyl) -α-dicyclohexylglyoxime, bis-O- (methanesulfonyl) -α-dimethylglyoxime, bis-O -(Trifluoromethanesulfonyl) -α-dimethylglyoxime, bis-O- (2,2,2-trifluoroethanesulfonyl) -α-dimethylglyoxime, bis-O- (10-campersulfonyl) -α-dimethyl Glyoxime, bis-O- (benzenesulfonyl) -α-dimethylglyoxime, bis-O- (4-fluorobenzenesulfonyl) -α-dimethylglyoxime, bis-O- (4-trifluoromethylbenzenesulfonyl)- α-Dimethylglyoxime, bis-O- (xylenesulfonyl) -α-dimethylglyoxime, bis-O- (trifluoromethanesulfonyl) -nioxime, bis-O- (2,2,2-trifluoroethanesulfonyl)- Nioxime, bis-O- (10-campersulfonyl) -nioxime, bis-O- (benzenesulfonyl) -nioxime, bis-O- (4-fluorobenzenesulfonyl) -nioxime, bis-O- (4- (trifluoro) Examples thereof include methyl) benzenesulfonyl) -nioxime and bis-O- (xylenesulfonyl) -nioxime.

(5- (p-Toluenesulfonyl) oxyimino-5H-thiophene-2-ylidene) phenylacetonitrile, (5- (10-camfersulfonyl), as long-conjugated oxime sulfonate-type photoacid generators mediated by thiophene or cyclohexadiene ) Oxyimimino-5H-thiophen-2-iriden) phenylacetonitrile, (5-n-octanesulfonyl oxyimimino-5H-thiophen-2-iriden) phenylacetonitrile, (5- (p-toluenesulfonyl) oxyimino-5H-thiophene- 2-Ilidene) (2-Methylphenyl) acetonitrile, (5- (10-camfersulfonyl) oxyimino-5H-thiophen-2-iriden) (2-methylphenyl) acetonitrile, (5-n-octanesulfonyloxyimino-5H) -Thiophen-2-iriden) (2-methylphenyl) acetonitrile, (5- (4- (p-toluenesulfonyloxy) benzenesulfonyl) oxyimino-5H-thiophen-2-iriden) phenylacetonitrile, (5- (2, 2,) Examples thereof include 5-bis (p-toluenesulfonyloxy) benzenesulfonyl) oxyimino-5H-thiophen-2-iriden) phenylacetonitrile.

2,2,2-trifluoro-1-phenylethanone = O- (methylsulfonyl) oxime, 2 as an oxime sulfonate-type acid generator whose compound stability is increased by an electron-withdrawing group such as a trifluoromethyl group. , 2,2-Trifluoro-1-phenylethanone = O- (10-campersulfonyl) oxime, 2,2,2-trifluoro-1-phenylethanone = O- (4-methoxybenzenesulfonyl) oxime, 2,2,2-Trifluoro-1-phenylethanone = O- (1-naphthylsulfonyl) oxime, 2,2,2-trifluoro-1-phenylethanone = O- (2-naphthylsulfonyl) oxime, 2,2,2-Trifluoro-1-phenylethanone = O- (2,4,6-trimethylphenylsulfonyl) oxime 2,2,2-trifluoro-1- (4-methylphenyl) etanone = O -(10-Camfersulfonyl) oxime, 2,2,2-trifluoro-1- (4-methylphenyl) etanone = O- (methylsulfonyl) oxime, 2,2,2-trifluoro-1- (2-) Methylphenyl) Etanone = O- (10-Camfersulfonyl) Oxime, 2,2,2-Trifluoro-1- (2,4-Dimethylphenyl) Etanone = O- (10-Camfersulfonyl) Oxime, 2,2, 2-Trifluoro-1- (2,4-dimethylphenyl) etanone = O- (1-naphthylsulfonyl) oxime, 2,2,2-trifluoro-1- (2,4-dimethylphenyl) etanone = O- (2-naphthylsulfonyl) oxime, 2,2,2-trifluoro-1- (2,4,6-trimethylphenyl) etanone = O- (10-camfersulfonyl) oxime, 2,2,2-trifluoro- 1- (2,4,6-trimethylphenyl) ethanone = O- (1-naphthylsulfonyl) oxime, 2,2,2-trifluoro-1- (2,4,6-trimethylphenyl) etanone = O- ( 2-naphthylsulfonyl) oxime, 2,2,2-trifluoro-1- (4-methoxyphenyl) etanone = O- (methylsulfonyl) oxime, 2,2,2-trifluoro-1- (4-methylthiophenyl) ) Etanone = O- (methylsulfonyl) oxime, 2,2,2-trifluoro-1- (3,4-dimethoxyphenyl) Etanone = O- (methylsulfonyl) oxime, 2,2,2-trifluoro-1 − (4-Methylphenyl) etanone = O- (4-methylphenylsulfonyl) oxime, 2,2,2-trifluoro-1- (4-methoxyphenyl) etanone = O- (4-methoxyphenylsulfonyl) oxime, 2,2,2-trifluoro- 1- (4-methoxyphenyl) etanone = O- (4-dodecylphenylsulfonyl) oxime, 2,2,2-trifluoro-1- (4-methoxyphenyl) etanone = O- (octylsulfonyl) oxime, 2, 2,2-Trifluoro-1- (4-thiomethylphenyl) etanone = O- (4-methoxyphenylsulfonyl) oxime 2,2,2-trifluoro-1- (4-thiomethylphenyl) etanone = O -(4-Dodecylphenylsulfonyl) oxime, 2,2,2-trifluoro-1- (4-thiomethylphenyl) etanone = O- (octylsulfonyl) oxime, 2,2,2-trifluoro-1-( 4-thiomethylphenyl) etanone = O- (2-naphthylsulfonyl) oxime, 2,2,2-trifluoro-1- (2-methylphenyl) etanone = O- (methylsulfonyl) oxime, 2,2,2 -Trifluoro-1- (4-methylphenyl) etanone = O- (phenylsulfonyl) oxime, 2,2,2-trifluoro-1- (4-chlorophenyl) etanone = O- (phenylsulfonyl) oxime, 2, 2,3,3,4,4,4-Heptafluoro-1-phenylbutanone = O- (10-campersulfonyl) oxime, 2,2,2-trifluoro-1- (1-naphthyl) etanone = O- (Methylsulfonyl) oxime, 2,2,2-trifluoro-1- (2-naphthyl) etanone = O- (methylsulfonyl) oxime, 2,2,2-trifluoro-1- (4-benzylphenyl) etanone = O- (methylsulfonyl) oxime, 2,2,2-trifluoro-1- (4- (phenyl-1,4-dioxa-but-1-yl) phenyl) etanone = O- (methylsulfonyl) oxime, 2,2,2-Trifluoro-1- (1-naphthyl) etanone = O- (propylsulfonyl) oxime 2,2,2-trifluoro-1- (2-naphthyl) etanone = O- (propylsulfonyl) Oxime, 2,2,2-trifluoro-1- (4-benzylphenyl) etanone = O- (propylsulfonyl) oxime, 2,2,2-trifluoro-1- (4-methylsulfonylphenyl) etanone = O -(Propylsulfoni Oxime, 2,2,2-trifluoro-1- (4-methylsulfonyloxyphenyl) etanone = O- (propylsulfonyl) oxime, 2,2,2-trifluoro-1- (4-methylcarbonyloxy) Phenyl) etanone = O- (propylsulfonyl) oxime, 2,2,2-trifluoro-1- (6H, 7H-5,8-dioxonaphth-2-yl) etanone = O- (propylsulfonyl) oxime, 2, 2,2-Trifluoro-1- (4-methoxycarbonylmethoxyphenyl) etanone = O- (propylsulfonyl) oxime, 2,2,2-trifluoro-1- (4- (methoxycarbonyl)-(4-amino) -1-oxa-penta-1-yl) phenyl) etanone = O- (propylsulfonyl) oxime, 2,2,2-trifluoro-1- (3,5-dimethyl-4-ethoxyphenyl) etanone = O- (Propylsulfonyl) oxime, 2,2,2-trifluoro-1- (4-benzyloxyphenyl) etanone = O- (propylsulfonyl) oxime, 2,2,2-trifluoro-1- (2-thiophenyl) Etanone = O- (propylsulfonate) oxime and 2,2,2-trifluoro-1- (1-dioxathiophen-2-yl) etanone = O- (propylsulfonate) oxime, 2,2,2-tri Fluoro-1- (4- (3- (4- (2,2,2-trifluoro-1- (trifluoromethanesulfonyloxyimino) ethyl) phenoxy) propoxy) phenyl) etanone = O- (trifluoromethanesulfonyl) oxime 2,2,2-Trifluoro-1-(4- (3- (4- (2,2,2-trifluoro-1- (1-propanesulfonyloxyimino) ethyl) phenoxy) propoxy) phenyl) etanone = O- (propylsulfonyl) oxime, 2,2,2-trifluoro-1-(4- (3- (4- (2,2,2-trifluoro-1- (1-butanesulfonyloxyimino) ethyl) ) Phenoxy) propoxy) phenyl) etanone = O- (butylsulfonyl) oxime, 2,2,2-trifluoro-1-(4- (3- (4- (2,2,2-trifluoro-1-) 4- (4-Methylphenylsulfonyloxy) phenylsulfonyloxyimino) ethyl) phenoxy) propoxy) phenyl) etanone = O- (4- (4-methylphenylsulfonyloxy) phenylsulfonyl) oxime, 2,2,2-Trifluoro-1-(4- (3- (4- (2,2,2-trifluoro-1-) ((2,5-bis (4-methylphenylsulfonyloxy) benzenesulfonyloxy) ) Phenylsulfonyloxyimino) ethyl) phenoxy) propoxy) phenyl) etanone = O-((2,5-bis (4-methylphenylsulfonyloxy) benzenesulfonyloxy) phenylsulfonyl) oxime and the like.

Examples of the oxime sulfonate type photoacid generator using the substituted acetonitrile derivative include α- (p-toluenesulfonyloxyimino) -phenylacetonitrile, α- (p-chlorobenzenesulfonyloxyimino) -phenylacetonitrile, and α- (4-nitrobenzene). Sulfonyloxyimino) -phenylacetonitrile, α- (4-nitro-2-trifluoromethylbenzenesulfonyloxyimino) -phenylacetonitrile, α- (benzenesulfonyloxyimino) -4-chlorophenylacetonitrile, α- (benzenesulfonyloxyimino) ) -2,4-Dichlorophenylacetonitrile, α- (benzenesulfonyloxyimino) -2,6-dichlorophenylacetonitrile, α- (benzenesulfonyloxyimino) -4-methoxyphenylacetonitrile, α- (2-chlorobenzenesulfonyloxyimino) -4-methoxyphenylacetonitrile, α- (benzenesulfonyloxyimino) -2-thienylacetonitrile, α- (4-dodecylbenzenesulfonyloxyimino) -phenylacetonitrile, α-((4-toluenesulfonyloxyimino) -4- Methoxyphenyl) acetonitrile, α-((dodecylbenzenesulfonyloxyimino) -4-methoxyphenyl) acetonitrile, α- (tosyloxyimino) -3-thienyl acetonitrile, α- (methylsulfonyloxyimino) -1-cyclopentenyl acetonitrile , Α- (Ethylsulfonyloxyimino) -1-cyclopentenylacetonitrile, α- (isopropylsulfonyloxyimino) -1-cyclopentenylacetonitrile, α- (n-butylsulfonyloxyimino) -1-cyclopentenylacetonitrile, α- (Ethylsulfonyloxyimino) -1-cyclohexenylacetonitrile, α- (isopropylsulfonyloxyimino) -1-cyclohexenylacetonitrile, α- (n-butylsulfonyloxyimino) -1-cyclohexenylacetonitrile and the like can be mentioned.

Examples of the bisoxime sulfonate type photoacid generator include bis (α- (p-toluenesulfonyloxy) imino) -p-phenylenediacetonitrile and bis (α- (benzenesulfonyloxy) imino) -p-phenylenediacetonitrile. , Bis (α- (methanesulfonyloxy) imino) -p-phenylenediacetonitrile, bis (α- (butanesulfonyloxy) imino) -p-phenylenediacetonitrile, bis (α- (10-camfersulfonyloxy) imino) -P-Phenylacetonitrile, bis (α- (trifluoromethanesulfonyloxy) imino) -p-phenylenediacetonitrile, bis (α- (4-methoxybenzenesulfonyloxy) imino) -p-phenylenediacetonitrile, bis (α) -(P-Toluenesulfonyloxy) imino) -m-phenylenediacetonitrile, bis (α- (benzenesulfonyloxy) imino) -m-phenylenediacetonitrile, bis (α- (methanesulfonyloxy) imino) -m-pheni Range acetonitrile, bis (α- (butanesulfonyloxy) imino) -m-phenylenediacetonitrile, bis (α- (10-camfersulfonyloxy) imino) -m-phenylenediacetonitrile, bis (α- (trifluoromethanesulfonyloxy) ) Imino) -m-phenylenediacetonitrile, bis (α- (4-methoxybenzenesulfonyloxy) imino) -m-phenylenediacetonitrile and the like can be mentioned.

In addition, an oxime sulfonate represented by the following formula (Ox-1) can also be used as a photoacid generator.

In the formula, R ¹ is a substituted or unsubstituted haloalkylsulfonyl group having 1 to 10 carbon atoms or a halobenzenesulfonyl group. R ² is a haloalkyl group having 1 to 11 carbon atoms. R ³ is a substituted or unsubstituted aryl group or heteroaryl group.

Examples of the oxime sulfonate represented by the formula (Ox-1) include 2- (2,2,3,3,4,4,5,5-octafluoro-1- (nonafluorobutylsulfonyloxyimino) pentyl) fluorene. , 2- (2,2,3,3,4,4-pentafluoro-1- (nonafluorobutylsulfonyloxyimino) butyl) fluorene, 2- (2,2,3,3,4,4,5, 5,6,6-decafluoro-1- (nonafluorobutylsulfonyloxyimino) hexyl) fluorene, 2- (2,2,3,3,4,4,5,5-octafluoro-1- (nonafluoro) Butylsulfonyloxyimino) pentyl) -4-biphenyl, 2- (2,2,3,3,4,4-pentafluoro-1- (nonafluorobutylsulfonyloxyimino) butyl) -4-biphenyl, 2- ( Examples thereof include 2,2,3,3,4,4,5,5,6,6-decafluoro-1- (nonafluorobutylsulfonyloxyimino) hexyl) -4-biphenyl.

Among them, preferably used photoacid generators are sulfonium salts, bissulfonyldiazomethanes, N-sulfonyloxyimides, and sulfonyloxime compounds.

The optimum anion of the generated acid differs depending on the easiness of breaking the acid-labile group used in the polymer, but generally, a non-volatile one or an extremely diffusible one is selected. In this case, suitable anions are benzenesulfonic acid anion, toluenesulfonic acid anion, 4- (4-toluenesulfonyloxy) benzenesulfonic acid anion, pentafluorobenzenesulfonic acid anion, 2,2,2-trifluoroethanesulfonic acid. Anion, nonafluorobutane sulfonic acid anion, heptadecafluorooctane sulfonic acid anion, camphor sulfonic acid anion.

The content of the photoacid generator (C) is preferably 0.2 to 20 parts by mass, more preferably 0.3 to 10 parts by mass, based on 100 parts by mass of the resin of the component (A). If the content is within the above range, it is possible to obtain a sensitivity and a pattern shape that do not cause any problem in practical use. (C) The photoacid generator can be used alone or in combination of two or more. Further, it is also possible to use a photoacid generator having a low transmittance at the exposure wavelength and control the light transmittance in the resist film by the addition amount thereof.

[(D) Crosslinking agent]
The cross-linking agent for the component (D) is not particularly limited, but a melamine compound, a guanamine compound, a glycoluril compound, a urea compound and the like containing two or more methylol groups and / or alkoxymethyl groups on average in one molecule and the like. Nitrogen-containing compounds and condensates thereof, phenol compounds having an average of 2 or more methylol groups or alkoxymethyl groups in one molecule, and epoxy compounds having an average of 2 or more epoxy groups in one molecule. One or more selected from the above can be used.

Examples of the melamine compound include those represented by the following formula (CL).

In the formula, R ^{11 to} R ¹⁶ are independently methylol groups, alkoxymethyl groups having 2 to 5 carbon atoms, or hydrogen atoms, but at least one is a methylol group or an alkoxymethyl group. Examples of the alkoxymethyl group include a methoxymethyl group and an ethoxymethyl group.

Examples of the melamine compound represented by the formula (CL) include hexamethylol melamine, hexamethoxymethyl melamine, trimethoxymethyl monomethylol melamine, dimethoxymethyl monomethylol melamine, trimethyl melamine, hexamethoxyethyl melamine and the like.

Examples of the guanamine compound include tetramethylolguanamine, tetramethoxymethylguanamine, tetramethoxyethylguanamine and the like.

Examples of the glycol uryl compound include tetramethylol glycol uryl and tetramethoxymethyl glycol uryl. Examples of the urea compound include tetramethylol urea, tetramethoxymethylurea, tetramethoxyethylurea, tetraethoxymethylurea, and tetrapropoxymethylurea.

Examples of the condensate of the nitrogen-containing compound include the above-mentioned condensate of the nitrogen-containing compound and formaldehyde. In particular, a condensate of a melamine compound or a condensate of a urea compound is preferable. The condensate of the nitrogen-containing compound can be produced by a conventionally known method.

Examples of the phenol compound having two or more methylol groups or alkoxymethyl groups in one molecule include (2-hydroxy-5-methyl) -1,3-benzenedimethanol, 2,2',. Examples thereof include 6,6'-tetramethoxymethylbisphenol A.

Further, examples of the epoxy compound having two or more epoxy groups in one molecule include bisphenol type epoxy resin such as bisphenol A type epoxy resin and bisphenol F type epoxy resin, phenol novolac type epoxy resin, and cresol novolac. Novolak type epoxy resin such as type epoxy resin, triphenol alkane type epoxy resin and its polymer, biphenyl type epoxy resin, dicyclopentadiene modified phenol novolac type epoxy resin, phenol aralkyl type epoxy resin, biphenyl aralkyl type epoxy resin, naphthalene ring Examples thereof include a contained epoxy resin, a glycidyl ester type epoxy resin, an alicyclic epoxy resin, and a heterocyclic epoxy resin.

Among these cross-linking agents, the condensate of the melamine compound and the condensate of the urea compound are particularly preferable because the reaction can be easily controlled.

The cross-linking agent (D) may be used alone or in combination of two or more. The content of the cross-linking agent (D) is preferably 0.1 to 50 parts by mass, more preferably 0.5 to 30 parts by mass with respect to 100 parts by mass of the resin of the component (A). When the addition amount is within the above range, the effect of the present invention can be sufficiently obtained and the storage stability is good.

[(E) Organic solvent]
The organic solvent of the component (E) is not particularly limited as long as it has sufficient solubility in other components and has good coating film properties. Examples of such an organic solvent include cellosolvent solvents such as methyl cellosolve, ethyl cellosolve, methyl cellosolve acetate and ethyl cellosolve acetate; propylene glycol solvents such as propylene glycol and dipropylene glycol; propylene glycol monomethyl ether, propylene glycol monobutyl ether and the like. Propylene glycol alkyl ether-based solvent; propylene glycol alkyl ether acetate-based solvent such as propylene glycol monomethyl ether acetate, propylene glycol dimethyl ether, propylene glycol monoethyl ether acetate; butyl acetate, pentyl acetate, methyl lactate, ethyl lactate, 3-methoxypropion. Ester solvents such as methyl acid, ethyl 3-ethoxypropionate; alcohol solvents such as methanol, ethanol, isopropanol, butanol, hexanol, diacetone alcohol; acetone, cyclohexanone, cyclopentanone, methyl ethyl ketone, methylpentyl ketone, methyl isobutyl Ketone-based solvents such as ketones; ether-based solvents such as methylphenyl ether and diethylene glycol dimethyl ether; high-polarity solvents such as N, N-dimethylformamide, N-methylpyrrolidone, and dimethylsulfoxide; and mixed solvents thereof.

Particularly preferable organic solvents include propylene glycol alkyl ether acetate-based solvents, lactic acid alkyl esters, and alkyl ketones. Examples of the alkyl group of the propylene glycol alkyl ether acetate include those having 1 to 4 carbon atoms, for example, a methyl group, an ethyl group, a propyl group and the like, but a methyl group and an ethyl group are preferable. In addition, propylene glycol alkyl ether acetate has 1,2 and 1,3 substituents, and there are three types of isomers depending on the combination of substitution positions, but these may be mixtures. The alkyl group of the lactic acid alkyl ester includes those having 1 to 4 carbon atoms, for example, a methyl group, an ethyl group, a propyl group and the like, but a methyl group and an ethyl group are preferable. Examples of the alkyl group of the alkyl ketone include those having 1 to 10 carbon atoms, for example, a methyl group, an ethyl group, a propyl group, an isobutyl group, a cyclopentyl group, a cyclohexyl group and the like, and in particular, an isobutyl group, a cyclopentyl group and a cyclohexyl group. Is preferable.

The content of the organic solvent (E) is 2 to 30% by mass, preferably 5 to 25% by mass in the negative resist film. If the content of the organic solvent exceeds 30% by mass, the film may not be formed. If the content of the organic solvent is less than 2% by mass, the organic solvent component is too small, so that cracks are likely to occur, and the flexibility of the film is not sufficient. The organic solvent (E) can be used alone or in combination of two or more. Further, in the present invention, the negative resist film is characterized in that (E) the organic solvent is retained in the film at room temperature for 2 hours or more, preferably 1 week or more, and more preferably 1 month or more. ..

[(F) Surfactant]
The negative resist film may further contain (F) a surfactant. (F) Examples of the surfactant include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene sterial ether, polyoxyethylene cetyl ether, and polyoxyethylene olein ether, polyoxyethylene octylphenol ether, and polyoxy. Polyoxyethylene alkylallyl ethers such as ethylene nonylphenol ethers, polyoxyethylene polyoxypropylene block copolymers, sorbitan monolaurates, sorbitan monopalmitates, sorbitan fatty acid esters such as sorbitan monostearate, polyoxyethylene sorbitan monolaurates Nonionic surfactants of polyoxyethylene sorbitan fatty acid esters such as rate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyether silicone, polyoxyethylene sorbitan trioleate, and polyoxyethylene sorbitan tristearate. EFTOP (registered trademark) EF301, EF303, EF352 (manufactured by Tochem Products Co., Ltd.), Megafuck (registered trademark) F171, F172, F173 (manufactured by DIC Co., Ltd.), FLUORAD (registered trademark) FC-4430, FC-430, FC-431 (manufactured by 3M), Orphine (registered trademark) E1004 (manufactured by Nisshin Chemical Industry Co., Ltd.), Asahi Guard (registered trademark) AG710 (manufactured by Asahi Glass Co., Ltd.), Surflon (registered trademark) Fluorine-based surface activity of S-381, S-382, SC101, SC102, SC103, SC104, SC105, SC106, KH-10, KH-20, KH-30, KH-40 (manufactured by AGC Seimi Chemical Co., Ltd.) Agent: Organosiloxane polymer KP-341, X-70-092, X-70-093 (manufactured by Shin-Etsu Chemical Industry Co., Ltd.); Acrylic acid-based or methacrylic acid-based polyflow No.75, No.95 (Kyoeisha Chemical Co., Ltd.) ), Etc. Of these, FLUORAD FC-4430, KP-341, and X-70-093 are preferable. These can be used alone or in combination of two or more.

The content of the surfactant (F) is 0 to 5 parts by mass with respect to 100 parts by mass of the resin of the component (A), but when it is contained, it is preferably 0.01 to 2 parts by mass.

[Other ingredients]
Further, other known additives can be further added to the negative resist film as long as the effects of the present invention are not impaired. Examples of the additive include various photobase generators, sensitizers, dissolution accelerators such as water-soluble cellulose, stress relievers such as polyvinyl alcohol and polyvinyl alkyl ether compounds, dyes such as azo compounds and curcumin, and benzotriazole. Adhesion improving agents such as system compounds and imidazole compounds, shape improving agents such as oxalic acid, and the like can be mentioned.

[Manufacturing method of negative resist film laminate]
The method for producing the negative resist film laminate of the present invention will be described. First, the above-mentioned (A) component, (B) component, (C) component and (D) component, and if necessary, the (F) component and other components are added to the (E) organic solvent at the same time or in any order. Dissolve to prepare a uniform negative resist solution. If necessary, the obtained uniform solution may be filtered using a filter.

When preparing the negative resist solution, the amount of the (E) organic solvent used is preferably 20 to 400 parts by mass, more preferably 30 to 200 parts by mass, based on 100 parts by mass of the resin of the component (A). When the amount of the organic solvent used is within the above range, the film can be produced with a uniform film thickness, and there is no possibility that defects will occur in the film. In the present invention, the constituent components are once uniformly dissolved in an excess organic solvent, and the desired negative resist film laminate is produced through a drying step described later. Therefore, the constituent components are used when the constituent components are dissolved. The amount of the organic solvent to be produced can be appropriately adjusted according to the film thickness of the film to be produced.

The negative resist solution is placed in a clean room having a cleanliness degree of 1000 or less in a region controlled at a temperature of 5 to 45 ° C., preferably 15 to 35 ° C., and a humidity of 5 to 90%, preferably 10 to 70%. Using forward roll coater, reverse roll coater, comma coater, die coater, lip coater, gravure coater, dip coater, air knife coater, capillary coater, lasing & rising (R & R) coater, blade coater, bar coater, applicator, extrusion molding machine, etc. , It is applied on a thermoplastic film (release base material) which is the first support. At this time, the coating speed is preferably 0.05 to 1,000 m / min, more preferably 0.1 to 500 m / min. Then, the thermoplastic film coated with the negative resist solution is organically placed in an in-line dryer (hot air circulation oven) at preferably 40 to 130 ° C. for 1 to 40 minutes, more preferably 50 to 120 ° C. for 2 to 30 minutes. The solvent and volatile matter are removed and dried to form a negative resist film laminate. It should be noted that instead of the in-line dryer, the solvent may be removed by using a plurality of drying methods such as solvent removal by infrared irradiation or the method of using the in-line dryer and infrared irradiation at the same time to form a negative resist film laminate. I do not care. Further, if necessary, the protective film (release base material) may be pressure-bonded onto the negative resist film laminate using a roll laminator and laminated.

In the present invention, a negative type resist solution is applied to a thermoplastic film on a production line using specific molding conditions and a molding machine to continuously form a roll film and produce a roll film that can be handled in a desired shape. This is also possible, and the same applies when a protective film is formed on the negative type resist film laminate.

For example, when the support film is unwound from the unwinding shaft of the film coater and passed through the film coater head, a negative resist solution is applied on the support film to a predetermined thickness, and a hot air circulation oven is used at a predetermined temperature and a predetermined time. And then dried on the support film, and then passed through the laminate roll at a predetermined pressure together with the protective film unwound from another unwinding shaft of the film coater to pass the negative resist layer on the support film. The negative type resist film laminate can be produced in the form of a roll by the method of winding the film on the take-up shaft of the film coater.

The protective film is not particularly limited as long as it can be peeled off from the negative resist film without impairing the form of the negative resist film, like the thermoplastic film, and a single or a plurality of polymer films are laminated. Multilayer film can be used. Specifically, nylon film, polyethylene (PE) film, polyethylene terephthalate (PET) film, polyethylene naphthalate film, polyphenylene sulfide (PPS) film, polypropylene (PP) film, polystyrene film, polymethylpentene (TPX) film, Examples thereof include plastic films such as polycarbonate films, fluorine-containing films, special polyvinyl alcohol (PVA) films, and mold-released polyester films.

Of these, as the protective film, a PET film or a PE film having appropriate flexibility is preferable. Commercially available products can be used for these, and as PET films, Therapy (registered trademark) WZ (RX), BX8 (R) (manufactured by Toray Film Processing Co., Ltd.), E7302, E7304 (manufactured by Toyobo Co., Ltd.), Examples thereof include PET38 × 1-A3, PET38 × 1-V8, PET38 × 1-X08 (manufactured by Nipper Co., Ltd.), and examples of the PE film include GF-8 (manufactured by Tamapoli Co., Ltd.) and PE film 0. Types (manufactured by Nipper Co., Ltd.), Tretec (registered trademark) 7332, 7111, 7721 (manufactured by Toray Film Processing Co., Ltd.) and the like can be mentioned.

The thickness of the thermoplastic film and the protective film is preferably 10 to 150 μm, more preferably 25 to 100 μm, from the viewpoints of manufacturing stability and curl prevention, that is, curl prevention.

The roll-shaped negative resist film laminate produced in this manner has excellent storage stability and can be used for a long period of time.

The negative resist film is form transferable on a second support onto the thermoplastic film. The thickness of the negative resist film is preferably 5 to 250 μm, more preferably 10 to 180 μm. The second support includes a plastic film or sheet, a semiconductor substrate such as Si, Cu, SiO ₂ , SiN, SiON, TiN, WSi, BPSG, SOG, Au, Ti, W, Cu, Ni-Fe, and the like. Examples thereof include metal substrates such as Ta, Zn, Co, and Pb, substrates such as organic antireflection films, and organic substrates. On the surface of the second support, a circuit formed by plating, sputtering, or the like, a step (unevenness) due to the formation of an insulating resin, or the like may be formed. The step is preferably in the range of about 0 to 200 μm, more preferably in the range of about 3 to 100 μm, and even more preferably in the range of about 10 to 50 μm.

The peeling force of the protective film against the negative resist film produced in the above step is usually in the range of 0.1 to 500 gf / 24 mm, and the measuring method is described below. The test method is performed according to the "adhesive strength test method for peeling off the peeling liner from the adhesive surface of the tape" described in JIS Z 0237. The test environment is in standard conditions (temperature 23 ± 1 ° C., relative humidity 50 ± 5%). The film width used in the test is 24 mm, which is not preferable because the peeling force changes when the film width fluctuates. When a film of a predetermined size is produced and then measured using a testing machine, the peeling angle of the protective film is 180 °, and the peeling speed is 5.0 ± 0.2 mm / sec. As the measured value, the first measured value of 25 mm is excluded, and the next average value of 50 mm is used as the test value.

[Pattern formation method]
The resist film of the negative resist film laminate of the present invention is attached onto a second support, particularly a semiconductor substrate, using various laminators such as a vacuum laminator and a roll laminator, and the thermoplastic film is peeled off. A negative resist film can be transferred. The second support may have a stepped structure, and by using an appropriate negative resist film thickness according to the height of the step, it is possible to embed the negative resist film in the step. However, it can be suitably used for a support having a step of about 0 to 200 μm. After the transfer, there is no problem even if heating is not performed, but if necessary, heat treatment can be performed. When heat treatment is performed, the temperature is 60 to 150 ° C. and 1 to 30 in a hot plate or an oven. It can be prebaked for minutes, preferably 80-130 ° C. for 1-10 minutes.

Then, it is exposed through a predetermined mask with radiation selected from ultraviolet rays, far ultraviolet rays, EB and the like, preferably with a wavelength of 300 nm or more, more preferably with a wavelength of 350 to 500 nm. Exposure is preferably about 10~5,000mJ / cm ^2, about 30~2,000mJ / cm ² is more preferable. After exposure, post-exposure baking (PEB) is preferably performed on a hot plate at 60 to 150 ° C. for 1 to 10 minutes, more preferably 80 to 120 ° C. for 1 to 5 minutes, if necessary.

Further, a developer of 0.1 to 5% by mass, preferably 2 to 3% by mass of an alkaline aqueous solution such as TMAH is used, and immersion is preferably performed for 0.1 to 60 minutes, more preferably 0.5 to 15 minutes. By developing by a known method such as a dip) method, a puddle method, or a spray method, a desired pattern is formed on the second support.

Further, in the present invention, after the development step, a metal plating layer can be formed on the second support, particularly the substrate, by electroplating or electroless plating to form a plating pattern. In the plating step, a conductor pattern is adhered and formed by an electrolytic plating method or an electroless plating method by a known method, and then the resist pattern is removed.

Examples of the electrolytic plating or electroless plating include electrolytic Cu plating, electroless Cu plating, electroless Ni plating, electroless Ni plating, and electroless Au plating, and plating can be performed under known plating baths and plating conditions. The plating thickness is generally 80 to 100% of the resist pattern thickness. For example, the seed layer is Cu, and a resist pattern having a thickness of 1 μm is formed on the seed layer, and then a Cu plating pattern having a thickness of 0.8 to 1 μm is formed by electrolytic Cu plating.

Hereinafter, the present invention will be described in more detail with reference to Synthesis Examples, Examples and Comparative Examples, but the present invention is not limited to the following Examples.

[1] Synthesis of novolak resin [Synthesis example 1] Synthesis of novolak resin 75.7 g (0.7 mol) of p-cresol and 32.5 g of m-cresol (32.5 g) in a three-necked flask equipped with a stirrer, a condenser and a thermometer. 0.3 mol), 52.3 g (0.549 mol) of 37 mass% formaldehyde aqueous solution and 0.30 g (2.40 × 10 ^-3 mol) of oxalic acid dihydrate which is a polycondensation catalyst, and put the flask in an oil bath. The internal temperature was maintained at 100 ° C., and polycondensation was carried out for 1 hour. After completion of the reaction, 500 mL of MIBK (methyl isobutyl ketone) was added, and after stirring for 30 minutes, the aqueous layer was separated, and the product extracted into the MIBK layer was washed with 300 mL of pure water 5 times, separated, and evaporated. A vacuum strip at 150 ° C. was carried out at 4 mmHg to obtain a novolak resin (87 g) having a weight average molecular weight (Mw) of 8,000. The Mw was measured using a GPC column (G-2000H6: 2, G-3000H6: 1, G-4000H6: 1) manufactured by Toso Co., Ltd., with a flow rate of 1.5 mL / min and an elution solvent THF. , The column temperature was 40 ° C.

[2] Preparation of Negative Resist Film Laminate [Examples 1 to 9, Comparative Examples 1 to 4]
A solution was prepared by mixing the components (A) to (F) and other components with the compositions shown in Table 1 below, and then filtered through a 1.0 μm membrane filter to prepare resist solutions 1 to 13.

In addition, each component in Table 1 is as follows.
(A) Alkali-soluble resin having a phenolic hydroxy group NP1: Novolac resin synthesized in Synthesis Example 1 M: Marukalinker M (Polyhydroxystyrene manufactured by Maruzen Petrochemical Co., Ltd., Mw = 10,000)
CMM: Marukalinker CMM (Hydroxystyrene-methyl methacrylate copolymer manufactured by Maruzen Petrochemical Co., Ltd., Mw = 10,000, molar ratio 1: 1)

(B) Polyester PE1: Polysizer W-2050 (Adipic acid-based polyester manufactured by DIC Corporation, Mw = 3,900)
PE2: ADEKA Sizer P-300 (Adipic acid polyester manufactured by ADEKA Corporation, Mw = 4,900)
PE3: D645 (Adipic acid polyester manufactured by J-Plus Co., Ltd., Mw = 5,600)

(C) Photoacid generator PAG1: HT-1CS (manufactured by Sun Appro Co., Ltd.)
PAG2: NAI-106 (manufactured by Midori Chemical Co., Ltd.)

ＣＬ３：下記式（Ｃ−２）で表される化合物

(D) Crosslinker CL1: Nicarac MW-30M (Methylated melamine manufactured by Sanwa Chemical Co., Ltd.)
CL2: Compound represented by the following formula (C-1)

CL3: Compound represented by the following formula (C-2)

(E) Organic Solvent EL: Ethyl Lactate CP: Cyclopentanone PMA: Propylene Glycol Monomethyl Ether Acetate

(F) Surfactant SF: KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.)

Other Ingredients BTA: Benzotriazole CR: Curcumin OA: Oxalic Acid UC: UC-3510 (Acrylic resin manufactured by Toagosei Co., Ltd.)

The resist solutions 1 to 13 are applied onto a PET film (thickness 38 μm) which is a thermoplastic film using a die coater as a film coater in a clean room having a cleanliness of 1000, a humidity of 40 to 45%, and a temperature of 22 to 26 ° C. The laminates 1 to 13 having a negative resist film having a thickness of 40 μm were prepared by drying in a hot air circulation oven at the oven temperature shown in Table 2 for 5 minutes.

Then, a PE film (thickness 50 μm) as a protective film was attached to the surface of the produced resist film at a pressure of 1 MPa to prepare a negative resist film laminate in a rolled state.

From the produced laminated film, 0.1 g of a negative resist film was collected, extracted with 10 mL of acetonitrile, centrifuged, and the supernatant was recovered, and gas chromatography measurement was performed to calculate the organic solvent content. The resist film of the example contained the amount shown in Table 2 by sustaining the organic solvent at 23 ° C. for 7 days.

[3] Evaluation of void generation With respect to the produced negative resist film laminate, first, the protective film was peeled off, and the inside of the vacuum chamber was set to a vacuum degree of 80 Pa using a vacuum laminator TEAM-100M (manufactured by Takatori Co., Ltd.). Then, the negative resist film on the thermoplastic film was transferred onto a 200 mm Cu substrate having a step of up to 50 μm. The temperature condition at this time was 60 ° C. After returning to normal pressure, the substrate was taken out from the vacuum laminator, the thermoplastic film was peeled off, and then an optical microscope (manufactured by Nikon Corporation) was used to evaluate whether or not voids were generated on the substrate. Each Example and Comparative Example were evaluated 5 times and judged by the average value. Those in which no voids were generated were evaluated as ◯, those in which 1 to 10 voids were generated on average were evaluated as Δ, and those in which 11 or more voids were generated on average were evaluated as ×. The results are shown in Table 3.

[4] Evaluation of storage stability The produced rolled negative resist film laminate was stored at 23 ° C., and the film state after one month was confirmed. The results are shown in Table 4.

[5] Pattern formation evaluation [Example 10]
From the negative resist film laminate prepared by using the resist solution 9 so that the oven temperature is 100 ° C. and the residual solvent amount is 12% by mass by the same method as the method for producing the negative resist film laminate described above, a negative is obtained. The mold resist film was transferred onto a 200 mm Cu substrate and soft-baked at 100 ° C. for 90 seconds on a hot plate. The thickness of the film after soft baking was confirmed by a light interference type film thickness measuring machine (M6100, manufactured by Nanometrics) and found to be 18 μm. Next, the formed resist film was exposed to an i-line stepper (NSR-2205i11D manufactured by Nikon Corporation) via a reticle, and after PEB at 110 ° C. for 90 seconds, a 2.38 mass% TMAH aqueous solution was applied. After paddle development for 100 seconds, pure water was rinsed and dried.
The obtained pattern was confirmed using a scanning electron microscope (S-4700 manufactured by Hitachi High-Technologies Corporation), and a repeating pattern of 20 μm lines and spaces was found at an exposure of 150 mJ / cm ² . It was resolved to a rectangle.
Further, after producing the pattern, the resist pattern and the substrate surface are ashed with 100 W oxygen plasma for 30 seconds using a dry etching apparatus (DEM-451 manufactured by Nichiden Anerva Co., Ltd.), and then a Cu plating solution (Tanaka Kikinzoku Kogyo Co., Ltd.) It was immersed in Microfab Cu200) manufactured by Co., Ltd., a constant current was applied at 25 ° C. for 5 minutes, Cu plating was performed, and Cu having a thickness of about 5 μm was laminated. Finally, after plating, the surface was washed with pure water, and the resist surface was observed with an optical microscope to observe the crack resistance of the plating against the growth stress. Regarding the crack resistance, 900 points of the corner portion on the resist pattern shown in FIG. 1 where cracks were particularly likely to occur were observed, but no cracks were observed, and the resist pattern had sufficient plating resistance. In FIG. 1, 1 is a crack confirmation portion, 6 × 5 = 30 points at 50 μm in one shot, and 30 × 30 = 900 points on the entire surface of the wafer (30 shots). Reference numeral 2 is an enlarged view of the pattern, and 3 is an overall view of the wafer.

1 Crack confirmation part 2 Pattern enlarged view 3 Wafer overall view

Claims (6)

A negative resist film laminate comprising a thermoplastic film as a first support and a negative resist film.
The negative resist film
(A) Alkali-soluble resin having a phenolic hydroxy group,
(B) Plasticizer containing polyester,
(C) Photoacid generator,
A negative resist film laminate containing (D) a cross-linking agent and (E) 2 to 30% by mass of an organic solvent. (B) The laminate according to claim 1, wherein the polyester is a polyvalent carboxylic acid-based polyester having 2 to 6 carboxy groups. (1) A step of transferring the negative resist film of the laminate according to claim 1 or 2 onto the second support.
(2) Step of exposing the resist film,
(3) A pattern forming method including a step of developing the resist film with an alkaline aqueous solution. The pattern forming method according to claim 3, wherein the heat treatment is performed after transfer in the step (1). The pattern forming method according to claim 3 or 4, wherein the heat treatment is performed after exposure in the step (2). The pattern forming method according to any one of claims 3 to 5, which comprises (4) forming a metal plating layer on a second support by electrolytic plating or electroless plating after the step (3).

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