JP4921230B2 - Negative resist composition for lift-off and pattern forming method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a negative resist composition for lift-off that can achieve both adhesiveness and detachability with a substrate and is excellent in halation preventive performance with less outgas generated from a resist film, and a resist pattern forming method. <P>SOLUTION: The negative resist composition for lift-off contains: 0.5-50 pts.wt. of (B) ethylene-based unsaturated compound; 0.01-30 pts.wt. of (C) silane coupling agents; 0.5-20 pts.wt. of (D) photopolymerization initiator; and 0.01-10 pts.wt. of (E) light absorption agents per 100 pts.wt. of acrylic resin having (A) a polymerizable unsaturated group. A resist pattern forming method that uses the composition is also provided. <P>COPYRIGHT: (C)2009,JPO&amp;INPIT

Description

  The present invention relates to a negative resist composition suitable for forming a metal pattern by a lift-off method and a pattern forming method thereof.

  Conventionally, when a metal pattern such as an electrode is formed on a substrate, a process such as dry etching or wet etching is used. A general process for forming a metal pattern by wet etching is a process of forming a resist film on a substrate having a metal thin film, irradiating the resist film with ultraviolet light having a certain pattern directly through a mask, and then developing the resist film. Thus, the method includes a step of forming a resist pattern, an etching step of dissolving the metal thin film, and a step of peeling the resist film.

  However, the above process has a problem in terms of processing accuracy and formation of a hard-to-etch metal pattern, and in recent years, a metal pattern formation process by a lift-off method is being used. The lift-off method includes, for example, a step of forming a resist pattern on a substrate, a step of forming a metal thin film on the substrate on which the resist pattern is formed, and a step of peeling the resist pattern, and requires an etching step. And a metal pattern can be formed on the substrate.

  As a resist composition used in the lift-off method, for example, Patent Document 1 discloses a resist composition including a base polymer, an ethylenically unsaturated compound, and a photopolymerization initiator. Patent Document 2 discloses a negative resist composition comprising an alkali-soluble resin, a photopolymerization initiator component comprising a specific combination, and a diluent. However, these resist compositions prevent adhesion to the substrate, releasability, suppression of outgas generated from the resist film, and the irradiation light transmitted through the resist film forming substrate is reflected on the stage to inhibit the resist pattern shape. We are not fully satisfied with the problem of doing halation.

JP 11-339574 A JP 2003-207904 A

  The present invention has been made in view of the above circumstances, and the object thereof is excellent in photocurability, compatible with adhesion and peelability with a substrate, and less outgas generated from a resist film, Furthermore, it is providing the negative resist composition for lift-off excellent in the halation prevention performance.

In the present invention, (A) 0.5 to 50 parts by weight of the ethylenically unsaturated compound and (C) the silane coupling agent are added to 0.1 part by weight with respect to 100 parts by weight of the acrylic resin having a polymerizable unsaturated group. 01 to 30 parts by weight, (D) 0.5 to 20 parts by weight of a photopolymerization initiator, and (E) 0.01 to 10 parts by weight of a monoazo compound as a light absorber that absorbs a wavelength of 400 nm or more. The present invention relates to a negative resist composition for lift-off.

Furthermore, the present invention provides
(1) A step of applying a lift-off negative resist composition on a substrate to form a resist film having a predetermined thickness;
(2) A step of irradiating the resist film with an active energy ray directly or through a negative mask and curing the resist film in a desired pattern, and
(3) It is related with the resist pattern formation method including the process of developing the resist film hardened | cured in the desired pattern shape, and forming a resist pattern on a base material.

  According to the present invention, a resist composition containing an acrylic resin having a polymerizable unsaturated group is used together with an ethylenically unsaturated compound, a silane coupling agent, and a light absorber, thereby providing excellent photocurability and a base material. Thus, a lift-off negative resist composition having both excellent adhesion and releasability, little outgas generated from the resist film, and excellent antihalation ability can be obtained.

  The negative resist composition for lift-off of the present invention comprises (A) 0.5 to 50 parts by weight of (B) an ethylenically unsaturated compound with respect to 100 parts by weight of an acrylic resin having a polymerizable unsaturated group, (C ) 0.01-30 parts by weight of silane coupling agent, (D) 0.5-20 parts by weight of photopolymerization initiator, and (E) 0.01-10 parts by weight of light absorber. And

  The acrylic resin (A) having a polymerizable unsaturated group is prepared by reacting the polymerizable unsaturated group with an active energy ray in the presence of the photopolymerization initiator (D) to cause an alkali developer or an acid developer. The portion that is substantially insoluble or hardly soluble in the developer and is not irradiated is soluble in the developer. For example, when the resin has many anionic groups, it is soluble in an alkaline developer, and when it has many cationic groups, it is soluble in an acid developer, and the resin contains ionic groups. If not, it is soluble in organic solvents.

The polymerizable unsaturated group is a group that can be polymerized by irradiation with active energy rays in the presence of the photopolymerization initiator (D). Specific examples thereof include (meth) acryloyl group [CH ₂ ═CR—CO -(Wherein R represents a hydrogen atom or a methyl group)], cinnamoyl group, allyl group, azide group, cinnamylidene group and the like.

  The concentration of the polymerizable unsaturated group in the resin (A) can be varied over a wide range depending on the type and molecular weight of the resin, but preferably 0.2 to 7.0 with respect to 1 kg of the resin solid content. It is suitable from the point of ensuring photocurability and suppressing outgas that it is contained at a concentration of 0.7 to 4.5 mol, more preferably 0.7 to 4.5 mol.

  Here, outgas is volatile gas generated from the resist film. When the amount of volatile gas generated is large, when the metal thin film is formed by vapor deposition or the like, the degree of reduced pressure in the chamber is reduced, and impurities are easily mixed into the metal thin film. As a result, the conductivity of the formed metal thin film may be reduced.

  The acrylic resin (A) having a polymerizable unsaturated group generally has a number average molecular weight in the range of 1,000 to 100,000, preferably 3,000 to 80,000, and its glass transition. The temperature (Tg) is preferably −20 ° C. to 100 ° C., and particularly preferably within the range of −10 to 90 ° C. from the viewpoint of ensuring tackiness and photocurability of the resist film.

  Here, in this specification, the number average molecular weight is a value obtained by converting the number average molecular weight measured with a gel permeation chromatograph (“HLC8120GPC” manufactured by Tosoh Corporation) based on the number average molecular weight of polystyrene. is there. Columns are “TSKgel G-4000H × L”, “TSKgel G-3000H × L”, “TSKgel G-2500H × L”, “TSKgel G-2000H × L” (both manufactured by Tosoh Corporation, trade names) ), Mobile phase: tetrahydrofuran, measurement temperature: 40 ° C., flow rate: 1 cc / min, detector: RI.

  In the present invention, the glass transition temperature (° C.) is a value measured using a differential scanning calorimeter “DSC-220U” (manufactured by Seiko Instruments Inc.). Take the sample in a measuring cup, remove the solvent completely by vacuum suction, measure the change in calorie in the range of -20 ° C to + 200 ° C at a rate of temperature increase of 10 ° C / min. The change point is defined as the glass transition temperature.

  Hereinafter, specific examples of the acrylic resin (A) having a polymerizable unsaturated group will be described.

  (A-1) Acrylic resin having a (meth) acryloyl group: This resin can be produced, for example, by adding a glycidyl group-containing unsaturated compound to a high acid value acrylic resin. The high acid value acrylic resin used in that case is, for example, an α, β-ethylenically unsaturated acid such as acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid and the like as an essential component, methyl (meth) acrylate, Ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, etc. (Meth) acrylic acid esters; obtained by copolymerizing other polymerizable unsaturated monomers such as styrene, (meth) acrylonitrile, (meth) acrylamide and the like.

  In the present specification, (meth) acrylate means both “methacrylate” and “acrylate”.

  The α, β-ethylenically unsaturated acid is used in an amount such that the acid value of the high acid value acrylic resin is generally in the range of 10 to 650 (mgKOH / g), preferably 20 to 500 (mgKOH / g). be able to. The number average molecular weight and glass transition temperature (Tg) of the high acid value acrylic resin have the number average molecular weight and Tg described above for the resin obtained by adding a glycidyl group-containing unsaturated compound to the high acid value acrylic resin. Is adjusted as appropriate.

  Here, in this specification, the acid value (mgKOH / g) is expressed in mg of potassium hydroxide when the amount of acid groups contained in 1 g of resin solid content is converted into potassium hydroxide. The molecular weight of potassium hydroxide is 56.1.

The acid value is measured according to JIS K-5601-2-1 (1999). A sample is dissolved in a mixed solvent of toluene / ethanol = 2/1 volume ratio, titrated with a potassium hydroxide solution using phenolphthalein as an indicator, and calculated by the following formula.
Acid value (mgKOH / g) = 56.1 × V × C / m
V: titration volume (ml), C: concentration of titrant (mol / l), m: weight of solid content of sample (g)

  On the other hand, specific examples of the glycidyl group-containing unsaturated compound added to the high acid value acrylic resin include glycidyl acrylate and glycidyl methacrylate.

  The addition reaction between the high acid value acrylic resin and the glycidyl group-containing unsaturated compound is carried out according to a method known per se, for example, at 80 to 120 ° C. for 1 to 5 hours using a catalyst such as tetraethylammonium bromide. Can be done easily.

  The acrylic resin having a (meth) acryloyl group can also be produced by adding a reaction product of a hydroxyl group-containing polymerizable unsaturated compound and a diisocyanate compound to a hydroxyl group-containing acrylic resin.

  Examples of the hydroxyl group-containing polymerizable unsaturated compound include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, N-methylol acrylamide and the like, and the diisocyanate compound is non-yellowing type. Are preferable, and examples include isophorone diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, and lysine diisocyanate.

  The hydroxyl group-containing acrylic resin has a hydroxyl group-containing polymerizable unsaturated compound such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate as an essential component, and does not have a hydroxyl group as necessary. It can be obtained by copolymerizing esters of (meth) acrylic acid, α, β-ethylenically unsaturated acid, and other polymerizable unsaturated monomers.

  (A-2) Acrylic resin having a cinnamoyl group: This resin reacts, for example, a hydroxyl group-containing acrylic resin and a substituted or unsubstituted cinnamic acid halide in the presence of a base, for example, in a pyridine solution. Can be manufactured. The hydroxyl group-containing acrylic resin used at that time can be the same as the hydroxyl group-containing acrylic resin described in the section (A-1).

  The substituted or unsubstituted cinnamic acid halide is generally used in an amount of 6 to 180 parts by weight, preferably 30 to 140 parts by weight per 100 parts by weight of the hydroxyl group-containing acrylic resin. it can.

  Examples of the substituted or unsubstituted cinnamic acid halide that can be used include cinnamic acid halides that may have 1 to 3 substituents selected from a nitro group, a lower alkoxy group, and the like on the benzene ring, More specifically, cinnamic acid chloride, p-nitrocinnamic acid chloride, p-methoxycinnamic acid chloride, p-ethoxycinnamic acid chloride and the like can be mentioned.

  (A-3) Acrylic resin having an allyl group: For example, this resin can be obtained by adding allyl glycidyl ether to the high acid value acrylic resin used in the previous (A-1) item, or (A-1) The hydroxyl group-containing acrylic resin described in the section can be produced by adding a reaction product of (meth) allyl alcohol and the diisocyanate compound described in the previous section (A-1).

  The addition reaction between the high acid value acrylic resin and allyl glycidyl ether is performed in the same manner as the reaction between the high acid value acrylic resin and the glycidyl group-containing (meth) acrylic acid ester described in the previous section (A-1). be able to.

  In the resist composition of the present invention, the acrylic resin (A) having a polymerizable unsaturated group is an anionic resin having an acid group such as a carboxyl group, a cationic resin having a cationic group such as an amino group, or an ion. Any of resins having no functional group may be used.

  As the resin having no ionic group, for example, in (A-1), (A-2), and (A-3), an acrylic resin is introduced when a polymerizable unsaturated group is introduced into a high acid value acrylic resin. It can be obtained by reacting substantially all of the acid groups in the resin to eliminate the acid groups.

  In this invention, the resin of (A-1)-(A-3) can be used individually or in combination of 2 or more types as an acrylic resin (A) which has a polymerizable unsaturated group.

  The ethylenically unsaturated compound (B) is a compound containing at least one ethylenically unsaturated double bond in its chemical structure, and is polymerized by irradiation with active energy rays to insolubilize the irradiated portion with respect to the developer. And a compound having a function of bringing about.

  Examples of the monofunctional ethylenically unsaturated compound include esterified products of monohydric alcohol and (meth) acrylic acid. Specifically, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (Meth) acrylate, neopentyl (meth) acrylate, t-butyl (meth) acrylate, cyclohexyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, isobornyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate Etc.

  Examples of the bifunctional or higher polyfunctional ethylenically unsaturated compound include an esterified product of a polyhydric alcohol and (meth) acrylic acid. Specifically, for example, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, 1,3-butylene glycol di (meth) Acrylate, 1,4-butanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, glycerin di (meth) acrylate, trimethylolpropane di (meth) acrylate, pentaerythritol di (meth) acrylate, Neopentyl glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, bisphenol A ethylene oxide modified di (meth) acrylate, polyester di (meth) acrylate, urethane Di (meth) acrylate compounds such as (meth) acrylate; glycerin tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane propylene oxide modified tri (meth) acrylate, trimethylolpropane ethylene oxide modified tri (meth) ) Acrylates, tri (meth) acrylate compounds such as pentaerythritol tri (meth) acrylate; tetra (meth) acrylate compounds such as pentaerythritol tetra (meth) acrylate; other dipentaerythritol penta (meth) acrylates, dipentaerythritol hexa Examples include (meth) acrylate. These ethylenically unsaturated compounds can be used alone or in combination of two or more.

  The ethylenically unsaturated compound (B) is preferably a bifunctional or higher polyfunctional ethylenically unsaturated compound from the viewpoint of ensuring photocurability and suppressing outgas.

  Content of an ethylenically unsaturated compound (B) is the range of 0.5-50 weight part with respect to 100 weight part of acrylic resin (A) which has a polymerizable unsaturated group. Preferably it is the range of 1-40 weight part. The lower limit of this range is significant in terms of ensuring photocurability, and the upper limit is significant in terms of tackiness of the resist film and suppression of outgassing.

  Examples of the silane coupling agent (C) include γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, and 2- (3,4-epoxy). Epoxy group-containing silane coupling agents such as cyclohexyl) -ethyltrimethoxysilane; N-β- (aminoethyl) -γ-aminopropylmethyldimethoxysilane, N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane Amino group-containing silane coupling agents such as N-β- (aminoethyl) -γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane; γ-chloropropyltrimethoxysilane Chloro group-containing silane coupling agent such as γ- (meth) a Liloyloxypropyltrimethoxysilane, γ- (meth) acryloyloxypropylmethyldimethoxysilane, γ- (meth) acryloyloxypropyltriethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, vinyltris (methoxyethoxy) silane, etc. Examples include vinyl group-containing silane coupling agents. Among these, it is preferable to use a vinyl group-containing silane coupling agent from the viewpoint of excellent peelability with respect to the stripping solution while maintaining adhesion to the substrate, securing photocurability, and suppressing outgas.

  Content of a silane coupling agent (C) is the range of 0.01-30 weight part with respect to 100 weight part of acrylic resin (A) which has a polymerizable unsaturated group. Preferably it is the range of 0.05-20 weight part, More preferably, it is the range of 0.1-15 weight part. The lower limit value of these ranges is significant in terms of improving the adhesion to the substrate, and the upper limit value is significant in terms of outgas suppression and peelability. In addition, when the content exceeds the upper limit, if the time from the creation of the resist film to the irradiation of the active energy ray is long, the line width of the resulting resist pattern becomes thicker or the boundary between the irradiated part and the unirradiated part Since sharpness is lost, it is not preferable.

  The photopolymerization initiator (D) can be used without particular limitation as long as it is an initiator that absorbs active energy rays and generates radicals. Examples of the photopolymerization initiator (D) include α-diketones such as benzyl and diacetyl; acyloins such as benzoin; acyloin ethers such as benzoin methyl ether, benzoin ethyl ether and benzoin isopropyl ether; thioxanthone, 2, 4 -Thioxanthones such as diethylthioxanthone, 2-isopropylthioxanthone, thioxanthone-4-sulfonic acid; Benzophenones such as benzophenone, 4,4'-bis (dimethylamino) benzophenone, 4,4'-bis (diethylamino) benzophenone; Michler's ketone Acetophenone, 2- (4-toluenesulfonyloxy) -2-phenylacetophenone, p-dimethylaminoacetophenone, α, α'-dimethoxyacetoxybenzophenone, 2,2'-dimethyl Xyl-2-phenylacetophenone, p-methoxyacetophenone, 2-methyl [4- (methylthio) phenyl] -2-morpholino-1-propanone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) Acetophenones such as -butan-1-one, α-isohydroxyisobutylphenone, α, α'-dichloro-4-phenoxyacetophenone, 1-hydroxy-1-cyclohexylacetophenone; 2,4,6-trimethylbenzoyldiphenylphosphine oxide Acylphosphine oxides such as bis (acyl) phosphine oxide; quinones such as anthraquinone and 1,4-naphthoquinone; phenacyl chloride, trihalomethylphenylsulfone, tris (trihalomethyl) -s-triazine, etc. Androgenic compounds; peroxides such as di -t- butyl peroxide and the like. These can be used alone or in combination of two or more.

  Commercially available products of the photopolymerization initiator (D) include, for example, IRGACURE-184, 261, 369, 500, 651, 907, CGI-1700 (manufactured by Ciba Specialty Chemicals, Inc., product) Name), Darocur-1173, 1116, 2959, 1664, 4064 (manufactured by Merck Japan Ltd., trade name), KAYACURE-DETX, MBP, DMBI, EPA, OA ( Nippon Kayaku Co., Ltd., trade name), VICURE-10, 55 (made by STAUFFER Co., LTD., Trade name), TRIGONAL P1 [AKZO Co., LTD. .), Product name], SANDORAY 1000 (manufactured by SANDOZ Co., LTD., Product name), Deep (DEAP) (manufactured by APJOHN Co., LTD., Product name) , Kang Cure (QUANTACURE) -PDO, the ITX, the EPD [Ward shake Kin Sopu, Inc. (WARD BLEKINSOP Co., LTD.), Trade name], and the like can be given. As the photopolymerization initiator (D), acetophenones are preferable from the viewpoints of ensuring photocurability and developability.

  Content of a photoinitiator (D) is the range of 0.5-20 weight part with respect to 100 weight part of acrylic resins (A) which have a polymerizable unsaturated group. Preferably it is the range of 1-10 weight part. The lower limit of this range is significant in terms of ensuring photocurability, and the upper limit is significant in terms of pattern formability and cost.

  As a light absorber (E), the light absorber which absorbs the wavelength of 400 nm or more is mentioned, for example. Examples of the light absorber that absorbs a wavelength of 400 nm or longer include a monoazo compound. Examples of the monoazo compound include compounds represented by the following general formula (I).

（ここで、Ｒ¹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、Ｒ²は５個以上の炭素原子を有するアルキル基を表し、Ｒ³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。）。

(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.

  Specific examples of the light absorber (E) include ORASOL YELLOW 4GN (trade name, manufactured by Ciba Specialty Chemicals), OIL COLORS YELLOW 3G SOLVENT YELLOW 16 (trade name, manufactured by Orient Chemical Co., Ltd.), OIL COLORS YELLOW GLS SOLV GTS SOLG (Same as left), OIL COLORS YELLOW 105 (same as left), OIL COLORS YELLOW 129 SOLVENT YELLOW 29 (same as left), NEPTU YELLOW 075 (trade name, manufactured by BASF) and the like.

  As the light absorber (E), it is preferable to use a compound represented by the following chemical formula (II) from the viewpoint of solubility in a resist composition and antihalation performance.

  Content of a light absorber (E) is the range of 0.01-10 weight part with respect to 100 weight part of acrylic resins (A) which have a polymerizable unsaturated group. Preferably it is the range of 0.1-7 weight part, More preferably, it is the range of 0.8-7 weight part.

  In addition to the above, the resist composition of the present invention can use a saturated resin. As this saturated resin, it can be used in order to adjust the solubility with respect to the developing solution of the resist composition of this invention. This includes, for example, polyester resin, alkyd resin, acrylic resin, vinyl resin, epoxy resin, phenol resin, natural resin, synthetic rubber, silicone resin, fluorine resin, polyurethane resin and the like. These resins can be used alone or in combination of two or more.

  In addition to the above, the resist composition of the present invention can also use a photosensitizer. Examples of the photosensitizer include thioxanthene, xanthene, ketone, thiopyrylium salt, base styryl, merocyanine, 3-substituted coumarin, coumarin, 3.4-substituted coumarin, cyanine, Examples include acridine, thiazine, phenothiazine, anthracene, coronene, benzanthracene, perylene, merocyanine, ketocoumarin, fumarine, and borate dyes. These can be used alone or in combination of two or more. Examples of the borate photosensitizing dye include those described in JP-A-5-241338, JP-A-7-5685, JP-A-7-225474, and the like.

  Moreover, the resist composition of this invention may contain the organic solvent, the surface adjusting agent, etc. as needed. The organic solvent is used for the purpose of adjusting the viscosity. The organic solvent is not particularly limited as long as it can dissolve the components (A) to (E). Specifically, for example, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl amyl ketone, ethyl isoamyl ketone, diisobutyl ketone, methyl hexyl ketone; ethyl acetate, butyl acetate, methyl benzoate, methyl propionate, etc. Esters such as tetrahydrofuran, dioxane and dimethoxyethane; cellosolves such as methyl cellosolve, ethyl cellosolve, diethylene glycol monomethyl ether, propylene glycol monomethyl ether acetate and 3-methoxybutyl acetate; alcohols such as ethyl alcohol and benzyl alcohol Aromatic hydrocarbons, aliphatic hydrocarbons and the like.

  Then, the resist pattern formation method using the negative resist composition for lift-off of this invention is demonstrated.

The resist pattern forming method of the present invention comprises:
(1) A step of applying a lift-off negative resist composition of the present invention on a substrate to form a resist film having a predetermined thickness;
(2) A step of irradiating the resist film with an active energy ray directly or through a negative mask and curing the resist film in a desired pattern, and
(3) A step of developing the resist film cured in a desired pattern to form a resist pattern on the substrate is included.

  In the present invention, the resist film to be coated on the substrate surface is a dry film obtained by coating the resist composition and volatilizing the organic solvent as necessary. In addition, a dry film formed by coating and drying an organic solvent resist composition on the surface of a base film such as a PET film and forming a dry resist film on the surface of the base film is in contact with the substrate surface and the dry resist film. The base film can be peeled off from the dry resist film to form a resist film.

  The base material used above is not particularly limited, and for example, a silicon wafer or glass can be used.

  The coating method is not particularly limited, and a conventionally known method can be used. Specifically, it can be applied by, for example, a roller, a roll coater, a spin coater, a curtain roll coater, a slit coater, spray, electrostatic coating, dip coating, silk printing, spin coating or the like.

  In the present invention, a conventionally known light source can be used as the light source of the active energy ray to be irradiated. Specific examples include ultra-high pressure, high pressure, medium pressure, and low pressure mercury lamps, chemical lamps, carbon arc lamps, xenon lamps, metal halide lamps, tungsten lamps, and the like.

  The active energy ray is not particularly limited, and examples thereof include ultraviolet light, visible light, and laser light (near infrared light, visible light laser, ultraviolet laser, etc.). In particular, ultraviolet rays are preferable, and those containing three mixed lines of i-line (wavelength 365 nm), h-line (wavelength 405 nm) and g-line (wavelength 436 nm) are more preferable.

The dose of the active energy ray is not particularly limited, is preferably in the range 100~10000J / ^{m 2,} more preferably of 300~7000J / ^{m 2.} The lower limit of this range is significant in terms of ensuring photocurability. The upper limit is significant in improving the pattern shape.

  The thickness of the resist film is 0.5 to 20 μm, preferably 1 to 10 μm, and more preferably 1 to 5 μm. The lower limit of these ranges is significant in terms of pattern formation, and the upper limit is significant in terms of outgas suppression.

Examples of the developer used in the development process include alkali developers such as triethylamine, diethanolamine, triethanolamine, ammonia, sodium metasilicate, potassium metasilicate, sodium carbonate, and tetraethylammonium hydroxide.
Examples of the acidic developer include acidic developers such as acetic acid, formic acid, and hydroxyacetic acid. The density | concentration of a developing solution is 0.1 to 3 weight% normally, Preferably it is the range of 0.2 to 2 weight%. The development processing is usually at a temperature of 20 to 50 ° C. and usually in a range of 20 to 120 seconds.

  A resist pattern is formed by the above process.

  Next, the metal pattern forming process after forming the resist pattern will be described.

  The metal pattern forming step includes a step of forming a metal pattern film on the entire surface of the substrate surface having the resist pattern, and a step of peeling the resist pattern.

  A metal film made of aluminum, copper, gold, ITO, tin oxide, tantalum or the like is formed on the entire surface of the substrate having the resist pattern by a method such as vapor deposition or sputtering. In addition, in order to improve the adhesion between the metal film and the substrate, it is also possible to perform the above-described deposition or the like after performing UV ozone ashing or oxygen plasma treatment after the resist pattern is formed.

  Thereafter, the resist pattern is peeled off by rinsing with a stripping solution such as an alkaline aqueous solution or an organic solvent. As the alkaline aqueous solution, an aqueous solution of sodium hydroxide, potassium hydroxide, ammonia, triethanolamine, triethylamine or the like can be usually used. Moreover, as an organic solvent, it can carry out by melt | dissolving an irradiation part using solvents, such as 1,1,1-trichloroethane, methyl ethyl ketone, a methylene chloride, for example. Peeling is usually performed by immersing in the stripping solution at a temperature of 20 to 80 ° C. for usually 1 to 30 minutes.

  Through the above process, a metal pattern is formed on the substrate.

  Hereinafter, the present invention will be described in more detail with reference to examples. “Part” and “%” indicate “part by weight” and “% by weight” unless otherwise specified.

<Synthesis Example 1 (Synthesis of Resin 1)>
It takes 3 hours in 90 parts of ethylene glycol monomethyl ether in which a mixed liquid composed of 60 parts of styrene, 10 parts of methyl acrylate, 30 parts of acrylic acid and 3 parts of azobisisobutyronitrile is maintained at 120 ° C. in a nitrogen gas atmosphere. And then dropped. After dropping, the mixture was aged for 1 hour, and a mixture of 1 part of azobisdimethylvaleronitrile and 10 parts of ethylene glycol monomethyl ether was added dropwise over 1 hour, and further aged for 5 hours to obtain a high acid value acrylic resin (resin acid value). About 230 mg KOH / g) solution was obtained. Next, 35 parts of glycidyl methacrylate, 0.13 part of hydroquinone and 0.6 part of tetraethylammonium bromide are added to this solution and reacted at 110 ° C. for 5 hours while blowing air, and an acrylic resin having a polymerizable unsaturated group (resin A solution (resin 1) having an acid value of about 70 mg KOH / g, a polymerizable unsaturated group concentration of 1.83 mol / kg, a Tg point of 45 ° C., and a number average molecular weight of about 15,000 was obtained. This resin solution had a solid content of about 57%.

<Synthesis Example 2 (Synthesis of Resin 2)>
3 hours in 90 parts of propylene glycol monomethyl ether in which a mixed liquid composed of 40 parts of methyl methacrylate, 40 parts of butyl acrylate, 20 parts of acrylic acid and 2 parts of azobisisobutyronitrile was maintained at 110 ° C. in a nitrogen gas atmosphere. In short, it was dripped. After the dropwise addition, the mixture was aged for 1 hour, and a mixture of 1 part of azobisdimethylvaleronitrile and 10 parts of propylene glycol monomethyl ether was added dropwise over 1 hour, and further aged for 5 hours to obtain a high acid value acrylic resin (resin acid value). About 155 mg KOH / g) solution was obtained. Next, 24 parts of glycidyl methacrylate, 0.12 part of hydroquinone and 0.6 part of tetraethylammonium bromide were added to this solution and reacted for 5 hours at 110 ° C. while blowing air, and an acrylic resin having a polymerizable unsaturated group (resin An acid value of about 50 mg KOH / g, a polymerizable unsaturated group concentration of 1.35 mol / kg, a Tg point of 20 ° C., and a number average molecular weight of about 20,000) (resin 2) were obtained. This resin solution had a solid content of about 54%.

<Synthesis Example 3 (Synthesis of Resin 3)>
A mixed solution consisting of 20 parts of methyl methacrylate, 60 parts of acrylic acid, 20 parts of methacrylic acid and 6 parts of t-butyl peroxyoctoate was placed in 90 parts of n-butyl alcohol maintained at 110 ° C. in a nitrogen gas atmosphere for 3 hours. Was added dropwise. After dropping, the mixture was aged for 1 hour, and a mixture of 1 part of azobisdimethylvaleronitrile and 10 parts of n-butyl alcohol was added dropwise over 1 hour, and further aged for 5 hours to obtain a high acid value acrylic resin (resin acid value). About 520 mg KOH / g) solution was obtained. Next, 114 parts of glycidyl methacrylate, 0.24 parts of hydroquinone and 1.0 part of tetraethylammonium bromide were added to this solution and reacted for 5 hours at 110 ° C. while blowing air, and an acrylic resin having a polymerizable unsaturated group (resin A solution (resin 3) having an acid value of about 70 mg KOH / g, a polymerizable unsaturated group concentration of 3.75 mol / kg, a Tg point of 8 ° C., and a number average molecular weight of about 18,000 was obtained. This resin solution had a solid content of about 68%.

<Synthesis Example 4 (Synthesis of Resin 4)>
In 90 parts of cellosolve maintained at 120 ° C. in a nitrogen gas atmosphere with a mixed solution consisting of 50 parts of styrene, 10 parts of n-butyl acrylate, 30 parts of methyl acrylate, 10 parts of acrylic acid and 0.5 part of azobisisobutyronitrile. It was dripped in 3 hours. After dropping, the mixture was aged for 1 hour, and a mixture of 1 part of azobisdimethylvaleronitrile and 10 parts of cellosolve was added dropwise over 1 hour, and further aged for 2 hours to obtain an acrylic resin (resin acid value of about 78 mgKOH / g, Tg). A solution (resin 4) having a point of 47 ° C. and a number average molecular weight of about 15,000 was obtained. This resin solution had a solid content of about 50%.

<Example 1>
After 175 parts (100 parts in solid content) of the acrylic resin solution (resin 1) having a polymerizable unsaturated group obtained in Synthesis Example 1 was dissolved in 330 parts of methyl amyl ketone, Aronix M-210 (trade name, Tojo) 20 parts by synthesizer, bisphenol A ethylene oxide modified diacrylate, 1 part by silicone KBM-503 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd., 3-methacryloyloxypropyltrimethoxysilane), Irgacure-369 (trade name, Ciba Specialty) 5 parts of Chemicals, photopolymerization initiator), 5 parts of NEPTU YELLOW 075 [trade name, manufactured by BASF, light absorber represented by chemical formula (II)] are added and mixed to obtain a uniform resist composition. It was.

<Examples 2 to 10 and Comparative Examples 1 to 6>
Each resist composition of Examples 2-10 and Comparative Examples 1-6 was manufactured by the method similar to Example 1 except having mix | blended the composition of the resist composition according to the compounding composition shown in Table 1 (in Table 1). The blending amount of the resins 1 to 4 is a solid content display).

<Evaluation test>
The resist composition obtained as described above was applied to a glass substrate having a thickness of 1.8 mm and a size of 100 mm × 100 mm using a spin coater, dried at 60 ° C. for 1 minute, and a resist having a dry film thickness of 3 μm. A membrane was obtained.

  The obtained resist film was subjected to the following evaluation test. The test results are shown in Table 1.

（注１）アロニックスＭ−３０９：商品名、東亞合成社製、トリメチロールプロパントリアクリレート
（注２）シリコーンＫＢＥ−５０３：商品名、信越化学工業社製、γ−メタクリロイルオキシプロピルトリエトキシシラン
（注３）イルガキュア−９０７：商品名、チバ スペシャルティ ケミカルズ社製、光重合開始剤
（注４）ＯＲＡＳＯＬ ＹＥＬＬＯＷ ４ＧＮ：商品名、チバ スペシャルティ ケミカルズ社製、光吸収剤

(Note 1) Aronix M-309: Trade name, manufactured by Toagosei Co., Ltd., trimethylolpropane triacrylate (Note 2) Silicone KBE-503: Trade name, manufactured by Shin-Etsu Chemical Co., Ltd., γ-methacryloyloxypropyltriethoxysilane (Note) 3) Irgacure-907: trade name, manufactured by Ciba Specialty Chemicals, photopolymerization initiator (Note 4) ORASOL YELLOW 4GN: trade name, manufactured by Ciba Specialty Chemicals, light absorber

<Photocurability>
3 lines of i-line (wavelength 365 nm), h-line (wavelength 405 nm), and g-line (wavelength 436 nm) are passed through a 21-step tablet film (manufactured by Hitachi Chemical Co., Ltd., Photec 21-step tablet film). An active energy ray of a UV lamp (35 atm) including a mixed line was irradiated at an irradiation amount of 500 J / m ² . Next, development was carried out with a 0.25 wt% sodium carbonate aqueous solution at 25 ° C. for 30 seconds.
Table 1 shows the step tablet sensitivity of the resist film after development. Here, the step tablet sensitivity is a photocurability (resist pattern) that is excellent when irradiated with light and developed using a film having a light transmittance that varies stepwise (here, a 21-step step tablet film). Means the number of steps of the minimum light transmittance. The larger the step number, the lower the light transmittance of the film, and the larger the step number, the better the photocurability.

<Adhesion>
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) is applied to the resist film forming substrate in a line-and-space (L / S) Irradiation was performed through a mask having a pattern of 30 μm / 100 μm. Here, the irradiation with active energy rays was performed at an irradiation dose at which the step tablet sensitivity was 7 steps for each resist film. Next, development was performed with a 0.25 wt% sodium carbonate aqueous solution at 25 ° C. for 30 seconds to obtain a resist pattern forming substrate.
The resulting resist pattern was evaluated for adhesion according to the following criteria.
“◯”: The resist pattern is not peeled off.
“Δ”: The resist pattern is partially peeled off.
“×”: Most of the resist pattern is peeled off.

<Pattern formability>
The resist film-forming substrate is left for 1 hour after being prepared, and then placed on a black alumite-treated aluminum stage where the irradiated light is not reflected. The resist film-forming substrate is coated with i-line (wavelength 365 nm), h-ray (wavelength 405 nm) and active energy rays of a UV lamp (35 atm) including three lines of g-line (wavelength 436 nm) were irradiated through a mask having a line & space (L / S) pattern of 30 μm / 100 μm. Here, the irradiation with active energy rays was performed at an irradiation dose at which the step tablet sensitivity was 7 steps for each resist film. Next, development was performed for 30 seconds with a 0.25 wt% sodium carbonate aqueous solution at 25 ° C. without taking time, and the shape of the formed resist pattern was observed.
“◎”: The line width was about the same as L / S by about 5%, and the boundary between the irradiated part and the unirradiated part was sharp, and a particularly good resist pattern could be formed.
“◯”: Although the line width is about 5 to 10% thicker than L / S, the boundary between the irradiated part and the unirradiated part is sharp, and a good resist pattern can be formed.
“X”: The line width was 10% or more thicker than L / S, or the boundary between the irradiated part and the non-irradiated part was not sharp, and the resist pattern was not practical.

<Anti-halation performance>
The resist film forming substrate is placed on an aluminum stage that reflects irradiated light, and three lines of i-line (wavelength 365 nm), h-ray (wavelength 405 nm), and g-line (wavelength 436 nm) are applied to the resist film-forming substrate. The active energy ray of a UV lamp (35 atm) containing was irradiated through a mask having a line & space (L / S) pattern of 30 μm / 100 μm. Here, the irradiation with active energy rays was performed at an irradiation dose at which the step tablet sensitivity was 7 steps for each resist film. Subsequently, development was performed with a 0.25 wt% sodium carbonate aqueous solution at 25 ° C. for 30 seconds, and the shape of the formed resist pattern was observed. The test was performed with the time from irradiation to development within 30 minutes after creation of the resist film-forming substrate.
“◎”: The boundary portion between the irradiated portion and the non-irradiated portion was particularly 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.

<Outgas evaluation>
A resist pattern forming substrate was obtained in the same manner as in the adhesion test. About the obtained resist pattern formation base material, the metal film which consists of a tin oxide was formed by vapor deposition, and the outgas performance of the resist composition was evaluated from the electroconductivity of the metal film. Conductivity is evaluated by forming a metal film (reference) made of tin oxide on a glass substrate on which the resist pattern is not formed under the same vapor deposition conditions. evaluated.
“◎”: Same as reference and good conductivity “◯”: Slightly inferior to reference but good conductivity and practicality “×”: Inferior to reference and poor conductivity and no practicality

<Peelability>
A resist pattern forming substrate was obtained in the same manner as in the adhesion test. About the obtained resist pattern formation base material, it immersed in 50 degreeC 5.0% sodium hydroxide aqueous solution. The time required for the resist pattern to peel from the substrate was measured, and the peelability was evaluated according to the following criteria.
“◯”: peeling time ≦ 1 minute “Δ”: 1 minute <peeling time ≦ 2 minutes “×”: 2 minutes <peeling time

Claims (5)

(A) 0.5 to 50 parts by weight of (B) ethylenically unsaturated compound and (C) 0.01 to 30 parts by weight of silane coupling agent with respect to 100 parts by weight of acrylic resin having a polymerizable unsaturated group Part (D) 0.5 to 20 parts by weight of a photopolymerization initiator, and (E) 0.01 to 10 parts by weight of a monoazo compound as a light absorber that absorbs a wavelength of 400 nm or longer. A negative resist composition for lift-off. The negative resist composition for lift-off according to claim 1, wherein the ethylenically unsaturated compound (B) is a polyfunctional ethylenically unsaturated compound. The negative resist composition for lift-off according to claim 1 or 2, wherein the silane coupling agent (C) is a vinyl group-containing silane coupling agent. The monoazo compound 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) Represents an alkyl group having one carbon atom, and B represents a benzene ring which may have a nitro group, a cyano group, an alkyl group, an alkoxy group, chlorine, bromine, a phenyl group or a phenoxy group. The negative resist composition for liftoff according to any one of claims 1 to 3, wherein the negative resist composition is a compound. (1) The process of apply | coating the negative resist composition for lift-off of any one of Claims 1-4 on a base material, and forming a resist film of predetermined thickness,
(2) A step of irradiating the resist film with an active energy ray directly or through a negative mask and curing the resist film in a desired pattern, 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.