TWI335491B - Photoresist composition for use in spray coating, and laminate body - Google Patents

Description

1335491 η ' Π) IX. Description of the Invention [Technical Field of the Invention] The present invention relates to a photoresist composition and a laminate for spraying. The present application claims priority from Japanese Patent Application No. 2005-34224 5, filed on Nov. 28, 2005, and the content of which is incorporated by reference. After the photoresist film formed by the photoresist material, the photoresist film is exposed to radiation by selective light, electron beam or the like through a mask having a certain pattern, and then subjected to development processing, and the photoresist film is formed thereon. The step of forming a photoresist pattern of a certain shape is performed. Further, the change of the characteristic to the exposure portion is dissolved in the developer liquid is regarded as a positive type photoresist material, and the characteristic change is that the exposed portion is insoluble in the developer liquid, and is regarded as a negative type photoresist material. The conventional photoresist coating method is known as a spray coating method in addition to the spin coating method (refer to Patent Document 1 below). • The spin coating method is applied to a method of forming a photoresist film having a uniform thickness on a flat substrate, and the spray coating method is applied to form a photoresist film having a concave-convex shape that tracks the unevenness of the substrate on a substrate having irregularities on the surface. method. Patent Document 1: Japanese Laid-Open Patent Publication No. 2004-307667. SUMMARY OF THE INVENTION PROBLEMS TO BE SOLVED BY THE INVENTION However, when the spray coating method is applied to a substrate having a stage portion on the surface, the thickness of the photoresist film at the corner of the stage tends to be locally thin. The problem of transformation. -5- 'sa 1335491 % Λ \ \ ' (2) In view of the above-mentioned matter, it is therefore an object of the present invention to provide a photoresist having a uniform film thickness even when a coated surface of a substrate is formed into a step portion. A photoresist composition of a film and a laminate of a film having a thickness uniformity formed on a substrate having a stage portion. - Means for Solving the Problems ^ In order to achieve the above object, the present invention consists of the following. φ The first embodiment of the present invention is a photoresist composition for spraying, characterized in that a photoresist composition for a method of spraying a photoresist film on a substrate contains a modified siloxane-based surfactant. A second embodiment of the present invention is characterized in that a laminate having a step portion of 10 to ΙΟΟΟμηη on a surface to be coated is composed of a photoresist containing a modified siloxane-based surfactant. In the laminate forming the photoresist film, the photoresist film continuously coats the upper surface and the side surface of the step portion, and the film thickness on the step portion of the photoresist film is 1 to 40 μπι, and the upper surface of the phase portion and the boundary of the side surface The film thickness of the portion is 77% or more of the film thickness of the upper portion adjacent to the boundary portion. Advantageous Effects of Invention According to the present invention, it is possible to form a photoresist composition of a photoresist film having a uniform film thickness even when a coated surface of a substrate is formed into a step portion. Further, in the present invention, a laminate having a photoresist composition having a uniform film thickness can be formed on a substrate having a stage portion.

-6- ί S 1335491 1 s ' ' (3) BEST MODE FOR CARRYING OUT THE INVENTION <Positive-type photoresist composition> [Modified siloxane-based surfactant] The photoresist composition of the present invention contains modification A decane-based surfactant (hereinafter also referred to simply as a surfactant). As described later, it is known that the photoresist composition used in the prior spraying method is completely free of a modified decane-based surfactant. The inventors have found for the first time that the prior photoresist composition is added with a modified siloxane. In the case of a surfactant, even if the coated surface of the substrate is formed into a step portion, a photoresist film having a uniform film thickness can be formed by a spray method. The modified base of the modified oxoxane surfactant is, for example, an alkyl group, an aralkyl group and an ester group, and specifically, a polyalkyl-modified decane-based surfactant, a polyester-modified oxime An alkyl surfactant, an aralkyl modified siloxane surfactant, or an alkyl aralkyl modified siloxane surfactant. In the name of the product, for example, SF8416 (manufactured by Toray Island Co., Ltd.), XL-121 (manufactured by Kuraray Co., Ltd.), and # TSF442 1 (GE Toshiba Polyoxane) of a polyalkyl-modified decane-based surfactant. Company system), KF-412, KF-413, KF-4 14 (all manufactured by Shin-Etsu Chemical Co., Ltd.); BYK-310 and BYK-3 1 5 of polyester modified siloxane surfactants Ju Chemical Co., Ltd.), KF-910, X-22-715 (all manufactured by Shin-Etsu Chemical Co., Ltd.): BYK-322, BYK-323, an aralkyl-modified siloxane surfactant, all of which are giant chemistry Company system); SH203 and SF8419 (all manufactured by Toray Island Co., Ltd.) and WACKER TN (made by Asahi Kasei Wacker Polyoxane Co., Ltd.) of cerium-based sulfonium-modified sand oxide surfactant. Further, the polyalkyl-modified decane-based surfactant is preferably a modified polyalkyl (4) 1335491 decane. The modified polyalkyl siloxane is, for example, a part of polydimethyl methoxy alkane and an active hydrogen of a methyl hydrogen polyoxy siloxane having a chain substituted by hydrogen, and [A-〇-(R-0-) is added. n-X'] (A is an allyl group in which the allyl group 'X' is a terminal substituent, R is a linear or branched chain of 1 to 30 carbon atoms, and η is an integer of 1 to 20) A compound obtained by modifying a polyether. The terminal substituent X' is preferably ?, and the acetate is introduced with an alkyl group such as a monovalent group (-〇C-CH3) and/or a butyl group. The modified siloxane-based surfactant is generally used in the form of a φ solution dissolved in a suitable solvent. The modified siloxane-based surfactants may be used singly or in combination of two or more. • The content of the modified oxoxane surfactant in the photoresist composition is preferably in the range of 0.01 to 1 mass% of the solid content of the surfactant in addition to the surfactant. More preferably, it is 0.05 to 0.50 mass%/〇» [Component other than surfactant (photoresist component)] Φ The composition of the photoresist other than the surfactant in the photoresist composition of the present invention is not particularly limited, and the known light is applied. The composition of the composition of the barrier composition. The photoresist composition of the present invention may be a positive or negative type, for example, a chemically strengthened photoresist composition which may be a positive or negative type, or a positively resistive composition of an azoquinone-novolak resin, or A polymeric negative photoresist composition. Among them, a chemically strengthened photoresist composition of positive or negative type is preferred. When it is a chemically amplified photoresist composition, the base resin may be an alkali-soluble resin or an alkali-soluble resin, the former being a negative-type photoresist composition and the latter being a positive-type photoresist composition. -8- 1335491

V \ ' ' (5) In the case of a negative type, the photoresist composition is simultaneously added with an alkali-soluble resin, an acid generator (photoacid generator), and a crosslinking agent. Therefore, when the photoresist pattern is formed, acid is generated by the acid generator under exposure, and the acid can cause cross-linking between the alkali-soluble resin and the crosslinking agent to change to alkali-insoluble. In the case of a positive type, the base resin is a so-called alkali-insoluble matter having an acid-dissociable dissolution inhibiting group, so that an acid generator generates an acid upon exposure, and the acid dissociates the acid-dissociable dissolution inhibiting group to make the basic resin component. Is alkali soluble φ. Therefore, when the photoresist pattern applied to the substrate is selectively exposed when the photoresist pattern is formed, alkali solubility and alkali development of the exposed portion can be increased. The present invention is more preferably a positive type chemically amplified photoresist composition. [First Embodiment] First, a chemically amplified positive resist composition of the first embodiment of the photoresist composition of the present invention will be described. The chemically-enhanced positive-type photoresist composition of the present embodiment contains (A) a compound which generates an acid under the action of a light or a radiation irradiation (B) a resin which increases solubility in a base under the action of an acid, and the above modification A siloxane based surfactant. (A) A compound which generates an acid under irradiation with active light or radiation: (A) A compound which generates an acid under active light or radiation (hereinafter referred to as (A) component) is an acid generator, which can be directly or indirectly produced by light. The acid compound is not particularly limited. Specifically, for example, 2,4-bis(trichloromethyl)-6-piperidin-1,3,5-triazine '-9- '(6) 1335491, 2.4-bis(trichloromethyl)-6- [2-(2-furyl)vinyl]-5-triazine, 2,4-bis(trichloromethyl)-6-[2-(5-methyl-2-furyl)vinyl]- S-triazine, 2,4-bis(trichloromethyl)-6-[2-(5-ethyl.2-furyl)vinyl]-s-triazine, 2.4-bis(trichloromethyl) )-6-[2-(5-propyl-2-furyl)vinyl]-3-triazine, 2,4-bis(trichloromethyl)-6-[2-(3,5-di Methoxyphenylvinyl)-3-triazine, 2,4-bis(trichloromethyl)-6-[2-(3,5-diethoxyphenyl)vinyl]-s- Triazine, 2,4-bis(trichloromethyl)-6-[2-(3,5-dipropyloxyphenyl)vinyl φ ]-5-triazine, 2,4-bis(trichloro) Methyl)_6-[2-(3-methoxy-5-ethoxyphenyl)vinyl]-s-triazine, 2,4-bis(trichloromethyl)-6-[2-( 3-methoxy-5-propoxyphenyl)vinyl]-s-triazine, 2,4-bis(trichloromethyl)-6-[2-(3,4--methylidene) Oxyphenyl)vinyl]-s-triazine, 2,4-bis(trichloromethyl)-6- _ (3,4-extended methyldioxyphenyl)-s-triazine, 2,4 ·Bis-trichloromethyl-6-(3-bromo- 4- Oxy)phenyl-s-triazine, 2,4-bis-trichloromethyl-6-(2-bromo-4-methoxy)phenyl-s-triazine, 2,4-di·three Chloromethyl-6-(2-bromo-4-methoxy)styrylphenyl-s-triazine, 2,4-bis-trichloromethyl-6-(3-bromo-4-methoxy Benzene • vinyl phenyl-s-triazine, 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-1.3.5-triazine, 2-(4- Methoxynaphthyl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-[2-(2-indolyl)vinyl]-4,6-bis ( Trichloromethyl)-1,3,5-triazine, 2-[2-(5-methyl-2-furyl)vinyl b 4,6-bis(trichloromethyl)-1,3, 5-triazine, 2-[2-(3,5-dimethoxyphenyl)vinyl]-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-[ 2-(3,4-Dimethoxyphenyl)vinyl]-4,6-bis(trichloromethyl)-],3,5-triazine, 2-(3,4-methylidene Methoxyphenyl)vinyl]-4,6.bis(trichloromethyl)-1,3,5-triazine, tris(1,3-dibromopropyl)- 1.3.5-triazine, three (2,3-dibromopropyl)-1,3,5-triazine, etc. containing halogen triazine-10- 1335491 * λ \ ' (7) compound and tris(2,3·dibromopropyl)isocyanate The following general formula (1) a halogen-containing triazine compound as shown;

(wherein R5 to R7 are each the same or a different halogenated alkyl group). • α-(ρ-toluenesulfonyloxyimido)-phenylacetonitrile, α-(phenylsulfonyloxyimino)-2,4-dichlorophenylacetonitrile, α-(phenylsulfonate) -iminophenylacetonitrile, α-(2-chlorophenylsulfonyloxyimino)-4-methoxyphenylacetonitrile, α·(ethylsulfonyloxy) Imino)-1-cyclopentenylacetonitrile, the following general formula (II); [Chemical 2]

Rhir CN N - 0 - S 〇 2 R9) n (Π) (wherein R 8 is a monovalent to trivalent organic group ' R 9 is a substituted, unsubstituted saturated hydrocarbon group, an unsaturated hydrocarbon group or an aromatic compound group, η is Natural number from 1 to 3. -11 - C s ) 1335491 « y \ ' ' (8) where the aromatic compound group refers to a group of a compound having physical and chemical properties peculiar to an aromatic compound, such as phenyl or naphthalene. a heterocyclic group such as a aryl group or a heterocyclic group such as a furyl group or a thiol group, and a ring may have one or more substituents, for example, a halogen atom, an alkyl group (for example, an alkyl group having 1 to 5 carbon atoms), or an alkane. An oxy group (for example, an alkoxy group having 1 to 5 carbon atoms), a nitro group or the like. R9 is particularly preferably an alkyl group having 1 to 4 carbon atoms, such as methyl 'ethyl, propyl or butyl R8. The monovalent to trivalent organic group is preferably an aromatic compound group, for example, a carbon number of 6 to 15. The aromatic compound is particularly preferably a compound in which R8 is an aromatic compound group and R9 is a fluorinated or unfluorinated lower alkyl group, for example, an alkyl group having 1 to 5 carbon atoms. Further, when η = 1, the acid generator represented by the above general formula (II) is such that R8 is any of a phenyl group, a methylphenyl group, a methoxyphenyl group, and R9 is a methyl compound, specifically, for example, α. -(methylsulfonyloxyimino)-1-phenylacetonitrile, α-(methylsulfonyloxyimino)-l-(p-methylphenyl)acetonitrile, α-(methyl Sulfomethoxyimino)-1-(indolylmethoxyphenyl)acetonitrile. When η = 2, the specific acid generator represented by the above general formula (Π) is, for example, an acid generator represented by the following chemical formula);

C = N-〇-S-CH3 I 〇2 CN

〇2H5-S-〇—N = c 〇9 I 2 CN

C—N—0—S—CjHs I 〇2 CM -12- 1335491 (9)

C4H9—S—0—N — C 〇z CN

C ~ N **〇—S— 〇4Hg I 〇2 CN

F3C-S-〇- N ~ C—ij^spC = N -O-S- CF 〇z

CN

CN 〇2

H3c-s-o-n=c „ 3 〇2 I ! 2 CN CN —\ C = N —0~S— CH3 °2 〇2H5-S-0 — N 〇2

Bis(p-toluenesulfonyl)diazomethane, bis(1,1-dimethylethylsulfonyl)diazomethane, bis(cyclohexylsulfonyl)diazomethane, bis(2,4· Dimethylsulfonium diazomethane such as dimethylphenylsulfonyl)diazomethane; 2-nitrobenzyl p-toluenesulfonate, 2,6-dinitrobenzyl p-toluenesulfonate, Nitrobenzyl derivatives such as nitrobenzyl p-toluenesulfonate, dinitrobenzyl p-toluenesulfonate, nitrobenzyl sulfonate, nitrobenzyl carbonate, dinitrobenzyl carbonate ; pyrogallol trimellitate, pyrogallol tri-p-toluenesulfonate 'benzyl p-toluenesulfonate, benzyl sulfonate, N-methylsulfonyloxy amber imine, N- Trichloromethylsulfonyloxyarene, imine, N-phenylsulfonyloxy-13-1335491 1 , (10) maleimide, N-methylsulfonyloxyimine, etc. Sulfonic acid ester, trifluoromethanesulfonate such as N-hydroxyquinone imine or N-hydroxynaphthyl imine: diphenyliodonium hexafluorophosphate, (4. methoxyphenyl) phenyl Iodine trifluoromethanesulfonate, bis(p-tert-butylphenyl) iodine trifluoromethanesulfonate 'three Based on hexafluorophosphate, (4-methoxyphenyl)diphenylphosphonium trifluoromethanesulfonate, (p-tert-butylphenyl)diphenylphosphonium trifluoromethanesulfonate, etc. Key salt; benzene ene p-toluenesulfonate, α-methyl benzoine p-toluene sulfonate, etc. Benzene φ couple p-toluenesulfonate; other diphenyl iodonium salt, triphenyl sulfonium Salt, phenyldiazepine salt, benzyl carbonate, and the like. The above-mentioned medium (Α) component is relatively ambiguous and has at least two general formulas (1): RS〇3〇-N = C (CN) - (1) (wherein R is substituted or unsubstituted, for example, carbon number 1 The compound of the oxime sulfonate group of the alkyl group or the aryl group of 8 is particularly preferably the following general formula (2): r -S 〇2〇_jsj=C (CN) _A-C (CN) = N -〇S 02-尺(2) (in the formula, the divalent of A, such as a substituted or unsubstituted alkyl or aromatic compound having 1 to 8 carbon atoms, and R is substituted or unsubstituted, for example, carbon number 1 to 8 alkyl or aryl) compounds. The aromatic compound group is a group having a compound of a specific physical or chemical substance of an aromatic compound, for example, an aromatic hydrocarbon group such as a phenyl group or a naphthyl group, or a heterocyclic group such as a furyl group or a thiol group. The ring can have 1 -14 - 1335491 1

I

V, '(11) or more appropriate substituents such as a halogen atom, an alkyl group (e.g., an alkyl group having a carbon number of 5 to 5), an alkoxy group (e.g., an alkoxy group having a carbon number of 5 to 5), a nitro group, etc. . Further, in the above general formula, A is a phenyl group, and R is preferably a lower alkyl group having 1 to 4 carbon atoms. In the present embodiment, the component (A) may be used singly or in combination of two or more. Further, the amount of the component (A) added is (B) component 丨〇〇 by mass of 〇. to 20 φ parts by mass, preferably 0.2 to 10 parts by mass. When the amount of addition is 0.1 part by mass or more, sufficient sensitivity can be obtained, and when the amount is 20 parts by mass or less, the solubility in a solvent is good, and a uniform solution can be obtained, so that the storage stability is improved. _ (B) A resin which increases the solubility to alkali under the action of an acid: (B) A resin which can increase the solubility to alkali under the action of an acid (hereinafter referred to as (B) component) may be a chemically enhanced positive light The resin used for the resist composition is not particularly limited. φ Among them, the use of excellent development, resolution and resistance to electric liquid, and good stability of the photoresist pattern and the shape of the product formed by electroplating, and is suitable for the manufacture of connecting terminals, etc., including the following general The resin of the constituent unit represented by the formula (ΙΠ) (hereinafter referred to as (bl) component) and the group of the resin having the constituent unit represented by the following general formula (VI) (hereinafter referred to as (b2) component) are selected. One type or two or more types are preferred. The "constituting unit" means a monomer unit constituting a polymer. (bl) Ingredients: The constituent units shown by the following general formula (ΠΙ). -15- 1335491 \ > % ' (12) 【化4】

(wherein R1 is a hydrogen atom or a methyl group, and R2 is an acid labile group). In the above general formula (ΠΙ), R1 is a hydrogen atom or a methyl group. R2 is an acid labile group. Further, various acid unstabilizing groups may be selected, and particularly preferably a linear group having a carbon number of 1 to 6 represented by the following formula (IV) or (V), a branched or cyclic alkyl group, or a tetrahydropyran. Base, tetrahydrofuranyl or trialkylsulfanyl. [5] • R1. I |2 -C-0-Rlz (iv) R11

[化6J Ο

II -<GH2)aG—0-R13 (v) (wherein R1() and R11 are each independently a hydrogen atom or a straight or branched alkyl group having 1 to 6 carbon atoms, and R12 is a carbon number of 1 Straight chain, branched or 1035491 * t \ \ ' (13) cyclic alkyl groups. R13 is a linear, branched or cyclic group with a carbon number of 1 to 6, a is 〇 Or 1). The linear or branched alkyl group is, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, an η-butyl group, an iso-butyl group or a tert-butyl group, or a cyclic alkyl group such as a cyclohexyl group. • Specific examples of the acid labile group represented by the above formula (IV), for example, methoxyethyl, ethoxyethyl, η-propoxyethyl, iso-propoxyethyl, η-butoxy φ group Ethyl, iso-butoxyethyl, tert-butoxyethyl, cyclohexyloxyethyl, methoxypropyl, ethoxypropyl, 1-methoxy-1-methyl-B The acid, the restless group of the above formula (V), such as a group, a 1-t-ethoxy-1-methyl-ethyl group, etc., such as tert-butoxycarbonyl, tert-butoxycarbonylmethyl and the like. Further, each of the above alkyl groups such as a trialkyl fluorenyl group such as a trimethyl decyl group 'tri-tert-butyl dimethyl decyl group is a carbon number of 1 to 6. The component (bl) may contain one of the constituent units represented by the above formula (III) or two or more constituent units having different structures. ® For the purpose of moderate control (bl), the physical and chemical properties of the component may contain constituent units derived from other polymeric compounds. The "polymerizable compound j" refers to a polymerizable compound other than the constituent unit represented by the above general formula (III). The polymerizable compound is a known radical polymerizable compound or an anionic polymerizable compound. For example, acrylic acid, a monocarboxylic acid such as methacrylic acid or crotonic acid, a dicarboxylic acid such as maleic acid, fumaric acid or itaconic acid, 2-methylpropenyloxyethyl succinic acid or 2-methylpropenyloxyethyl Maleic acid, 2-methylpropenyloxy<S) -17- 1335491 t * \

a radically polymerizable compound such as a methacrylic acid derivative having a carboxyl group or an ester bond, such as ethyl phthalic acid, 2-methylpropenyloxyethyl hexahydrophthalic acid, or the like: methyl (methyl) (meth)acrylic acid alkyl esters such as acrylate, ethyl (meth) acrylate, butyl (meth) acrylate; 2 hydroxyethyl (meth) acrylate, 2-hydroxy propyl ( (meth)acrylic acid hydroxy group such as methyl acrylate. Alkyl esters: aryl (meth) acrylates such as phenyl (meth) acrylate and benzyl (meth) acrylate; Malay Dicarboxylic acid diesters such as diethyl diester, dibutyl fumarate φ; styrene, α-methylstyrene, chlorostyrene, chloromethylstyrene, vinyltoluene, hydroxystyrene, α a vinyl-containing aromatic compound such as methyl hydroxystyrene or α-ethyl hydroxy styrene; a vinyl-containing aliphatic compound such as vinyl acetate: conjugated with butadiene, isopentadiene or the like Diolefins; nitrile-containing polymerizable compounds such as acrylonitrile and methacrylonitrile; vinyl chloride and vinylidene chloride The chlorine-containing polymerizable compound; acrylamide, methyl acrylamide, etc. means containing one of acrylates and methacrylates of Amides # bond polymerizable compound wherein the (meth) acrylate, or both. (Methyl)-propyl citrate refers to one or both of methyl propyl sulphuric acid vinegar and acrylic vinegar. In the total constituent unit constituting the component (bl), the ratio of the constituent unit represented by the above formula (in) is preferably from 10 to 90 mol%, more preferably from 20 to 80 mol%/〇, most preferably 3 0 to 70 0% by mole. When the lower limit is 値 or more, it can be used as a resistive composition, and when it is equal to or greater than the upper limit, it can be balanced with other constituent units. The (bl) component can be polymerized and derivatized by a known radical polymerization method using, for example, azobisisobutyronitrile (Aibn)-free -18-1335491%\' (15)-based polymerization initiator. Get it for you. The mass average molecular weight (Mw) of the (bl) component (the same as the polystyrene conversion standard determined by gel permeation chromatography, the same applies hereinafter) is not particularly limited, and is preferably 1,000 to 20,000, more preferably 1, 〇〇〇 To 1 〇, 〇〇〇, the best is 】, 〇〇〇 to 5,000. When it is less than the upper limit of the range, it can be used as a photoresist for better solubility in a photoresist solvent and larger than the lower limit of the range, thereby obtaining a better dry etching resistance and a cross-sectional shape of the resist pattern. . (b2) Ingredients: (b2) The composition is a resin having the following constituent units of the general formula (VI). I 7]

Ch2-c- c=o I ο (VI)

Ox

(wherein R3 is a hydrogen atom or a methyl group, R4 is an alkyl group having 1 to 4 carbon atoms, and X is a hydrocarbon ring having 5 to 20 carbon atoms bonded to each of the carbon atoms bonded thereto). In the above general formula (VI), R3 is a hydrogen atom or a methyl group. The lower alkyl group represented by R4 may be linear or branched, and is, for example, methyl, ethyl 'η-propyl, isopropyl, n-butyl, isobutyl, sec-butyl-19- (16) 1335491 \ 'base, tert-butyl, various pentyl groups, etc., in which high resolution can obtain good resolution, depth of focus and other viewpoints, and carbon number 2 to 4 to lower grades are preferred. Further, X is a monocyclic or polycyclic hydrocarbon ring having 5 to 20 carbon atoms bonded to each of the carbon atoms bonded thereto. A monocyclic hydrocarbon ring such as cyclopentane, cyclohexane, cycloheptane, cyclooctane or the like 〇 a polycyclic hydrocarbon ring such as a 2-ring hydrocarbon ring, a 3-ring hydrocarbon ring, a 4-ring hydrocarbon ring or the like. Specific examples thereof include a polycyclic hydrocarbon ring such as adamantane, nordane, isobornane, tricyclodecane or tetracyclodecane. When X is a hydrocarbon ring having 5 to 20 carbon atoms formed by each of the carbon atoms bonded thereto, a cyclohexane ring and an adamantane ring are particularly preferable. The component (b2) may be one of the constituent units represented by the above general formula (VI) or two or more constituent units having different structures. The component (b2) is preferably a constituent unit derived from a polymerizable compound having an ether bond. When the constituent unit is contained, good adhesion to the substrate and plating resistance can be obtained. A polymerizable compound having an ether bond such as 2-methoxyethyl (meth) acrylate or 2-ethoxyethyl (meth) acrylate 'methoxy triethylene glycol (meth) acrylate , 3-methoxybutyl (meth) acrylate, ethyl carbitol (meth) acrylate, phenoxy polyethylene glycol (meth) acrylate, methoxy polypropylene glycol (methyl) A radical polymerizable compound such as an (meth) acrylate derivative having an ether bond or an ester bond such as an acrylate or tetrahydroindenyl (meth) acrylate, preferably 2-methoxyethyl (A) Acrylate, 2·B-20-(17) 1335491 ethoxyethyl (meth) acrylate, methoxy triethylene glycol (meth) acrylate. These compounds may be used alone or in combination of two or more. In order to moderately control the physical and chemical properties of the (b2) component, it may contain constituent units derived from other polymerizable compounds. The "polymerizable compound j" is a polymerizable compound other than the constituent unit derived from the structural unit represented by the above general formula (VI) and the polymerizable compound having an ether bond. For example, a specific example of the other polymerizable compound of the above (bl) component may be a known radical polymerizable compound or an anion polymerizable compound. - In the entire constituent unit of the component (b2), the above general formula (VI) The ratio of the constituent units is preferably from 10 to 90 mol%, more preferably from 20 to 80 mol%, and most preferably from 30 to 70 mol%. When the lower limit is 値 or more, it is used as a resist composition. When the type 'the upper limit is less than 値, it can be balanced with other constituent units. Φ (b2) When the component contains a constituent unit derived from an ether bond-polymerizable compound, the content of the component is preferably the total constituent unit of the component (b2). 1〇至9〇莫耳%' More preferably 20 to 80 moles. /, preferably 3〇 to 70mol%. The lower limit 値 above gives a good effect of containing the constituent unit, and the upper limit値 can be taken with other constituent units when The component (b2) can be obtained by polymerizing and deriving a monomer of each constituent unit by a known radical polymerization method using, for example, an azobisisobutyronitrile (AIBN)-like radical polymerization initiator. The mass average molecular weight (Mw) is not particularly limited, and is preferably -1 to 18,500,000, more preferably 50,000 to 450,000, and most preferably 1,500 to 400,000. When the photoresist is sufficiently soluble in a photoresist solvent and is larger than the lower limit of the range, a good dry etching resistance and a cross-sectional shape of the photoresist pattern can be obtained. In the present embodiment, the component (B) contains (b) Ingredient and (b2), if one or more of the components are selected, the effect of the component is used, and the content of the component (B) is preferably 20% by mass or more, more preferably 30% by mass or more. The optimum φ is preferably 100% by mass. In addition, in the component (B), the resin content selected in the component (b2) is 20% by mass or more, in terms of contrast, electric shovel resistance, cracking property, and peeling property. More preferably, it is 50% by mass or more, and most preferably 100% by mass. Alkali-soluble resin: In order to appropriately control the physical and chemical properties of the positive-type resist composition of the present embodiment, it is preferable to further contain (C) an alkali-soluble resin (hereinafter referred to as (C) component). The component C) may be suitably selected from known chemically-strength resists as an alkali-soluble resin, preferably containing (cl) novolak resin, (c2) having a hydroxystyrene constituent unit, and styrene. One or more resins selected from the group consisting of copolymers, (c3) acrylic resin and (c4) vinyl ester resin, more preferably containing (cl) novolak resin and/or (c2) having hydroxystyrene constituent units and benzene A copolymer of ethylene in units. Because it is easy to control the coating property and the developing speed. -22- (19) (19)1335491 y (cl) Novolac resin = (c 1 ) component of the awake varnish resin, for example, an aromatic compound having a phenolic hydroxyl group (hereinafter referred to as "phenol" under acid catalyst Class") is obtained by condensation with the wake-up addition. The phenols used at this time are, for example, phenol, 0. cresol, formic acid, p-cresol, hydrazine-ethylphenol, m-ethylphenol, P-ethylphenol' 〇 butyl benzoquinone, m- Butylphthalide, p-butylphenol, 2,3-xylene, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 3,4-xylenol , 3,5-xylenol, 2,3,5-trimethylphenol, 3,4,5-trimethylphenol, p-phenylphenol, resorcinol, hydroquinone, hydroquinone-methyl ether, Pyrogallol's phloroglucinol, hydroxydiphenyl ester, bisphenol A, gallic acid, gluten-free acid ester 'α-naphthol, point-naphthol, and the like. And aldehydes such as formaldehyde 'furfural, benzaldehyde, nitrobenzaldehyde, acetonide, etc. The catalyst used in the addition condensation reaction is not particularly limited, and examples thereof include acid catalysts such as hydrochloric acid, nitric acid, sulfuric acid, formic acid, and oxalic acid 'acetic acid. In particular, the phenol type only uses a novolac resin of m-cresol, and a particularly excellent development profile is preferred. The mass average molecular weight of the (cl) component is preferably from 3,000 to 50,000. (c2) a copolymer having a hydroxystyrene constituent unit and a styrene constituent unit: The component (c2) is a copolymer having at least a hydroxystyrene constituent unit and a styrene constituent unit. That is, a copolymer formed of a hydroxystyrene constituent unit and a styrene constituent unit, or a copolymer composed of a hydroxystyrene constituent unit, a phenylethylene-23-'(20) 1335491 olefin constituent unit, and other constituent units. The hydroxystyrene constituent unit is, for example, hydroxystyrene such as p-hydroxystyrene, α-methylhydroxystyrene, α-ethylhydroxystyrene or the like α-alkylhydroxystyrene (the number of carbon atoms of the alkyl group is higher Preferably, the hydroxystyrene unit is 1 to 5). • Styrene constituent units such as styrene, chlorostyrene, chloromethylphenylene, vinyl, toluene, α-methylstyrene, etc. The mass average molecular weight of the φ (c2) component is preferably from 1, 〇〇〇 to 30,000. (c3) Acrylic resin: • The (c 3.) component acrylic resin may be an alkali-soluble acrylic resin and is not particularly limited, and is particularly preferably a constituent unit derived from a polymerizable compound having an ether bond, and a carboxyl group. A constituent unit derived from a polymerizable compound. A polymerizable compound having an ether bond such as 2-methoxyethylene (meth) acrylate, methoxy triethylene glycol (meth) acrylate, 3-methoxybutyl (meth) acrylate Ethyl carbitol (meth) acrylate, phenoxy polyethylene glycol (meth) acrylate, methoxy polypropylene glycol (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, etc. The (meth)acrylic acid derivative having an ether bond and an ester bond is preferably 2-methoxyethyl acrylate or methoxy triethylene glycol acrylate. These compounds may be used alone or in combination of two or more. The (meth) acrylate means one or both of methacrylate and acrylate, and the (meth) acrylate means one or both of methacrylic acid and acrylic acid. These compounds may be used singly or in combination of two or more kinds. -24- (21) 1335491 A polymerizable compound having a hydroxyl group such as a monocarboxylic acid such as acrylic acid, methacrylic acid or crotonic acid, a dicarboxylic acid such as maleic acid, fumaric acid or itaconic acid or 2-methylpropene oxime Oxyethyl succinic acid, 2 methacryl oxiranyl ethyl maleic acid, 2-methyl propylene methoxyethyl phthalic acid, 2- methacryloxyethyl hexahydro phthalic acid, etc. The compound of a carboxyl group and an ester bond is preferably acrylic acid and methyl methacrylate. These compounds may be used alone or in combination of two or more. (c3) The mass average molecular weight of the component is, for example, 10,000 to 80,000, preferably • 30,000 to 500,000 ° (c4) vinyl ester resin: - the vinyl ester resin of the component (c4) is poly(vinyl lower alkyl ether). It can be formed by a (co)polymer obtained by polymerizing a single or a mixture of two or more kinds of vinyl lower alkyl ethers represented by VIU. [Chem. 8] Lu HC=CH2 (m) ο R14 (General In the formula (VII), R14 is a linear or branched alkyl group having a carbon number of 5. In the general formula (VII), a linear or branched alkyl group having 1 to 5 carbon atoms, for example, Base, ethyl, propyl, i-propyl, n-butyl, i-butyl, n-pentyl, i-pentyl, etc. Preferred among the alkyl groups are methyl, ethyl, and i. Butyl, special

-25- 1335491 » l

V (22) is preferably methyl. Poly(vinyl lower alkyl ether) is particularly preferably poly(vinyl methyl ether). The mass average molecular weight of the component (c4) is preferably from 10,000 to 200,000, more preferably from 50,000 to 100,000. The amount of the component (C) added is from 0 to .300 parts by mass, preferably from 〇 to 200 parts by mass, per 100 parts by mass of the component (B). When the amount of addition is 300 parts by mass or less, the contrast φ drop and film reduction of the exposed portion and the unexposed portion for pattern formation can be suppressed. (D) Acid Diffusion Inhibitor: The positive-type photoresist composition is used to enhance the post-resistance of the latent image formed by the pattern-wise exposure of the resist layer. It is preferable to further contain (D) an acid diffusion inhibitor (hereinafter referred to as (D) component). The component (D) can be suitably selected from known chemically enhanced photoresists for use as an acid diffusion inhibitor. Particularly preferably, it contains (dl) a nitrogen-containing compound, and if necessary, may contain (d2) an organic carboxylic acid, a phosphorus oxyacid or a derivative thereof (dl) a nitrogen-containing compound: (dl) a component of a nitrogen-containing compound such as Methylamine, diethylamine, triethylamine, di-η-propylamine, tri-n-propylamine, tribenzylamine, diethanolamine, triethanolamine, η-hexylamine, η-heptyl Amine, η-octylamine, η-decylamine 'ethylidene diamine, hydrazine, hydrazine, hydrazine', hydrazine, -tetramethylethylidene diamine, tetraexene -26- (23) (23) 1335491 methyldiamine, hexamethylenediamine, 4,4'-diaminodiphenylcarbamate, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl Methyl ketone, 44, diaminodiphenylamine, formamide, N-methylformamide 'Ν, Ν·dimethylformamide, acetamide, Ν-methyl acetamide, hydrazine , Ν dimethyl acetamide 'propanolamine, benzoguanamine, pyrrolidone, hydrazine-methylpyrrolidone, methyl urea, methyl urea, 1,3-dimethylurea' 1,1,3,3 -tetramethylurea, 1,3-diphenylurea, imidazole, benzimidazole, 4-methylimidazole, 8-oxoquinoline, acridine, hip-hop, guanidine, 2,4,6-three 2-pyridyl)-s-triazine, morpholine, 4-methylmorpholine, piperazine, 1,4-dimethylpiperazine, 1,4-diazabicyclo[2.2.2]octane Wait. Among them, an alkanolamine of triethanolamine is particularly preferred. They may be used singly or in combination of two or more. When the component (B) is 100% by mass, the amount of the component (d) is generally 5% to 5% by mass, particularly preferably 0 to 3% by mass. (02) Organic carboxylic acid, phosphorus oxyacid or derivative thereof: Organic carboxylic acid such as malonic acid, citric acid, malic acid, succinic acid, benzoic acid, salicylic acid, etc., particularly preferably salicylic acid. Phosphorus oxyacid or its derivatives such as phosphoric acid, di-n-butyl phosphate, diphenyl phosphate, and the like, and ester-like derivatives thereof, phosphonic acid, dimethyl phosphonate, phosphonic acid- Phosphonic acid such as di-n-butyl ester, phenylphosphonic acid, diphenyl phosphonate, dibenzyl phosphonate, and ester derivatives thereof, phosphinic acid such as phosphinic acid and phenyl hypophosphorous acid, and An ester-like derivative, particularly preferably a phosphonic acid. They may be used singly or in combination of two or more. When the (Β) component is 100% by mass, the amount of the component (d2) is generally -27-(24) (24) 1335491 〇 to 5 mass%, particularly preferably 3 to 3 mass%. It is preferable to use the same amount of the (d2) component to the (dl) component. This is because the (d2) component can form a salt with the (dl) component and is stabilized. Under the nature of non-destructive nature, the positive photoresist composition may contain additive additives such as additional resins, plasticizers, adhesion aids, stabilizers, colorants, and surfaces for improving the properties of the photoresist film. Conventional materials such as active agents. Further, an organic solvent for adjusting the viscosity can be appropriately added to the positive resist composition. Specific examples of the organic solvent include ketones such as acetone, methyl ethyl ketone, cyclohexanone, methyl isoamyl ketone, and 2-heptanone; ethylene glycol, ethylene glycol monoacetate, and diethylene glycol. Diethylene glycol monoacetate, propylene glycol, propylene glycol monoacetic acid vinegar, dipropylene glycol or dipropylene glycol monoacetate methyl ether, monoethyl ether, monopropyl ether, monobutyl ether or monophenyl ether Polyols and their derivatives; dioxane-like cyclic ethers; methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, ethyl pyruvate, A An ester such as methyl oxypropionate or ethyl ethoxypropionate. Among them, propylene glycol monomethyl ether acetate (PGMEA) is preferred. Further, in order to obtain good coatability upon spraying, some or all of the organic solvent used is preferably a highly volatile solvent. Specifically, it is preferably an organic solvent having a boiling point of 130 ° C or lower, and specific examples thereof include acetone, methyl isobutyl ketone (MIBK), propylene glycol monomethyl ether (PGME), and the like. The amount of the highly volatile organic solvent added is preferably from 10 to 90% by mass, more preferably from 10 to 80% by mass, most preferably from 20 to 60% by mass, based on the total of the organic solvent contained in the positive resist composition. . -28- (25) 1335491

In the present embodiment, the organic solvent may be used singly or in combination of two or more kinds. The amount of the organic solvent to be used is not particularly limited, and is preferably such that the solid content of the photoresist composition is from 5 to 50% by mass, more preferably from 5 to 40% by mass, most preferably from 5 to 30% by mass. The solid content concentration is the lower limit. When the temperature is above 値, good coating properties are obtained during spraying, and when the upper limit is less than 値, the coating property is good. • When the positive resist composition of the present embodiment is adjusted, for example, each component can be mixed by a general method and stirred and prepared. If necessary, it can be dispersed and mixed using a dispersing machine such as a decomposing rod, a homogenizer, or a 3-roll mill. Further, it can be filtered by using a sieve or a membrane filter. [Second Embodiment] Next, a chemically-reinforced negative-type photoresist composition according to a second embodiment of the photoresist composition of the present invention will be described. ® The chemically amplified negative photoresist composition of the present embodiment contains (A) a compound which generates an acid under active light or radiation, (acid generator), (B') novolak resin, (C') plasticizer And (E) a crosslinking agent and the above modified oxoxane surfactant. (A) Acid generator The component (A) of the present embodiment may be a compound which generates an acid by direct or indirect light irradiation, and is not particularly limited, and the positive chemically amplified photoresist composition of the first embodiment described above may be used. a compound for the component (A). -29- (26) 1335491 In particular, the triazine compound has a high acid generator performance for light and preferably has good solubility when using a solvent. Among them, the use of a bromine-containing triazine compound, in particular 2,4·bis-trichloromethyl-6-(3-bromo-4-methoxyphenyl-s-triazine, 2,4-bis- Trichloromethyl-6-(3-bromo-4-methoxy)styryl-s-triazine or tris(2,3-bromodibromopropyl)isocyanate is preferred. - In this embodiment ( A) The components may be used singly or in combination of two or more kinds. φ In the present embodiment, the amount of the component (A) added is 100 parts by mass of the total of the components (A), (B'), (C'), and (E). It is preferably from 0.01 to 10 parts by mass, more preferably from 0.05 to 2 parts by mass, particularly preferably from 0.1 to 1 part by mass. (A) Ingredient - when it is more than 1 part by mass, it can be sufficiently crosslinked and hardened by heat or light. _, and the resulting photoresist film is improved in electroplating resistance, chemical resistance, and adhesion. When the amount is less than 1 part by mass, development defects can be suppressed during development. (B') Novolak resin # In this embodiment ( B') The novolak resin is preferably alkali-soluble. The (B,) novolak resin can be obtained by, for example, an aromatic compound having a phenolic hydroxyl group (hereinafter referred to as "phenol") and an aldehyde under an acid catalyst. Shrink The benzoic acids used at this time are, for example, benzoquinone, hydrazine-methylhydrazine 'm-formamidine, p-cresol, hydrazine-ethylphenol, m-ethylphenol, p-ethylphenol, hydrazine- Butylphenol, m-butylphenol 'p-butylphenol, 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 3, 4-xylenol, 3,5·xylenol, 2,3,5-trimethylphenol, 3,4,5-trimethylphenol, 3,4,5- 30- (27) 1335491 Methylphenol, P-phenylphenol, resorcinol, hydroquinone, hydroquinone monomethyl ether, pyrogallol, phloroglucinol, hydroxydiphenyl ester, bisphenol A, gallic acid, no food Acidic vinegar, α · naphthyl, jS - naphthalene, etc. Also aldehydes such as formaldehyde, paraformaldehyde 'furfural, benzaldehyde, nitrobenzaldehyde, acetaldehyde, etc. Addition of the catalyst used in the condensation reaction There is no particular limitation, such as an acid catalyst such as hydrochloric acid, nitric acid, sulfuric acid, formic acid, oxalic acid, and acetic acid. The mass average molecular weight (Mw) of the novolac resin is not particularly limited, and is preferably 3,000 to 50,000. ') The addition amount of novolac resin to (A), (B'), (C') and The sum of the components (E) is preferably from 5 to 95 parts by mass, more preferably from 6 5 to 80 parts by mass, and the (B') component is available in the range, and the inhibitor is developed. (C') plasticizer # (C') a plasticizer such as a polymer having an ethylenic double bond, and preferably an acrylic polymer or a vinyl polymer. The (C') component will be described by using an acrylic-based polymer or a vinyl-based polymer as an example. Among the components (C'), especially when the acrylic-based polymer is alkali-soluble, it is preferable to contain an ether. A constituent unit derived from a polymerizable compound of a bond, and a constituent unit derived from a polymerizable compound having a carboxyl group. Specific examples of the polymerizable compound having an ether bond and the polymerizable compound having a carboxyl group are, for example, the monomeric example of the (c3) acrylic resin of the first embodiment described above. <S) -31 - (28) (28) 1335491 Acrylic group In the polymer, the constituent unit ratio derived from the polymerizable compound having an ether bond is preferably from 30 to 90 mol%, more preferably from 40 to 80 mol%. When the ratio is 90 mol% or less, the compatibility of the (B,) novolak resin solution can be improved, and the Benat unit can be prevented from being generated during the prebaking (the surface of the coating film is uneven due to the inclination of gravity or surface tension, etc.) A five-to-seven-dimensional network pattern), resulting in a uniform photoresist film. When it is more than 30% by mole, it can suppress cracking during plating. In the acrylic-based polymer, the constituent unit ratio derived from the carboxyl group-containing polymerizable compound is 2 to 50 mol%, preferably 5 to 40 mol%. When the ratio is 2 mol% or more, the alkali solubility of the acrylic resin can be improved to obtain sufficient developability, and the peeling property can be improved to suppress the photoresist residue on the substrate. When the content is less than 50% by mol, the residual film rate after development can be improved. The mass average molecular weight of the acrylic based polymer is preferably from 10,000 to 800,000, more preferably from 30,000 to 500,000. When the amount is 10,000 or more, the photoresist film can have sufficient strength to suppress the profile expansion and cracking during plating. When it is 800,000 or less, the adhesion and the peelability can be improved. In order to appropriately control the physical and chemical properties of the acrylic-based polymer, a constituent unit derived from another radically polymerizable compound may be additionally contained. The "other radical polymerizable compound" means a radical polymerizable compound other than the above polymerizable compound. Such a radical polymerizable compound such as methyl (meth) acrylate '-32- (29) 1335491

Alkyl (meth) acrylate such as V ethyl (meth) acrylate or butyl (meth) acrylate; 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (methyl) Hydroxyalkyl (meth)acrylates such as acrylates; aryl (meth)acrylates such as phenyl (meth) acrylate 'benzyl (meth) acrylate; diethyl maleate a dicarboxylic acid diester such as an ester or dibutyl fumarate; a vinyl-containing aromatic compound such as styrene or α-methylstyrene; a vinyl-containing aliphatic compound such as vinyl acetate; a conjugated diene such as a diene or an isoprene; a nitrile group-containing polymerizable compound such as acrylonitrile or methacrylonitrile; a chlorine-containing polymerizable compound such as vinyl chloride or vinylidene chloride; A guanamine-containing polymerizable compound such as acrylamide or the like. • The compounds may be used alone or in combination of two or more. Among them, η-butyl acrylate, benzyl methacrylate, methyl methacrylate and the like are particularly preferred. The ratio of the constituent units derived from the other radical polymerizable compound in the acrylic-based polymer is preferably from 5 to 60 mol%, more preferably from 5 to 40 mol%. ® Polymerization solvent used in the synthesis of acrylic-based polymers, such as alcohols such as ethanol 'diethylene glycol; ethylene glycol monomethyl ether, diethylene glycol methyl ether, diethylene glycol ethyl methyl An alkyl ether of a polyhydric alcohol such as an ether; an alkyl ether acetate of a polyhydric alcohol such as ethylene glycol ethyl ether acetate or propylene glycol methyl ether acetate; an aromatic hydrocarbon such as toluene or xylene; acetone; Ketones such as methyl isobutyl ketone; esters such as ethyl acetate and butyl acetate. Among them, particularly preferred are alkyl ethers of polyhydric alcohols and alkyl ether acetates of polyhydric alcohols. The polymerization catalyst used in the synthesis of the acrylic-based polymer may be a general -33-(30)1335491 radical polymerization initiator such as 2,2'-azo dimer; benzoquinone peroxide, bis-1. The butyl peroxide oxime (C') component is preferably an alkali-soluble ethylene. The vinyl-based polymer means a vinyl compound. For example, polyvinyl chloride, polystyrene, polyhydroxy olefin ester, polyvinyl benzoic acid, polyvinyl alcohol, acrylic acid, polyacrylate, polymaleimide acrylonitrile, polyvinyl phenol and copolymers thereof. It is preferred to have a carboxyl group or a phenolic hydroxyl group in the branched or main chain. Particularly preferably, the mass average of the carboxyl group-containing vinyl polymer having a high alkali developability is 200,000, more preferably 50,000 to 100,000 < (C) component (A), (B,), (C' 1 〇〇 parts by mass is 5 to 30 parts by mass, preferably 1) When the (C') component is 5 parts by mass or more, the material floats and cracks, and the plating solution can be raised to be improved when it is less than the plating solution. The strength of the photoresist film; the sharp outline and the resolution are not obtained. (E) The amine compound of the (E) component used in the crosslinking agent, for example, the three resin, the guanamine resin, the glycoluril-formaldehyde resin, the isobutyronitrile An organic peroxide such as an oxynitride or the like; a polymer obtained from a polymer, a polystyrene obtained from a polymer, a polyacetic acid polyacrylic acid, a polymethyl group, a polyacrylamide, and a resin which is a resin. The image is developed as a resin. The amount of F is preferably 1 〇, and the sum of 〇〇〇) and (E) components is 〇 to 20 parts by mass. It can suppress photoresistance during plating. Further, 30 parts by mass of polycyanamide resin, urea succinimide-formaldehyde tree-34-(31) (31)1335491, and ethyl urea-formaldehyde resin, etc., particularly preferably alkoxy groups, are inhibited by swelling or the like. Alkoxymethylated amine-based resin such as methylated melamine resin or alkoxymethylated urea resin, etc. The oxy group, methylated amine-based resin can be, for example, melamine or urea and formalin in a boiling aqueous solution. After the reaction, the obtained condensate is etherified with a lower alcohol such as methanol, ethanol, propanol, butanol or isopropanol, and the reaction liquid is cooled and precipitated. Specific examples of the alkoxymethylated amine-based resin include methoxymethylated melamine resin, ethoxymethylated melamine resin, propoxymethylated melamine resin, butoxymethylated melamine resin, A methoxymethylated urea resin, an ethoxymethylated urea resin, a propoxymethylated urea resin, a butoxymethylated urea resin, or the like. The alkoxymethylated amine-based resin preferably has a mass average molecular weight of from 100 to 500. The alkoxymethylated amine-based resins may be used singly or in combination of two or more kinds. In particular, it is preferred that the alkoxymethylated melamine-based resin has a small amount of change in the size of the photoresist pattern under the irradiation of the radiation, and it is preferable to form a resist pattern. Among them, one or more selected from the group consisting of methoxymethylated melamine resin, ethoxymethylated melamine resin, propoxymethylated melamine resin and butoxymethylated melamine resin are preferred. The total amount of the component (E) to (A), (B')' (C,) and (E) is 100 parts by mass, preferably 1 to 30 parts by mass, preferably 5 to 20 parts by mass. When the component (E) is at least 1 part by mass, the plating resistance, chemical resistance and adhesion of the photoresist film can be improved. When the amount is more than 30 parts by mass, the development of the image -35 - 1335491 \ ι \ (32) is inhibited. Further, an organic solvent for adjusting the viscosity can be appropriately added to the negative resist composition. Specific examples of the organic solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol dimethyl ether, and ethylene glycol. Diethyl ether, ethylene glycol dipropyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, two Ethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monophenyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, ethylene glycol monomethyl Ether acetate, ethylene glycol-ethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monophenyl ether acetate, two Ethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monopropyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol Alcohol monophenyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, 2-methoxybutyl acetate, 3-methyl Oxybutyl acetate, 4-A Oxybutyl acetate, 2-methyl-3-methoxybutyl acetate, 3-methyl-3.methoxybutyl acetate, 3·ethyl-3-methoxy Butyl acetate, 2-ethoxybutyl acetate, 4-ethoxybutyl acetate ' 4 · propoxy butyl acetate, 2-methoxypentyl acetate, 3-methoxypentyl acetate, 4-methoxypentyl acetate, 2-methyl-3-methoxypentyl acetate, 3-methyl-3-methoxypentyl Acetate, 3-methyl-4-methoxypentyl acetate, 4-methyl-4-methoxypentyl acetate, acetone, methyl ethyl ketone, diethyl ketone, A Isobutyl ketone, ethyl isobutyl ketone, tetrahydrofuran, cyclohexanone, methyl propionate, ethyl propionate, propyl propionate, isopropyl propionate-36-(33) 1335491, 2-hydroxyl Methyl propionate, ethyl 2-hydroxypropionate, 2-hydroxy-2-methyl ester, methyl-3-methoxyacrylic acid, ethyl-3-methoxyacrylic acid, ethyl-3-ethoxyl Acrylic acid, ethyl-3-propoxyacrylic acid, propyl-3-methoxyacrylic acid, isopropyl-3-methoxyacrylic acid, ethyl ethoxyacetate, ethyl oxyacetate' 2_hydroxyl group Methyl 3-methylbutyrate, B Methyl ester, ethyl acetate, • propyl acetate, isopropyl acetate, butyl acetate, isoamyl acetate, methyl carbonate, ester, ethyl carbonate, propyl carbonate, butyl carbonate, methyl pyruvate, acetone • Ethyl acetate, propyl pyruvate, butyl pyruvate, methyl acetate, ethyl acetate, benzyl methyl ether, benzyl ethyl ether, dihexyl ether, benzyl acetate, benzoic acid Ester, diethyl oxalate, diethyl maleate, r-butyl 'lactone, benzene, toluene, xylene, cyclohexanone, methanol, ethanol, propanol, . butanol, hexanol, cyclohexanol, Ethylene glycol, diethylene glycol, glycerin, etc. Further, in the first embodiment, it is preferable that some or all of the organic solvent is a highly volatile solvent. Specific examples of the highly volatile solvent and preferred addition amounts are the same as in the first embodiment. In the present embodiment, the organic solvent may be used singly or in combination of two or more kinds. The amount of the organic solvent to be used is not particularly limited, and the solid content concentration of the photoresist composition is preferably in the preferred range of the first embodiment. In addition to the above components, in order to enhance light, if necessary. The pattern shape, the stability over time, and the like are preferably further contained (D) an acid diffusion inhibitor. The (D) component can be used as an acid diffusion in previously chemically enhanced photoresists

-37- (34) (34) 1335491 Inhibitors are suitably selected for use. It is preferable to contain (d1) a nitrogen-containing compound and, if necessary, a (d2) organic carboxylic acid, a phosphorus oxyacid or a derivative thereof (d) nitrogen-containing compound, which is specifically the same as the first embodiment. (dl) ingredients. (d2) Specific examples of the organic carboxylic acid, the phosphorus oxyacid or the derivative thereof may be the same as the component (d2) of the first embodiment. When the (B') component is 00% by mass, the amount of the (dl) component is generally from 〇 to 5% by mass, particularly preferably from 0 to 3% by weight. When the component (B') is 100% by mass, the amount of the component (d2) is usually from 0 to 5% by mass, particularly preferably from 0 to 3% by mass. Further, in the first embodiment, it is preferred to use the same amount of (d2) component and (d1) component. The negative-type photoresist composition of this embodiment may contain a bonding aid for improving the adhesion to the substrate. A suitable auxiliaries which can be used effectively are functional decane coupling agents. The functional decane coupling agent is a decane coupling agent having a reactive substituent such as a carboxyl group, a methacryl group, an isocyanate group or an epoxy group, and specifically, for example, a trimethoxydecyl benzoic acid, r-methyl propylene Oxypropyltrimethoxydecane, vinyltriethoxydecane, vinyltrimethoxydecane, r-glycidoxypropyltrimethoxydecane, θ-(3,4-epoxy ring Hexyl) ethyltrimethoxydecane, and the like. The amount of the (B') novolak resin to be added is preferably 20 parts by mass or less per 1 part by mass. -38- (35) (35)1335491 Further, the negative-type photoresist composition of the present embodiment may be added with acetic acid, propionic acid, η-butyric acid or iso-butyric acid in order to slightly adjust the solubility of the alkali developing solution. Monocarboxylic acid such as η-valeric acid, iso-pentanoic acid, benzoic acid, cinnamic acid; lactic acid, 2-hydroxybutyric acid, 3-hydroxybutyric acid, salicylic acid, hydroxybenzoic acid 'p-hydroxybenzoic acid, 2- Hydroxymonocarboxylic acid such as hydroxycinnamic acid, 3-hydroxycinnamic acid, 4-hydroxycinnamic acid, 5-hydroxyisophthalic acid, or syringic acid; oxalic acid, succinic acid, glutaric acid, adipic acid, maleic acid, Itaconic acid, hexahydrononanoic acid, citric acid, isophthalic acid, terephthalic acid, 1,2-cyclohexanedicarboxylic acid, 1,2,4-cyclohexanetricarboxylic acid, trimellitic acid a polycarboxylic acid such as pyromellitic acid, cyclopentane tetracarboxylic acid, butane tetracarboxylic acid, 1,2,5,8-naphthalenetetracarboxylic acid: itaconic anhydride, succinic anhydride, citraconic anhydride, twelve Carboxy succinic anhydride, barium triphenylcarbamate, maleic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, biscycloheptylene anhydride, 1,2,3,4-butane tetracarboxylic acid' ring Pentane tetracarboxylic dianhydride, phthalic anhydride, homophenyl Anhydride such as an acid anhydride, trimellitic anhydride, benzophenone tetracarboxylic anhydride, ethylene glycol trimellitic anhydride, or glycerol trimellitic anhydride. Further, N-methylformamide, hydrazine, hydrazine-dimethylformamide, N-methylformamide, hydrazine-methylacetamide, hydrazine, hydrazine-dimethylacetamide, hydrazine may be added. -Methyl-brondenanone, dimethyl hydrazine, benzyl ethyl ether, dihexyl ether, acetone acetone, isophorone, hexanoic acid, octanoic acid, 1-octanoic acid, 1-nonanol, benzyl alcohol , high boiling point solvents such as benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, butyrolactone, ethylene carbonate, propylene carbonate, phenyl cellosolve acetate. The amount of the compound for slightly adjusting the solubility of the alkali developing solution can be appropriately adjusted to suit the purpose of mixing the composition uniformly, and there is no particular limitation -39-1335491

The product obtained by V ' (36) may be 60% by mass or less, preferably 40 i or less. Further, if necessary, ruthenium, a colorant, a viscosity adjuster, or the like may be added to the negative resist composition of the present embodiment. Filling materials such as cerium oxide, oxygen, talc, bentonite, chromic acid citrate, glass powder, and the like. • Colorants such as aluminum white, clay, barium carbonate, barium sulfate, etc.: zinc white, lead white, yellow lead, lead dan, ultramarine blue, Prussian blue, oxidized φ zinc chromate, iron oxide red, carbon black and other inorganic Pigments: 艶红红6B, red 6B, permanent red R, benzidine yellow, phthalocyanine blue, phthalocyanine green, etc.; magenta, rhodamine and other basic dyes; direct scarlet, direct orange-dye dye; Luo Lingling, Acid dyes such as Mitanier Yellow. _ Further viscosity modifiers such as bentonite, silicone, aluminum powder, etc. Under the essential characteristics of the additive composition, the obtained composition is preferably 50% or less. The negative-type photoresist composition of the present embodiment is obtained by mixing and stirring in a general manner without adding an entangled material or a pigment #. When the chelating agent or the pigment is added, it is dispersed and mixed by a dispersing machine such as a disintegrating rod, a homogenizer, or a 3-roll mill, and if necessary, it can be filtered using a sieve or a membrane filter. [Third Embodiment] Further, (A) an acid generator, (B") an alkali-soluble resin, and (E) a cross-linking of the modified siloxane-based surfactant as an essential component, and a (B") base The soluble resin is at least one selected from the group consisting of lower alkyl esters of α-(hydroxyalkyl)acrylic acid and α-alkylalkyl)acrylic acid. Aluminized pigments such as titanium, permanent skin and the like are used in the massing agent. Can be combined. The agent and the - (hydroxyl--40-(37) (37) 1335491 negative-type photoresist composition can reduce the formation of a good photoresist pattern by swelling. Among them, the carbon atom of the hydroxyalkyl group The number is preferably from 1 to 5, and the number of carbon atoms of the lower alkyl group is preferably from 1 to 5. The above α-(hydroxyalkyl)acrylic acid is acrylic acid having a hydrogen atom bonded to a carbon atom at the α position of the carboxyl group. And one or both of the α-hydroxyalkylacrylic acids bonded to the hydroxyalkyl group at the carbon atom of the α-position. The (Ε) crosslinking agent used is a glycoluril having a methylol group or an alkoxymethyl group. In the case of the amine-based crosslinking agent, it is preferred to reduce the formation of a good photoresist pattern by swelling. The additive of the crosslinking agent is preferably from 1 to 50 parts by mass per 100 parts by mass of the alkali-soluble resin. The present invention is the same as the second embodiment. The photoresist composition of the present invention is used for forming a photoresist film on a substrate by a spray coating method. The spray coating method can be carried out using any spraying device. The photoresist composition of the present invention is particularly It is suitable for a method of forming a photoresist film on a substrate by spraying on a substrate on which a coated surface is provided. The coated surface refers to the surface on which the photoresist composition is applied, and is generally the entire surface of the substrate. As shown in Fig. 1, the stage portion 1 of the present invention has a slope corresponding to the upper surface 1a and the bottom surface 1c. The shape of the side surface 1 b. The upper surface 1 a, the side surface 1 b and the bottom surface I c are formed by a flat surface. The difference of the stage portion 1 is that the phase portion 1 is perpendicular to the direction of the upper la, and the upper surface is la to the bottom surface lc. In the present invention, the step Η of the step portion 1 of the substrate-coated surface is preferably 10 to Ι, ΟΟΟμπ!. When the step Η is ΙΟμπι -41 - (38) (38) 1335491 or more, the photoresist of the present invention can be sufficiently utilized. The effect of the composition. The angle 0 formed by the upper surface 1 a of the phase portion 1 and the side surface 1 b is 90 ° or more. When Θ is approximately 90°, the photoresist is caused by the angle ' of the phase portion I in the previous photoresist composition' The problem of partial thinning of the film thickness of the film is conspicuous, and the effect of using the photoresist composition of the present invention is preferably 90. The above is less than 180°, more preferably 100° or more. <Laminate> The laminate of the present invention is as shown in Fig. 1, and the coated surface is provided with the above A laminate of the photoresist film 2 is formed of the photoresist composition of the present invention on the substrate of the stage portion 1 having the difference in the range. In the laminate of the present invention, the photoresist film 2 is continuously coated on the top of the stage portion. 1 a, side surface 1 b and bottom surface 1 c 0 In the laminate of the present invention, the film thickness of the photoresist film 2 on the upper side of the stage portion 1 is 1 to 40 μm. The film thickness means that the measurement is performed later. The film thickness of the above film (Τ1). When the film thickness of the photoresist film 2 is Ιμηι or more, an excellent exposure amount limit can be obtained, and when the film thickness is 40 μm or less, sufficient resolution and adhesion can be obtained. The film thickness of the photoresist film 2 is further increased. Preferably, it is from 1.5 to 20 μηι, particularly preferably from 2 to 10 μm. Further, in the laminate of the present invention, when the film thickness (T2) of the boundary portion between the upper surface la and the side surface lb of the step portion 1 is 75% or more of the film thickness (T1) of the upper surface portion of the boundary portion, the achievable Good level of film thickness uniformity. The above-mentioned film thicknesses (T1) and (T2) of the present invention are obtained by using the cross-sectional electron micrograph of the stage portion 1 and are obtained by the following steps: -42- (39) (39) 1335491 First, the section electrons at the stage portion 1 On the microscope photograph, the extension line L1 of the upper side la of the stage portion 1 and the extension line L2' of the side surface lb of the stage portion 1 are determined so that the intersection of the L1 and the L2 is 〇. Next, starting from point 0, at least three or more measurement points having an interval of 30 μm are determined along the upper surface 1 a of the stage portion 1, and then the film thickness of the photoresist film 2 on the upper surface of the phase portion 1 of each measurement point is measured. , t2, t3... Thereafter, the average enthalpy of each of the obtained film thicknesses 11, t2, t3, ... is "the film thickness (T1) above the stage portion". Then, the point at which the distance from the point L of the phase portion L1 is r(T1)/2" is X, the line L3 perpendicular to the line L1 passing through the point X is set, and the intersection of the line L3 and the surface of the photoresist film 2 is Y. Then, a straight line L4 passing through the point Y perpendicular to L2 is set. When the intersection of the straight line L4 and the surface of the stage portion 1 is Z, the distance from the point Z to the point Y is the film thickness (T2) of the boundary portion between the upper portion and the side surface of the stage portion. The photoresist composition for spraying of the present invention is used. The film thickness (T2) can be made 75% or more of the film thickness (T1), so that a uniform film thickness uniformity can be obtained. The ratio of the film thickness (T2) to the film thickness (T1) [(T2)/ (T1)] The closer to 100%, the higher the uniformity of the film thickness, and more preferably 85% or more. Although it may exceed 100%, the upper limit is actually 100%. The inventors have also used the previous light. When the composition is blocked, the film thickness at the position where the thickness of the photoresist film is the thinnest at the time of the phase portion is changed, and even if the cross-sectional shape and the film thickness of the step portion are changed, most of the experiments can be accurately performed. The measurement method is obtained by the point where the intersection of the extension line L 1 and L2 -43- (40) 1335491 is outside the line of [(Tl)/2] and the line perpendicular to the line L1 intersects the surface of the photoresist film 2 Y is the film thickness (T2) of the boundary between the upper surface and the side surface obtained by the measurement position, and is consistent with the experimentally determined enthalpy. Although it is preferable to measure the thickness of each film thickness tl, t2, and t3 on the upper portion of the phase portion, and determine the starting point for the point X from [(Tl)/2] as the angle of the phase portion, the corner portion of the phase portion When the circle is used, the starting point cannot be determined, so the intersection point 0 of L 1 and L2 can be used as the starting point. The corner of the phase is an acute angle so that when it is split at the vertex, Ο will coincide with the vertex. The laminate of the present invention can be obtained by spraying the photoresist composition of the substrate onto the coated surface of the substrate. That is, the photoresist is formed by the spray coating method using the photoresist composition of the present invention, and even if the step portion is provided on the substrate, the above-mentioned [(Τ2)/(Τ1)] can be formed, and light having excellent film thickness uniformity can be formed. Resistance film. Further, the surface of the substrate can be flat to form a photoresist film having excellent film thickness uniformity. • Although the reason cannot be determined, it is presumed that the photoresist composition contains the above-mentioned surfactant, and it is ensured that the photoresist film coated on the substrate has a uniform film thickness with a uniform film thickness at the uneven portion of the corner. It is known that when a photoresist composition is applied by a spin coating method, a surfactant is added to prevent radial streaks from being generated in the film, but the specific surface activity is added to the photoresist composition used in the spray coating method. Further, the inventors have found for the first time that the effect of improving the flatness of the film in the spin coating method is completely different from the effect of improving the uniformity of the stage portion of the substrate in the spray coating method. That is, the photoresist composition used in the spray coating method is added with L3, and the apex of the segment is measured at the apex long-line surface when the film is deposited at 75%. The specific phase of the photoresist is not covered by the surface film thickness of the above-mentioned -44 - (41) (41) 1335491 When a specific surfactant is used, the film thickness uniformity at the corners of the step substrate can be improved, which is an unpredictable and surprising effect. <Formation Method of Photoresist Pattern> The method of forming the photoresist pattern using the layered composition of the present invention is not particularly limited, and a step including selective exposure to the photoresist film and a post-exposure photoresist film can be suitably used. A photoresist pattern forming method in which a base image is developed to form a photoresist pattern. For example, the photoresist pattern can be formed in the following steps. (Exposure step) Selective exposure is carried out by irradiating the above-mentioned laminate with a reactive pattern or a radiation such as ultraviolet rays or visible light having a wavelength of 30,000 to 5 ΟΟηπι. The active light or radiation source used is, for example, a low pressure mercury lamp, a high pressure mercury lamp, an ultra high pressure mercury lamp, a metal halide lamp, an air laser or the like. The active light means a light which activates an acid generator for the purpose of producing acid. Radiation refers to ultraviolet light, visible light, far ultraviolet light, X, electron lines and ion lines. The amount of active light or radiation to be irradiated can be appropriately set in accordance with the type of each component in the photoresist composition, the amount of addition, and the film thickness of the photoresist layer. Further, after selective exposure, it is preferred to carry out heat treatment (ΡΕΒ treatment) to moderately diffuse the acid generated by the acid generator. -45- ' (42) 1335491 (Exposure step) After selective exposure, use alkali imaging solution to develop. When a photoresist film is formed using a positive photoresist composition, a photoresist pattern is formed in addition to the exposed portion of the photoresist film. When a photoresist film is formed using a negative photoresist composition, • a photoresist pattern is formed in addition to the unexposed portion of the photoresist film. The developing solution used, for example, sodium hydroxide, hydrogen oxyhydroxide, sodium citrate, partial Sodium citrate, ammonia, ethylamine, η-propyl, di-η-propylamine, triethylamine, methyldiethylguanamine, triethanolamine, tetramethylammonium hydroxide (ΤΜΑΗ), Aqueous solution of pyrrole, piperidine, 1,8-diazabicyclo[5,4,〇]. alkaloids such as diazabicyclo[4,3,0]-5-decane to 10% by mass An aqueous solution is preferred. Further, an appropriate amount of an aqueous solution of a methanol organic solvent and a surfactant may be added to the aqueous solution of the base as a development method. The development method may be such that the dipping method, the pulverization method, and the spray development time may vary depending on conditions, and generally, for example, 1 to image formation It is preferably washed with running water of 30 to 90 seconds or dried in an oven. The laminate of the present invention can be used in a photoresist film having a basis thickness uniformity at the stage portion, and therefore the in-plane uniformity of the pattern thickness (height) of the light formed by the film is used. [Embodiment] The developing solution can be dissolved and the developing solution can be dissolved to remove potassium telluride, sodium carbonate, base amine, diethylamine, dimethyl alcohol, tetraethylammonium hydroxylated -7--(-- Burn '1,5 -, and use a concentration of 0.1, ethanol and other water-soluble liquid. Development method, etc. 30 minutes. Then form a good film resistance pattern on the air gun air drying plate can be excellent -46 - (43) 1335491 « Examples of the present invention will be described below, but the scope of the present invention is not limited to the examples. [Synthesis Example 1] <Synthesis of (b 2) acid to increase alkali solubility] < Agitator, reflux, thermometer, and drip tank are provided. After the flask, the propylene glycol methyl ether acetate is added to the solvent to start stirring. After #, the temperature of the solvent is raised to 80 ° C. The polymerization catalyst is added. 2,2,-azobisisobutyronitrile, 50% by mass of 1-ethylcyclohexyl methacrylate and 50% by mass of 2-ethoxyethyl acrylate were placed in a dropping tank and stirred. After the polymerization was completely dissolved, the solution was uniformly dropped into the flask over 3 hours, and polymerization was continued for 5 hours at 80 ° C. Thereafter However, the resin of the component (b2) is obtained at room temperature. The resin is separately treated to obtain two resins (b2-l) and (b2-2) having the following mass average molecular weights: • (b2-l): quality Average molecular weight 250,000 (b2-l): mass average molecular weight 3 50,000 [Synthesis Example 2] <Synthesis (cl) novolak resin> M-methylhydrazine and p-methyl hydrazine were mixed at a mass ratio of 60:40. Formaldehyde water is further condensed with a oxalic acid catalyst to obtain a cresol novolak resin. The resin is separately treated to remove a novolak resin having a mass average molecular weight of 1 5,000 in a low molecular domain, and the resin is (C-1) -47-(44) (44)1335491 [Synthesis Example 3] <Synthesis (c2) Copolymer having a hydroxystyrene constituent unit and a styrene constituent unit> The monomer used was hydroxystyrene 75 except The resin (C-2) having a mass average molecular weight of 3,000 was obtained in the same manner as in Synthesis Example 1 except for the mass% and the styrene content: (Synthesis Example 4) <Synthesis (c3) Acrylic Resin> , 2-methoxyethyl acrylate 130 parts by mass, benzyl methacrylate 50 And 20 parts by mass of acrylic acid, the other resin of the same mass synthesis molecular weight of 250,000 (C-3) [Synthetic Example 5] <Synthesis (c4) Vinyl Resin> Using a rotary evaporator to propylene glycol monomethyl Ethyl acetate was subjected to solvent substitution of a poly(ethyl succinyl methyl ether) (mass average molecular weight: 50,000) methanol solution (manufactured by Tokyo Chemical Industry Co., Ltd., concentration: 50% by mass) to obtain a solution having a concentration of 5% by mass ( C-4). [Examples 1 to 4] <Chemically-enhanced positive type light-48-(45) 1335491 resisting composition containing modified oxoxane-based surfactant> The components shown in Tables 1 and 2 were mixed with propylene glycol. After monomethyl ether acetate (PGMEA) was obtained as a homogeneous solution, it was filtered through a membrane filter having a pore size of Ιμηη, and then diluted with acetone to chemically strengthen to a positive resist composition. The acid generator used for the (Α) component is the following two types. (Α-1) : 2,4-bis(trichloromethyl)·6-piperidin-1 ,3,5-triazine φ (Α-2): used in the compound of the following chemical formula (VIII) The surfactant is (S -1 ) : SF 8 4 1 6 (product name, manufactured by Toray Island Co., Ltd.) and (S-2): ΒΥΚ-315 (product name, manufactured by Jue Chemical Co., Ltd.). Further, the surfactant is supplied in the form of a solution, and the number in the table is the mass of the solid component in the solution of the surfactant. 【化9】

C4H9_S_〇— Ν = 〇2

C = Ν - 0 - S - 'C4H9 I 02 CN (W) Further, in Tables 1 and 2, (D-1) is salicylic acid, and (D-2) is triethanolamine. The number in Table 1 is the mass part of each component. (8-1)(6-2)〇2-1)〇2-2)(<:-1)(C-2)(C-3)(C-4)(D-1)(D- 2) (S-1) (S-2) (S_3) is a solid component [Comparative Example], 3] <Preparation of a chemically-reinforced positive-type photoresist composition containing no surfactant> -49- ( 46) 1335491 A chemically amplified positive photoresist composition was prepared in the same manner as in Examples 1 and 3 except that no surfactant was added. A chemically amplified positive photoresist composition having the composition shown in Tables 2 and 2. [Comparative Examples 2 and 4] <Chemically-enhanced positive-type photoresist composition containing a surfactant other than the modified siloxane-based surfactant> In addition to changing the surfactant to (S-3): An alkylbenzenesulfonic acid ammonium salt (product name: Newcol 210, manufactured by Nippon Emulsifier Co., Ltd.) was prepared in the same manner as in Examples 1 and 3 to prepare a chemically amplified positive resist composition. That is, the chemically amplified positive resist composition of the composition shown in Tables 1 and 2. Further, the surfactant is supplied in the form of a solution, and the number in the table is the mass of the solid component in the solution of the surfactant.

[Table 1] Example 1 Example 2 Comparative Example 1 Comparative Example 2 A-2 1 1 1 1 b2-2 50 50 50 50 C-1 20 20 20 20 C-2 20 20 20 20 C-3 5 5 5 5 C-4 5 5 5 5 PGMEA 10 10 10 10 嗣 40 40 40 40 S-1 0.1 • • • S-2 • 0.1 • • S-3 - • 0.1 -50- (47) 1335491 [Table 2] Example 3 Example 4 Comparative Example 3 Comparative Example 4 A-1 1 .5 1.5 1.5 1.5 b2-1 50 50 50 50 C-1 50 50 50 50 D-1 0.2 0.2 0.2 0.2 D-2 0.2 0.2 0.2 0.2 PGMEA 10 1 0 10 10 Acetone 40 40 40 40 S-1 0.1 • . S-2 • 0.1 . S-3 - 0.1

[Evaluation Method] The photoresist compositions of Examples 1 to 4 and Comparative Examples to 4 were sprayed on the surface of the substrate having no surface portion by using a spraying device (manufactured by SUSS MicroTec Co., Ltd., product name: Delta Alta Spray) to form a photoresist. membrane. The substrate used was a 4 inch crucible circuit board provided with a layer of a layer. The upper surface, the side surface, and the bottom surface of the stage portion are flat, and the step portion of the step portion is 300 μm, and the angle 0 formed by the upper surface portion and the side surface portion is 120. . The film thickness (Τ1) on the upper surface portion of the obtained photoresist film and the film thickness (Τ2) at the boundary portion between the upper surface and the side surface of the step portion were measured by the above-described measurement method, and then the ratio of Τ2 to Τ2 was determined [(Τ2)/( Τ1)] (unit: %). [g-evaluation result] Using the photoresist compositions of Examples 1 to 4 and Comparative Examples 1 to 4, the photoresist films of -51 - (48) 1335491 were both the upper surface and the side surface of the continuous coating step portion. The measurement results of T 1 , T 2 and [(Τ2)/(Τ1 )] are shown in Table 3. [Table 3] Example Comparative Example 1 2 3 4 1 2 3 4 Τ 1 ( μιη ) 4.3 5.3 4.5 4.5 5.0 4.9 5.0 5.2 Τ 2 ( μηι) 4.2 4.2 4.4 4.3 3.4 3.5 3.4 3.7 Γ (Τ1)/(Τ1)1 (%) 97.6 79.2 97.8 95.6 68.0 72.2 68.3 70.5

As is apparent from Table 3, when a photoresist film was formed using the photoresist compositions of Examples 1 to 4 containing a modified siloxane-based surfactant, it was found that 75% or more was higher (Τ1)/(Τ1)] Therefore, it was confirmed that the photoresist film of the stage portion has excellent film thickness uniformity. Further, when a photoresist film was formed using the photoresist compositions of Comparative Examples 1 to 4 containing no modified siloxane surfactant, the obtained [(Τ 1 ) / (τ 1 )] 値 was less than 7 5 %. Therefore, it is confirmed that the film thickness uniformity of the photoresist film in the stage portion is poor. Industrial Applicability The photoresist composition of the present invention can be spray-coated with a photoresist film having a good film thickness uniformity on a substrate having a stage portion, and is therefore particularly suitable for forming a photoresist film having a concavo-convex shape. BRIEF DESCRIPTION OF THE DRAWINGS -52- (49) (49)1335491 Fig. is a cross-sectional view of a laminate example of the present invention [Description of main components] 1 : Stage part 2: Photoresist film

-53-

Claims (1)

1335491 (1) X. Patent application scope No. 95 1 43764 Special Chinese patent application scope revision '1 ·" τ PW Amendment of July 5, 1999. 1. A photoresist composition for spraying, which is a photoresist composition used for a method of forming a photoresist film by spraying on a substrate, characterized in that the photoresist composition contains Modified siloxane-based surfactants and photoresist components, The photoresist component is a resin containing (A) active light or a compound which generates an acid under irradiation with radiation, and (B) a resin which increases solubility to the alkali by an acid, and (A) a component added amount (B) 100 parts by mass of the chemically-strength type positive resist of 〇.1 to 20 parts by mass: (A) a compound which generates an acid under active light or radiation, (B') novolak resin, (C') Plasticizer and (E) crosslinker, further, 100 parts by mass of the components (A), (B'), (C') and (E), (A) component The amount added is 至.〇1 to 10 parts by mass, the (B') component is added in an amount of 50 to 95 parts by mass, the (C') component is added in an amount of 5 to 30 parts by mass, and (E) the amount of the component is added. a chemically-enhanced negative photoresist of 1 to 30 parts by mass; or a compound containing (A) active light or radiation to generate an acid, (B") having α-(hydroxyalkyl)acrylic acid, or a An alkali-soluble resin of at least one selected from the group consisting of lower alkyl esters of (hydroxyalkyl)acrylic acid, and (Ε) a crosslinking agent, and (Α) a component relative to (Β) a component ( Ε) The total amount of the components is 100 parts by mass, and the (Α) component is added in an amount of 0.01 to (2) (2) 1335494 1 〇 by mass, relative to the (B') component of 100 parts by mass, and the (E) component is added. It is a negative resist of 1 to 50 parts by mass. 2. The photoresist composition for spraying according to the first aspect of the invention, wherein the coated surface of the substrate is provided with a stage portion. a laminate comprising a photoresist film obtained by forming a photoresist composition of the second aspect of the patent application, on a substrate having a step of 1 〇 to 1, and 〇〇〇μηι on the coated surface. The laminate characterized in that the photoresist film is continuously coated on the upper surface and the side surface of the step portion, and the film thickness on the upper surface portion of the photoresist film is 1 to 40 μm. The film thickness of the boundary portion is 75% or more of the film thickness of the upper surface adjacent to the boundary portion. 4. The laminate of claim 3, wherein the angle formed by the upper surface and the side surface of the stage portion is 9 Å. Above, less than 18〇. .