JP4979368B2 - Active energy ray-curable resin composition and resist pattern forming method - Google Patents

Description

  The present invention relates to an active energy ray-curable resin composition and a resist pattern forming method using the resin composition.

  Conventionally, it is known that when a resist pattern is formed, light reflection from the surface of the base substrate of the resist film causes halation, thereby inhibiting the resist pattern shape. As a method for solving this problem, for example, a method of blending a dye into a resist composition (see Patent Document 1 and Patent Document 2), a method of forming an antireflection layer on the base substrate surface (see Patent Document 3) ), An alkali-soluble resin, a compound that generates an acid upon irradiation with actinic radiation, a cross-linking agent that cross-links with the generated acid, and a negative-type chemically amplified photosensitive composition containing a light absorber having a specific structure (patent) Reference 4).

However, the method of blending a dye into the resist composition has a problem that the resolution of the resist pattern is deteriorated or the antihalation effect is not sufficient when the resist film is a thin film. Further, the method of forming the light reflection preventing layer has a big problem that the burden of etching increases. Further, the method using the negative chemical amplification type photosensitive composition has a problem that the heat treatment is required, so that the cost is high and the process management is troublesome.
JP 47-38037 A JP-A-11-160860 JP-A-5-343314 JP 2000-258904 A

  An object of the present invention is to provide a resist pattern forming method for reducing light reflection from the surface of a base material, and a resin composition used in the method, particularly when forming a thin resist pattern.

（ここで、Ｒ ¹ は水素原子、アルキル基、アリール基、シクロアルキル基又はアラルキル基を表し、Ｒ ² は５個以上の炭素原子を有するアルキル基を表し、Ｒ ³ は水素原子又は１〜６個の炭素原子を有するアルキル基を表し、Ｂはニトロ基、シアノ基、アルキル基、アルコキシ基、塩素、臭素、フェニル基又はフェノキシ基を有していてもよいベンゼン環を表す。）
で表される化合物であるレジスト膜形成用活性エネルギー線硬化型樹脂組成物である。 The present invention
(A) a base resin containing an unsaturated group and an ionic group,
(B) a photo radical initiator, and
(C) A light absorber is contained, and the base resin (A) is obtained by reacting glycidyl (meth) acrylate with a polycarboxylic acid resin to introduce unsaturated groups and carboxyl groups into the resin. (C) is an active energy ray-curable resin composition comprising only 0.1 to 5 parts by weight of a yellow light absorber with respect to 100 parts by weight of the base resin (A),
When a 10 μm or 5 μm thick resist film is coated on the substrate, i-line (wavelength 365 nm), h-line (wavelength 405 nm), and g-line (wavelength 436 nm) in the spectral sensitivity wavelength region of the resist film The ratio (Y / X) of the initial active energy dose (X) before irradiation with active energy rays including three mixed lines and the transmitted active energy dose (Y) after passing through the resist film is 10% or less. The
The light absorber (C) is represented by the following general formula (I)

(Wherein R ¹ represents a hydrogen atom, an alkyl group, an aryl group, a cycloalkyl group or an aralkyl group, R ² represents an alkyl group having 5 or more carbon atoms, and R ³ represents a hydrogen atom or 1 to 6) And represents a benzene ring optionally having a nitro group, a cyano group, an alkyl group, an alkoxy group, chlorine, bromine, a phenyl group, or a phenoxy group.
An active energy ray-curable resin composition for forming a resist film, which is a compound represented by the formula:

Furthermore, the present invention provides
(1) A step of applying the active energy ray-curable resin composition according to claim 1 on a substrate to form a resist film having a predetermined thickness;
(2) The resist film is irradiated with an active energy ray including three mixed lines of i-line (wavelength 365 nm), h-line (wavelength 405 nm) and g-line (wavelength 436 nm) directly or through a negative mask to form a desired pattern Curing to, and
(3) A resist pattern forming method including a step of developing a resist film cured in a desired pattern to form a resist pattern on a substrate.

  According to the present invention, a remarkable effect can be obtained that a desired resist pattern can be formed by preventing halation due to light reflection even in a thin resist film.

  In particular, an active energy ray is used as irradiation light, and an unsaturated group-containing resin that is cured by the active energy ray is used as a resist resin composition, and the resist resin composition absorbs a specific wavelength of the active energy ray. The said effect becomes remarkable by mix | blending an absorber.

When the active energy ray-curable resin composition of the present invention is coated on a substrate to form a resist film having a thickness of 10 μm or 5 μm, the initial active energy dose (X) before irradiation in the spectral sensitivity wavelength region of the resist film. ) And the transmitted active energy dose (Y) after passing through the resist film (Y / X) is 10% or less, preferably 5% or less. If the ratio (Y / X) is such a low value, the unirradiated portion of the resist film is not cured and a delicate pattern can be formed. Here, the active energy dose (X) before irradiation is the active energy dose measured on the resist film surface on the irradiation surface side. The transmitted active energy dose (Y) after passing through the resist film is measured under the same irradiation conditions (light source, distance from the light source, and irradiation time) as the active energy dose (X) is measured. Is the active energy dose after passing through the resist film measured on the resist film surface opposite to the irradiated surface.

  The ratio (Y / X) between the initial active energy dose (X) and the transmitted active energy dose (Y) can be determined as follows.

First, an active energy ray-curable resin composition is coated on one side of a transparent substrate (for example, a glass substrate) prepared for measurement to form a 10 μm or 5 μm resist film . Normally was measured at 10μm or 5 [mu] m, it is particularly preferable ratio even in the case of 5μm (Y / X) is 10% or less. Next, the active energy ray is irradiated under the actual irradiation conditions, and the transmitted active energy dose (Y ′) after passing through the resist film is measured. Here, the transmitted active energy dose (Y ′) after passing through the resist film is the value after passing through the resist film-covered transparent base material measured on the resist film-covered transparent base material surface opposite to the irradiated surface. Active energy dose. Moreover, the transparent active material dose (Z) after permeate | transmitting a transparent base material is measured beforehand using the transparent base material used by this measurement as a blank. Here, the transmitted active energy dose (Z) after passing through the transparent base material, that is, the same irradiation conditions (light source, distance from the light source, and irradiation) as in the case of measuring the transmitted active energy dose (Y ′). This is the active energy dose measured on the surface of the transparent substrate that is the opposite surface of the irradiated surface when measured in terms of time. The unit of dose is J / m ² .

  The value of the ratio (Y / X) can be obtained by calculating the equation [Y ′ / Z] using the energy dose thus obtained.

The active energy ray-curable resin composition of the present invention, the base resin (A) containing an unsaturated group and an ionic group, a photo-radical initiator (B), and you-containing light absorbing agent (C).

<Base resin (A)>
The base resin (A ) is a photocurable resin having an unsaturated group that can be polymerized by radicals generated from the photoradical initiator (B) by irradiation with active energy rays, and the unexposed film is formed by alkaline development. Ru resin der having an ionic group (anionic group) to give the ability to remove dissolved by a liquid or an acidic developer.

  The weight average molecular weight of the base resin (A) is preferably from 2,000 to 100,000, more preferably from 3,000 to 80,000. The lower limits of the above ranges are significant in that the boundary surface between the unirradiated part and the irradiated part becomes clear. The upper limit is significant in terms of the solubility of the uncured part (unirradiated part) in the developer. By these actions, a delicate pattern can be formed more satisfactorily.

  The glass transition temperature of the base resin (A) is preferably -20 to 100 ° C, more preferably -10 to 90 ° C. The lower limits of the above ranges are significant in that the boundary surface between the unirradiated part and the irradiated part becomes clear. The upper limit is significant in terms of the solubility of the uncured part in the developer. By these actions, a delicate pattern can be formed more satisfactorily.

  The average concentration of unsaturated groups in the base resin (A) is preferably 0.1 to 10 and more preferably 0.5 to 8 per molecule. The lower limits of the above ranges are significant in terms of curability. The upper limit is significant in terms of peelability.

Unsaturated groups contained in the base resin (A), Ru acryloyl group or a methacryloyl group der.

Ionic groups contained in the base resin (A), Ru mosquito carboxyl groups der with anionic groups. The lower limit of the content of the A anion groups, the acid value of the resin is preferably from about 10~300mgKOH / g, from about 20 to 200 mg KOH / g is more preferable. The lower limits of the above ranges are significant in terms of the solubility of the uncured part in the developer. The upper limit is significant in terms of preventing film removal at the hardened portion .

Based resins of the present invention, Ru der that by reacting grayed Rishijiru (meth) acrylate bets on port polycarboxylic acid resin by introducing unsaturated groups and carboxyl groups in the resin.

As the base resin containing an anionic group , for example, a photocurable resin described in JP-A-3-223759 can be used.

<Photoradical initiator (B)>
Examples of the photo radical initiator (B) include aromatic carbonyl compounds such as benzophenone, benzoin methyl ether, benzoin isopropyl ether, benzylxanthone, thioxanthone, and anthraquinone; acetophenone, propiophenone, α-hydroxyisobutylphenone, α, α '-Dichloro-4-phenoxyacetophenone, 1-hydroxy-1-cyclohexylacetophenone, acetophenones such as diacetylacetophenone; benzoyl peroxide, t-butylperoxy-2-ethylhexanoate, t-butylhydroperoxide, di- organic peroxides such as t-butyldiperoxyisophthalate, 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone; Diphenylhalonium salts such as romide and diphenyliodonium chloride; organic halides such as carbon tetrabromide, chloroform and iodoform; 3-phenyl-5-isoxazolone, 2,4,6-tris (trichloromethyl) -1,3 Heterocyclic and polycyclic compounds such as 1,5-triazinebenzanthrone; 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2-azobisisobutyronitrile, 1,1′-azobis (Cyclohexane-1-carbonitrile), azo compounds such as 2,2′-azobis (2-methylbutyronitrile); iron monoarene complex (see European Patent No. 152377); titanocene compound (Japanese Patent Laid-Open No. 63-221110) Bisimidazole compounds; N-aryl glycidyl compounds; acridine compounds; Combinations of aromatic ketones / aromatic amine; peroxy ketal (see Japanese Patent Laid-Open No. 6-321895) and the like. Of these, acetophenones are preferred because of their high activity with respect to crosslinking or polymerization.

  Examples of commercial names that can be used as the photoradical initiator (B) include Irgacure 651 (Ciba Specialty Chemicals, acetophenone photoradical polymerization initiator), Irgacure 184 (Ciba Specialty Chemicals). , Acetophenone photoradical polymerization initiator), Irgacure 1850 (manufactured by Ciba Specialty Chemicals, acetophenone photoradical polymerization initiator), Irgacure 907 (manufactured by Ciba Specialty Chemicals, aminoalkylphenone photoradical polymerization initiator) ), Irgacure 369 (manufactured by Ciba Specialty Chemicals, aminoalkylphenone photoradical polymerization initiator), Irgacure 379 (manufactured by Ciba Specialty Chemicals, aminoalkylphenone optical radical) Polymerization initiator), lucillin TPO (manufactured by BASF, 2,4,6-trimethylbenzoyldiphenylphosphine oxide), Kayacure DETXS (manufactured by Nippon Kayaku Co., Ltd.), CGI-784 (manufactured by Ciba Specialty Chemicals) And titanium complex compounds).

  These photo radical initiators can be used alone or in combination of two or more. Among these, Irgacure 907 and Irgacure 369 are particularly preferable.

  The blending ratio of the photo radical initiator (B) is preferably 0.1 to 25 parts by mass, more preferably 0.2 to 10 parts by mass with respect to 100 parts by mass of the base resin (A). The lower limit of each range is significant in terms of curability. Further, the upper limit value is significant in terms of reducing the cost while maintaining sufficient curability.

<Light absorber (C)>
Light absorbing agent (C) made of a light absorbing agent of yellow, in particular Ru compound der represented by the following general formula (I).

(Wherein R ¹ represents a hydrogen atom, an alkyl group, an aryl group, a cycloalkyl group or an aralkyl group, R ² represents an alkyl group having 5 or more carbon atoms, and R ³ represents a hydrogen atom or 1 to 6) Represents an alkyl group having one carbon atom, and B represents a benzene ring optionally having a nitro group, a cyano group, an alkyl group, an alkoxy group, chlorine, bromine, a phenyl group or a phenoxy group.

What is necessary is just to mix | blend the mixture ratio of a light absorber (C) so that the said ratio (Y / X) may not exceed 10%. The blending ratio within the ratio (Y / X) varies depending on the resist film thickness. In this invention, it is 0.1-5 mass parts with respect to 100 mass parts of base resins , Most preferably, it is 1-5 mass parts.

  In addition to the components described above, a polyfunctional unsaturated compound can be further blended in the resin composition of the present invention. Examples of the polyfunctional unsaturated compound include esterified products of polyhydric alcohol and (meth) acrylic acid. Specific examples of the polyfunctional unsaturated compound include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, and 1,3-butylene glycol. Di (meth) acrylate, 1,4-butanediol diacrylate, 1,9-nonanediol di (meth) acrylate, glycerin di (meth) acrylate, trimethylolpropane di (meth) acrylate, pentaerythritol di (meth) acrylate , Neopentyl glycol diacrylate, 1,6-hexanediol diacrylate, bisphenol A ethylene oxide modified diacrylate, polyester di (meth) acrylate, urethane di (meth) acrylate Di (meth) acrylate compounds such as: glycerin tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane propylene oxide modified tri (meth) acrylate, trimethylolpropane ethylene oxide modified tri (meth) acrylate, penta Tri (meth) acrylate compounds such as erythritol tri (meth) acrylate; tetra (meth) acrylate compounds such as pentaerythritol tetra (meth) acrylate; other dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate Etc. These polyfunctional unsaturated compounds can be used alone or in combination of two or more.

  The blending ratio of the polyfunctional unsaturated compound is preferably 1 to 100 parts by mass, more preferably 5 to 50 parts by mass with respect to 100 parts by mass of the base resin (A).

  In addition to the components described above, a saturated resin can be further blended in the resin composition of the present invention. The saturated resin is used, for example, for the purpose of suppressing the solubility of the base resin (A). Specifically, for example, it is used as an inhibitor of solubility in a strong alkali solution for adjusting the solubility of the resist film in an alkali developer and the removability of the photocured film. Examples of the saturated resin include polyester resin, alkyd resin, (meth) acrylic resin, vinyl resin, epoxy resin, phenol resin, natural resin, synthetic rubber, silicon resin, fluorine resin, polyurethane resin, and the like. These saturated resins can be used alone or in combination of two or more.

  Furthermore, a photosensitizer can also be used. Specific examples thereof include thioxanthene, xanthene, ketone, thiopyrylium salt, base styryl, merocyanine, 3-substituted coumarin, coumarin, 3,4-substituted coumarin, cyanine, acridine, Examples of the dye include thiazine, phenothiazine, anthracene, coronene, benzanthracene, perylene, ketocoumarin, fumarine, and borate. These photosensitizers can be used alone or in combination of two or more. Examples of the borate dye include those described in JP-A-5-241338, JP-A-7-5585, JP-A-7-225474, and the like.

  In the resin composition of the present invention, the composition containing the above components (A) to (C) and other components as necessary is replaced with an organic solvent (for example, ketones, esters, ethers, cellosolves, aromatics). (Hydrocarbons, alcohols, halogenated hydrocarbons, etc.) can be used as an organic solvent-based composition dissolved or dispersed. It can also be used as an aqueous composition dispersed in water using ionic groups in the resin component.

  In the present invention, the resist film coated on the substrate is, for example, a dry film obtained by coating the organic solvent-based or aqueous composition described above and volatilizing the organic solvent or water as necessary. Further, a dry film made of the resin composition of the present invention can be heated and pressure-bonded on a substrate to form a resist film. In this case, the dry film is obtained, for example, by coating an organic solvent-based or water-based composition on the surface of a base film such as a PET film and volatilizing the organic solvent or water. The dry film on the base film thus obtained is heated and pressure-bonded on the substrate, and then the base film is peeled off.

  The coating of the resin composition can be performed by means of, for example, a roller, a roll coater, a spin coater, a curtain roll coater, spray, electrostatic coating, dip coating, silk printing, spin coating or the like.

  In the present invention, conventionally known active energy rays can be used as the active energy rays to be irradiated. The light source is not particularly limited. For example, ultra high pressure, high pressure, medium pressure, low pressure mercury lamp, chemical lamp, carbon arc lamp, xenon lamp, metal halide lamp, tungsten lamp, etc. can be used.

  The resin composition of the present invention is particularly excellent in the antihalation effect when the active energy ray is an active energy ray containing three mixed lines of i-line (wavelength 365 nm), h-line (wavelength 405 nm) and g-line (wavelength 436 nm). .

The resist pattern forming method of the present invention comprises:
(1) A step of applying the active energy ray-curable resin composition according to claim 1 on a substrate to form a resist film having a predetermined thickness;
(2) The resist film is irradiated with an active energy ray including three mixed lines of i-line (wavelength 365 nm), h-line (wavelength 405 nm) and g-line (wavelength 436 nm) directly or through a negative mask to form a desired pattern Curing to, and
(3) A step of developing the resist film cured in a desired pattern to form a resist pattern on the substrate is included.

The dose of the active energy rays are usually 100~10000J / m ^2, preferably 500~7000J / m ^2.

  A base material is a base material used for semiconductor element manufacture and liquid crystal display element manufacture, for example. The surface of the base material on which the resist film is formed is a surface made of, for example, a silicon oxide film, a silicon nitride film, polysilicon, molybdenum, tantalum, tantalum oxide, chromium, chromium oxide, aluminum, ITO, or the like.

  The thickness of the resist film is preferably 0.5 to 20 μm, more preferably 1 to 10 μm, and particularly preferably 1 to 5 μm.

  As the developer used in the development process, either an alkaline developer or an acidic developer can be used. Examples of the alkaline developer include aqueous solutions such as triethylamine, diethanolamine, triethanolamine, ammonia, sodium metasilicate, potassium metasilicate, sodium carbonate, and tetraethylammonium hydroxide. Examples of the acidic developer include acetic acid, formic acid, and hydroxyacetic acid. The density | concentration of a developing solution is 0.5-3 mass% normally, Preferably it is 0.6-2 mass%. The temperature of the development processing is usually 20 to 50 ° C., and the time is usually 20 to 120 seconds.

  After the development, an etching process is usually performed. Etching includes dry etching and wet etching, and either method can be applied. In the case of manufacturing a liquid crystal display element, wet etching is generally used particularly in the case of an ITO substrate. In this way, a predetermined pattern can be formed on the substrate through the etching process.

  Thereafter, the resist film is usually peeled off. For example, the resist film may be washed away using a solution such as an alkaline aqueous solution or an organic solvent. Examples of the alkaline aqueous solution include aqueous solutions of caustic soda, caustic potash, ammonia, triethanolamine, triethylamine, and the like. Examples of the organic solvent include 1,1,1-trichloroethane, methyl ethyl ketone, methylene chloride and the like. In the case of using an organic solvent, it can be removed also by dissolving the resist film. The peeling treatment can be performed by immersing the substrate in a solution usually at a temperature of 20 to 80 ° C., usually for 1 to 30 minutes.

  Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. However, the scope of the present invention is not limited to these. In the following description, “part” means “part by mass”.

<Synthesis Example 1 (Synthesis of Resin 1)>
Acrylic resin (resin acid value 600 mgKOH / g, styrene / acrylic acid = 20/80 mass ratio) is reacted with 125 parts of glycidyl methacrylate to give resin 1 (resin solid content 55 mass%, propylene glycol monomethyl ether organic solvent, resin acid Value 55 mg KOH / g, weight average molecular weight about 50,000).

<Synthesis Example 2 (Synthesis of Resin 2)>
199 parts of a trisphenol methane type epoxy resin having an epoxy equivalent of 205 (g / eq) was dissolved in 370 parts of epichlorohydrin. Thereafter, tetramethylammonium chloride was added, an aqueous NaOH solution was further added dropwise, and the reaction was carried out at 70 ° C. for 3 hours. After completion of the reaction, it was washed with water, and epichlorohydrin was distilled off under reduced pressure. Further, the reaction product was dissolved in methyl isobutyl ketone, an aqueous NaOH solution was added, and the reaction was performed at 70 ° C. for 1 hour. After completion of the reaction, the reaction product was washed with water, and then methyl isobutyl ketone was distilled off to obtain 195 parts of an epoxy resin (a) having an epoxy equivalent of 189 (g / eq).

  189 parts of epoxy resin (a) was dissolved in 68.5 parts of acrylic acid and carbitol acetate. Thereafter, the reaction was carried out at 95 ° C. in the presence of methoquinone and triphenylphosphine. After confirming that the acid value was 1.0 (mgKOH / g) or less, 101.3 parts of tetrahydrophthalic anhydride and carbitol acetate were added and reacted. The reaction was terminated when the acid value reached 104 (mgKOH / g) to obtain an acid-modified epoxy acrylate resin (Resin 2).

<Synthesis Example 3 (Synthesis of Resin 3)>
240 parts of a cresol novolac type epoxy resin having an epoxy equivalent of 199 (g / eq) was dissolved in 370 parts of epichlorohydrin and dimethyl sulfoxide. Then, NaOH was added and reaction was performed at 70 degreeC for 3 hours. Subsequently, unreacted epichlorohydrin and dimethyl sulfoxide were distilled off under reduced pressure, and the reaction product was further dissolved in methyl isobutyl ketone. Then, NaOH aqueous solution was added and reaction was performed at 70 degreeC for 1 hour. After completion of the reaction, the reaction product was washed with water, and then methyl isobutyl ketone was distilled off to obtain 241 parts of an epoxy resin (b) having an epoxy equivalent of 190 (g / eq).

  190 parts of the epoxy resin (b) was dissolved in 68.5 parts of acrylic acid and carbitol acetate. Thereafter, the reaction was carried out at 95 ° C. in the presence of methoquinone and triphenylphosphine. After confirming that the acid value was 1.0 (mgKOH / g) or less, 121.6 parts of hexahydrophthalic anhydride and carbitol acetate were added to carry out the reaction. The reaction was terminated when the acid value reached 110 (mgKOH / g) to obtain an acid-modified epoxy acrylate resin (Resin 3).

<Synthesis Example 4 (Synthesis of Resin 4)>
371 parts of a bisphenol F type epoxy resin having an epoxy equivalent of 650 (g / eq) was dissolved in 925 parts of epichlorohydrin and dimethyl sulfoxide. Then, NaOH was added and reaction was performed at 70 degreeC for 3 hours. Subsequently, unreacted epichlorohydrin and dimethyl sulfoxide were distilled off under reduced pressure, and the reaction product was further dissolved in methyl isobutyl ketone. Then, NaOH aqueous solution was added and reaction was performed at 70 degreeC for 1 hour. After completion of the reaction, the reaction product was washed with water, and then methyl isobutyl ketone was distilled off to obtain 365 parts of an epoxy resin (c) having an epoxy equivalent of 379 (g / eq).

  After 379 parts of epoxy resin (c) was dissolved in 68.5 parts of acrylic acid and carbitol acetate, the reaction was carried out in the presence of methoquinone and triphenylphosphine. After confirming that the acid value was 1.0 (mg KOH / g) or less, 99 parts of maleic anhydride and carbitol acetate were added to carry out the reaction. The reaction was terminated when the acid value reached 100 (mgKOH / g) to obtain an acid-modified epoxy acrylate resin (resin 4).

<Examples 1 to 5, Reference Examples 6 to 8 and Comparative Example 1>
It compounded according to the compounding composition shown in Table 1, and obtained the active energy ray hardening-type resin composition (the compounding quantity in Table 1 is a solid content compounding).

<Evaluation>
The active energy ray-curable resin compositions of Examples 1 to 5, Reference Examples 6 to 8 and Comparative Example 1 were coated on a glass substrate (thickness 1 mm, length 200 mm, width 200 mm) with a curtain flow coater, and then dried. A resist film having a thickness shown in Table 1 was prepared. The obtained resist film was subjected to the following evaluation. The results are also shown in Table 1.

(1) Measurement of active energy dose ratio (Y / X):
The obtained resist film was irradiated with an active energy ray of a UV lamp (35 atm) including three mixed lines of i-line (wavelength 365 nm), h-line (wavelength 405 nm) and g-line (wavelength 436 nm), and in the spectral sensitivity wavelength region. The ratio (Y / X) between the initial active energy dose (X) before irradiation and the transmitted active energy dose (Y) after passing through the resist film was determined from the formula [Y ′ / Z] by the above method. .

(2) Developability:
Table 1 shows the irradiation amounts of active energy rays of a UV lamp (35 atm) including three mixed lines of i-line (wavelength 365 nm), h-line (wavelength 405 nm) and g-line (wavelength 436 nm) on the obtained resist film surface. Then, exposure was performed through a wiring mask. Subsequently, development was performed with a 1% by mass aqueous sodium carbonate solution at 30 ° C. for 120 seconds, and the shape of the formed resist pattern was observed.
“◎”: The boundary between the irradiated portion and the unirradiated portion was sharp, and a particularly good resist pattern could be formed.
“◯”: The boundary between the irradiated part and the non-irradiated part was sharp, and a good resist pattern could be formed.
“X”: The boundary between the irradiated portion and the unirradiated portion was not sharp, and the resist pattern was not practical.

Claims (2)

(A) a base resin containing an unsaturated group and an ionic group,
(B) a photo radical initiator, and
(C) A light absorber is contained, and the base resin (A) is obtained by reacting glycidyl (meth) acrylate with a polycarboxylic acid resin to introduce unsaturated groups and carboxyl groups into the resin. (C) is an active energy ray-curable resin composition comprising only 0.1 to 5 parts by weight of a yellow light absorber with respect to 100 parts by weight of the base resin (A),
When a 10 μm or 5 μm thick resist film is coated on the substrate, i-line (wavelength 365 nm), h-line (wavelength 405 nm), and g-line (wavelength 436 nm) in the spectral sensitivity wavelength region of the resist film The ratio (Y / X) of the initial active energy dose (X) before irradiation with active energy rays including three mixed lines and the transmitted active energy dose (Y) after passing through the resist film is 10% or less. The
The light absorber (C) is represented by the following general formula (I)

(Wherein R ¹ represents a hydrogen atom, an alkyl group, an aryl group, a cycloalkyl group or an aralkyl group, R ² represents an alkyl group having 5 or more carbon atoms, and R ³ represents a hydrogen atom or 1 to 6) And represents a benzene ring optionally having a nitro group, a cyano group, an alkyl group, an alkoxy group, chlorine, bromine, a phenyl group, or a phenoxy group.
An active energy ray-curable resin composition for forming a resist film, which is a compound represented by the formula: (1) A step of applying the active energy ray-curable resin composition according to claim 1 on a substrate to form a resist film having a predetermined thickness;
(2) The resist film is irradiated with an active energy ray including three mixed lines of i-line (wavelength 365 nm), h-line (wavelength 405 nm) and g-line (wavelength 436 nm) directly or through a negative mask to form a desired pattern Curing to, and
(3) A resist pattern forming method including a step of developing a resist film cured in a desired pattern to form a resist pattern on a substrate.