WO2007069585A1 - Positive resist composition for circuit board, and positive dry film for circuit board, and process for producing circuit board with use thereof - Google Patents

Abstract

A positive resist composition for circuit board, and positive dry film for circuit board, characterized by containing a vinyl polymer having monomer units having an alkali-soluble group blocked with an alkyl vinyl ether. Further, there is provided a process for producing a circuit board with the use thereof.

Description

 Specification

 Circuit board positive resist composition, circuit board positive dry film, and circuit board manufacturing method using the same

 Technical field

 The present invention relates to a positive resist composition and a positive dry film useful for manufacturing a circuit board such as a printed wiring board, and a method for manufacturing a circuit board using the same. Background art

 In recent years, with the progress of surface mounting technology for circuit boards such as printed wiring boards, the demand for highly integrated circuit boards has further increased. In addition, a photosensitive resist or a photosensitive dry film can be used for forming the wiring pattern of the circuit board.

 [0003] Various photosensitive resists and photosensitive dry films that can form fine patterns have been proposed. For example, Japanese Patent Laid-Open No. 2002-122987 discloses a negative photosensitive resin that can form a sharp pattern using a benzopyran ring condensation compound having a photosensitizing ability for visible light having a specific wavelength as a photosensitizer. A rosin composition has been proposed. In addition, JP-A-2001-22067 discloses a (co) polymer, carboxyl group of p-hydroxy mono-α-methylstyrene compound and, if necessary, other unsaturated monomer copolymerizable with the compound. There has been proposed a positive-type ultraviolet-sensitive resin composition containing an olefin resin, an ether bond-containing olefinic unsaturated compound, and a photoacid generator and capable of forming a good fine line circuit pattern. Japanese Patent Laid-Open No. 2001-33967 discloses a positive-type active energy linear dry powder that can form a fine circuit pattern by using an active energy linear resin composition having a urethane bond as a positive dry film. A film has been proposed.

 [0004] However, there is room for further improvement in these prior arts in terms of exposure processing in a completely bright room, high-definition and high-precision wiring, and easier wiring pattern formation process. To one.

 Disclosure of the invention

[0005] An object of the present invention is to provide a positive resist composition and a positive dry composition for producing a circuit board. It is a film with sensitivity and resolution that enables high definition and high accuracy of wiring patterns, and excellent adhesion to the substrate during pattern formation and releasability from the substrate after pattern formation. It is an object of the present invention to provide a positive resist composition and a positive dry film, and a method for producing a circuit board using the same.

 [0006] The positive resist composition for a circuit board and the positive dry film for a circuit board according to the first aspect of the present invention include a bulle polymer having a monomer unit having an alkali-soluble group blocked with an alkyl bur ether. It is characterized by this. In particular, it preferably contains an acid generator and a photosensitizer.

 [0007] The method for producing a circuit board according to the first aspect of the present invention comprises a step of forming a layer of the positive resist composition on the substrate or a step of laminating the positive dry film, and an active portion of the layer. A step of irradiating energy rays, and a step of removing the irradiated portion from the substrate by alkali development to form a pattern of the positive resist composition in accordance with a circuit pattern on the substrate. is there.

 [0008] The positive resist composition for a circuit board and the positive dry film for a circuit board according to the second invention are:

 (A) a vinyl polymer having a monomer unit having an alkali-soluble group blocked with an alkyl butyl ether;

 (B) a photothermal conversion substance that generates heat by active energy rays;

 And (C) an acid generator that generates an acid by heat (hereinafter sometimes simply referred to as “acid generator”).

 [0009] A method for producing a circuit board according to a second aspect of the present invention includes a step of forming a layer of the positive resist composition on the substrate or a step of laminating the positive dry film, and an active portion of the layer. A step of irradiating energy rays, and a step of removing the irradiated portion from the substrate by alkali development to form a pattern of the positive resist composition in accordance with a circuit pattern on the substrate. is there.

[0010] Since the positive resist composition and the positive dry film of the present invention have excellent sensitivity and resolution, it is possible to achieve high definition and high accuracy of the wiring pattern. In addition, it has excellent adhesion to the substrate when forming a no-turn and excellent peelability after forming the pattern. Therefore, it is possible to easily perform the wiring pattern forming process.

 [0011] Furthermore, the positive resist composition and the positive dry film of the first invention preferably contain an acid generator. As the acid generator, either an acid generator that generates acid by heat or an acid generator that generates acid by active energy rays may be used. In particular, in addition to the vinyl polymer [(A) component] having a monomer unit having an alkali-soluble group blocked with an alkyl ether, an acid generator [(C) component] and a photosensitizer [( D) component], and a mechanism that generates acid mainly by active energy rays is preferable.

 [0012] Further, the positive resist composition and the positive dry film of the second invention are a vinyl polymer having a monomer unit having an alkali-soluble group blocked with an alkyl ether (component (A)). In addition to photothermal conversion material [component (B)] that generates heat by active energy rays and acid generator [component (C)], exposure processing in a completely bright room such as under white light The desired sensitivity and resolution can be obtained.

 BEST MODE FOR CARRYING OUT THE INVENTION

 In order to produce a circuit board using the positive resist composition and the positive dry film of the present invention, for example, first, a conductor portion (copper or the like) is formed on the substrate, and then a positive type is formed thereon. A layer of a resist composition is formed or a positive dry film is laminated. Then, a predetermined pattern (pattern corresponding to the circuit pattern) is irradiated with active energy rays, and the resist pattern is formed on the substrate by removing the irradiation force on the substrate by alkali development. Further, by removing the exposed conductor portion by etching and then removing the resist film, a circuit board having a desired pattern of wiring can be obtained. For example, when the conductor is made of copper, the conductor can be etched with an acidic etchant such as cupric chloride or an ammonia etchant.

 [0014] Further, a positive resist composition layer is formed directly on the substrate or a positive dry film is laminated, irradiated with active energy rays, and developed to form a resist pattern on the substrate. By forming a conductor portion (copper or the like) on the exposed portion of the substrate and then removing the resist film, a circuit substrate having a desired pattern of wiring can be obtained.

[0015] For removal of the remaining resist film, a release agent that dissolves the resist film but does not substantially attack the circuit pattern on the substrate and the substrate surface is used. Here, re-exposure before removing the resist film By performing this process, the resist film can be removed more easily by improving the peelability from the substrate.

[0016] The wavelength of the active energy ray is not particularly limited, and the active energy ray irradiation portion (exposed portion) in the resist film is exposed to the active energy ray having a wavelength that causes alteration so that it can be removed by alkali development. Just do it.

 [0017] As the active energy rays, for example, those selected from ultraviolet rays, visible rays, near infrared rays, infrared rays, and far infrared rays can be used. When a photothermal conversion material is included in the positive resist composition in order to induce acid generation due to heat, the maximum absorption wavelength (λ max) of the photothermal conversion material is 10 nm, its lZn wavelength (λ maxZn) and An active energy ray including any one of wavelengths selected from η times wavelength (η · λ max) (n represents an integer of 1 or more) or a combination of two or more of them can be used. Further, this maximum absorption wavelength is preferably in the range of 200 to 900 nm. As the laser beam irradiation apparatus, either a pulse method or a continuous irradiation method can be used.

 The positive resist composition according to the first aspect of the present invention and the positive dry film comprising the resist composition (collectively referred to as “positive resist composition”) are alkyl butyl ethers. It contains at least a bur polymer having a monomer unit having a blocked alkali-soluble group. In particular, it is preferable to use the bulle polymer as the component (A) and further contain at least the following components (C) and (D).

 (A) A vinyl polymer having a monomer unit having an alkali-soluble group blocked with an alkyl butyl ether.

 (C) Acid generator.

 (D) Photosensitizer.

 [0019] The positive resist composition of the second aspect of the present invention and the positive dry film comprising the resist composition (they are collectively referred to as "positive resist composition") include the following (A) It contains at least each component of (C).

 (A) A vinyl polymer having a monomer unit having an alkali-soluble group blocked with an alkyl butyl ether.

(B) A photothermal conversion substance that generates heat by active energy rays. (c) An acid generator that generates an acid by heat.

 [0020] The component (A) is a bulle polymer obtained by using at least a compound having a polymerizable ethylenically unsaturated bond as a monomer. This vinyl polymer is a unit obtained from a monomeric force having an ethylenically unsaturated bond, as an alkyl butyl ether in which an alkali-soluble group can be removed by an acid (hereinafter referred to as block alkyl butyl ether (I)). And V, u) are blocked using! /,

 [0021] As the compound having an ethylenically unsaturated bond and an alkali-soluble group, the alkali-soluble group can be blocked using an alkyl butyl ether (I) for blocking, and further, this block is formed by the action of an acid. There is no particular limitation as long as it can constitute a structural unit that is dissociated and the part becomes alkali-soluble. Such alkali-soluble groups include phenolic hydroxyl groups, carboxyl groups, sulfo groups, imide groups, sulfonamido groups, N-sulfonamido groups, N-sulfone urethane groups, and active methylene groups with 11 pKa. The following alkali-soluble groups can be mentioned.

 [0022] As the structural unit of the vinyl polymer of the component (A), those including those represented by the following formula (1) having a structural unit in which a carboxyl group is blocked are preferable.

 [0023] [Chemical 1]

(Wherein R ¹ represents a hydrogen atom or a lower alkyl group, and R ² represents a substituted or unsubstituted alkyl group.)

Examples of the lower alkyl group represented by R ¹ in the general formula (1) include a linear or branched alkyl group having 1 to 8 carbon atoms, and specifically include a methyl group, an ethyl group, and a propyl group. Group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert- Examples include butyl group, pentyl group, hexyl group, heptyl group, octyl group and the like.

[0024] Examples of the alkyl group for R ² include linear or branched alkyl groups having 1 to 18 carbon atoms, and specifically include a methyl group, an ethyl group, a propyl group, and an isopropyl group. Butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, heptyl group, octyl group, nor group, decyl group, dodecyl group and octadecyl group Among these, an alkyl group having 1 to 6 carbon atoms is preferable, and an alkyl group having 1 to 3 carbon atoms is more preferable.

[0025] Examples of the substituent in the substituted alkyl represented by R ² include a lower alkoxy group, a lower alkanol group, a cyano group, a nitro group, a halogen atom, and a lower alkoxy carbo yl.

[0026] In the above definition of substituents, the lower alkyl group of the lower alkoxy group, lower alkanol group and lower alkoxycarbo ol group is exemplified by the lower alkyl group for R ¹ Are the same. Examples of the lower alkanoyl group include linear or branched ones having 2 to 9 carbon atoms, and specific examples thereof include an acetyl group, a propionyl group, a butyryl group, an isobutyryl group, a valeryl group, Examples include isovaleryl group, bivaloyl group, hexanol group, heptanol group and the like. Examples of the halogen atom include fluorine, chlorine, bromine and iodine atoms.

 The monomer for forming the structural unit represented by the general formula (1) is represented by the following formula (2):

[0028] [Chemical 2]

R ¹

CH ₂ = CH c = o

OH (2)

[Wherein R ¹ is defined in the same manner as the general formula (1) above]

(Meth) acrylic acid and its derivatives represented by and corresponding alkyl vinyl for block It can be obtained as a monomer having the structure of the following formula (3) by reacting with ether (I) to block the carboxyl group of the compound of the general formula (2).

[0029] [Chemical 3]

[Wherein R ¹ and R ² are defined in the same manner as in general formula (1). ]

 The alkyl butyl ether for block (I) used in the above monomer formation reaction includes a carboxyl of a compound having an ethylenically unsaturated bond constituting a monomer unit and having an alkali-soluble group such as a carboxyl group. For example, those having a structure represented by the following general formula (4) are preferable as long as they can block the group.

[0030] [Chemical 4]

V ⁰

H H 8 H

 ( Four )

[Wherein R ² is defined in the same manner as in general formula (1). ].

[0031] Alkyl butyl ether for block used as component (A) of the composition according to the present invention

The bulle polymer having a structural unit blocked with (I) has an alkali-soluble group of a compound having a polymerizable ethylenically unsaturated bond and an alkali-soluble group as described above for alkyl vinyl ether (I ) Can be obtained by carrying out the polymerization reaction in the state blocked with). Block with alkali butyl ether (I) for blocking alkali-soluble groups Can be carried out according to known methods such as those described in WO 03Z6407 pamphlet.

 [0032] Furthermore, the vinyl polymer of the component (A) can have a constitution as a copolymer having two or more structural units, and is not polymerizable ethylenic acid as long as the effects of the present invention are not impaired. It may contain a structural unit obtained from a monomer other than a compound having a saturated bond and an alkali-soluble group. Further, it is not necessary for all the alkali-soluble groups of the vinyl polymer to be blocked. Alkali-soluble groups are blocked by 50 mol% or more, preferably 70 mol% or more of the monomer units having alkali-soluble groups. If it is, please. The greater the proportion of blocked alkali-soluble groups, the better the storage stability of the polymer itself and the resist composition containing it. In addition, the alkali-soluble group is blocked with alkyl butyl ether (I) for blocking, and the monomer unit is contained in the polymer, so that another type of alkenyl ether is used as a blocking agent. Compared to, the sensitivity is excellent.

 [0033] In the case where a desired property is added by introducing a monomer unit without being blocked in the above-mentioned copolymer, the block alkyl butyl ether (I) is used. The ratio of the monomer units having a block is preferably 50 to 70% of the total of the monomer units blocked and blocked with the alkyl butyl ether (I) for blocking.

 [0034] As the form of the copolymer, various forms such as a random copolymer and a block copolymer can be used.

 [0035] When the monomer represented by the general formula (3) mentioned above is used, the monomer represented by the general formula (3) is used in the raw material of the bull polymer as the component (A). The content of the monomer is preferably 2 to 60% by mass, more preferably 5 to 40% by mass. When the monomer represented by the general formula (3) is 2% by mass or more, the developability of the resulting positive resist composition is more excellent, and when it is 60% by mass or less, a film (coating material) obtained from the composition Excellent mechanical properties of the membrane

[0036] As a monomer for forming a bulle polymer, as another monomer that can be used in addition to a compound having an ethylenically unsaturated double bond in which an alkali-soluble group is blocked, Can include compounds having a polymerizable ethylenically unsaturated bond. In the case of such a copolymer, the ratio of the monomer unit in which the alkali-soluble group is blocked to the total monomer unit in the copolymer is preferably 5% or more, more preferably 10% or more.

The compound having a polymerizable ethylenically unsaturated bond is not particularly limited, but for example, butyl acetate, (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) Atarylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethyl hexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) (Meth) acrylic acid alkyl esters consisting of alcohols with 1 to 18 carbon atoms such as talylate and (meth) acrylic acid, aromatics such as styrene, a-methylstyrene, p-methylstyrene, dimethylstyrene, dibutenebenzene Bulle compounds, 2-hydroxyethyl (meth) atarylate, 2-hydroxypropyl ( ) Hydroxyalkyl (meth) acrylates such as acrylate, ethylene glycol di (meth) acrylate, glycol di (meth) acrylates such as butanediol di (meth) acrylate, dimethylaminoethyl (meth) acrylate Alkylaminoalkyl (meth) atalylates such as rate, trifluoroethyl (meth) acrylate, pentafluoropropyl (meth) acrylate, perfluorocyclohexyl (meth) acrylate, 2, 2, 3, 3—tetrafluoropropyl (meth) atarylate, fluorine-containing butyl monomer such as — (perfluorooctyl) ethyl (meth) atalylate, 1— [ ₃ — (meth) atalyloxypropyl] — _{L Χ) 3, 3, 3} - pentamethyldisiloxane, 3- (meth) Atari b propyl tris (trimethyl siloxanyl ) Silane, ΑΚ-5 Siloxane-containing butyl monomers such as [Silicone macromonomer, manufactured by Toa Gosei Chemical Co., Ltd.], butyltrimethoxysilane, butylmethyldimethoxysilane, 3— (methoxysilane, 3- Hydrolyzable silyl group-containing vinyl monomers such as (meth) atalyloxypropyltriethoxysilane, 3- (meth) ataryloxypropylpropyloxysilane, vinylmethyl etherenole, vinylenoethylenotenole, vinylenoisobuty Binoreetenoles such as Noreetenole, polybasic unsaturated carboxylic acids such as fumaric acid, maleic acid, maleic anhydride, flax fatty acid, tall oil fatty acid or dehydrated castor oil fatty acid or their monovalent or Esters of polyhydric alcohols, dimethylaminoethyl (meth) acrylate methyl chloride salt, isobornyl (meth) acrylate, allyl alcohol, allyl alcohol ester, butyl chloride, salt vinylidene, trimethylolpropane tri (meta) ) Known vinyl monomers such as acrylate, propionate butyl, (meth) acrylonitrile, macromonomer AS-6, AN-6, AA-6, AB-6 [Toa Gosei Chemical Co., Ltd.] Such as body. One or more of these can be selected and used.

 In the present invention, “(meth) acrylic acid” means acrylic acid and methacrylic acid, and other (meth) acrylic acid derivatives have the same meaning.

 [0039] Polymerizing at least one monomer having a polymerizable unsaturated double bond in which an alkali-soluble group is blocked and at least one other monomer added as necessary. A vinyl polymer that can be used as the component (A) can be obtained. The polymerization can be performed according to a known method.

 [0040] For the polymerization, a reaction solvent may be used. The reaction solvent is not particularly limited as long as it is inert to the reaction. For example, benzene, toluene, xylene, hexane, cyclohexane Xanthine, Ethyl acetate, Butyl acetate, Methyl lactate, Ethyl lactate, Dioxane, Dioxolan, Ί Butyrolatatone, 3-Methyl-3-methoxybutyl acetate, Acetone, Methyl ethyl ketone, Methyl isobutyl ketone, Diisoptyl ketone, Cyclohexanone, Nisonore, methanole, ethanol, propanole, 2-propanore, butanol, N-methylpyrrolidone, tetrahydrofuran, acetonitrile, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, diethylene glycoleno monobutinore Tenole, Diethylene glycol monobutyl ether acetate, Propylene glycol monomethyl ether, Dipropylene glycol monomethyl ether, Propylene glycol nore monoethylenoate ethere, Propylene glycol nole monomethinoatenoate acetate, Dipropylene glycol monomethyl ether acetate, Methoxybutanol, Acetic acid Examples include methoxybutyl, 3-methyl-3-methoxy-1-butanol, water, dimethyl sulfoxide, dimethylformamide, dimethylacetamide and the like.

[0041] The polymerization initiator has different power depending on the polymerization mode. For example, in radical polymerization, 2, 2, monoazobisisobutyryl-tolyl (AIBN), 2, 2'-azobis-2-methylbutane. Thio-tolyl (AMBN), 2, 2, -azobisvalero-tolyl, benzoyl peroxide, acetyl peroxide, lauroyl peroxide, 1, 1 bis (tert-butylperoxy) 3, 3, 5 trimethylcyclohexane, tert butyl peroxy 2-ethyl hexanoate, cumene hydride peroxide, tert butyl peroxy benzoate, tert-butyl peroxide, methyl ethyl ketone peroxide, m-peroxyperbenzoic acid, persulfate, sodium persulfate, peroxy Ammonium sulfate and the like can be mentioned, and the amount used is preferably 0.01 to 20% by mass in the total raw materials.

 [0042] Examples of the chain transfer agent include thio β naphthol, thiophenol, η butyl mercaptan, ethyl thioglycolate, mercapto'ethanol, isopropyl 'mercaptan, tert-butyl mercaptan, diphenyl' disulfide, jetyl di Examples thereof include thioglycolate, jetyl disulfide and the like, and the amount used is preferably 0.01 to 5% by mass in the total raw materials.

 [0043] The weight average molecular weight of the vinyl polymer is preferably 2,000 to 300,000, more preferably <3,000 to 200,000, and even more preferably <500,000 to 100,000. It is.

 [0044] The monomer composition of the bulle polymer as the component (A) can be used as a positive resist for producing a desired circuit board by itself or in combination with each component added as necessary. Characteristics such as adhesion to the substrate, patterning accuracy, durability during formation of the conductive film, and shape stability of the no-turn are selected. It is preferable to select each component so that the desired sensitivity and resolution can be obtained in the intensity of active energy rays such as laser light used for exposure.

 [0045] It should be noted that in the preparation of the bull polymer as the component (A), a monomer having a polymerizable ethylenic double bond in which an alkali-soluble group is previously blocked with a block alkyl bull ether (I). In addition to the method of preparing by a polymerization reaction using at least a polymer, a method is also available in which a bully polymer having an alkali-soluble group is prepared in advance and the alkali-soluble group is blocked with an alkyl butyl ether (I) for block. it can.

 [0046] The content of the bulle polymer as the component (A) in the positive resist composition is preferably 60 to 95% by mass, more preferably 70 to 85% by mass.

[0047] In the second invention, as the photothermal conversion substance to be contained in the positive resist composition, It is not particularly limited as long as it is a light-to-heat conversion substance that generates heat by active energy rays and does not impair the use for manufacturing a circuit board by being combined with a positive resist composition. Examples of such a photothermal conversion substance include various organic or inorganic dyes and pigments, organic dyes, metals, metal oxides, metal carbides, metal borides and the like. Of these, light-absorbing dyes are useful. As the photothermal conversion substance, those having a maximum absorption wavelength (λ max) in the range of 200 to 900 nm are suitable. Specific examples include those that generate heat by absorbing wavelengths of 266 nm, 351 nm, 355 nm, 405 nm, 436 nm, 650 nm, 610 nm, 760 nm, or 830 nm. For example, when a wavelength of 405 nm is used, light having a wavelength range of 380 to 430 nm (λ 1) and a wavelength range of 760 to 860 nm (λ 1 X n = 2) is efficiently introduced into the photoresist type resist composition. Absorbing light-absorbing dyes can be used.

 [0048] Specific examples include various pigments such as carbon black, cyanine dyes, phthalocyanine dyes, naphthalocyanine dyes, merocyanine dyes, azo dyes, polymethine dyes, squalium dyes, chromium dyes, pyrylium. Examples thereof include dyes and thiopyrylium dyes. Of these, cyanine dyes and phthalocyanine dyes are preferred. One of these or two or more can be used as necessary. Specific examples of the dye are given below. The wavelength and solvent name appended to the chemical formula indicate the maximum absorption wavelength (e max) and the solvent when measured by a conventional method. In the following formulae, Me represents methyl.

 [0049] Specific examples of cyanine dyes include the following.

[0050] [Chemical 5]

[9 ^] [TSOO]

Ζί Ζ £ / 900Ζάΐ / 13ά S8S690 / .00Z OAV [seoo]

PZLPZ £ / 900Zd £ / 13d S8S690 / .00Z OAV

(The wavelengths of the above three types of dyes are all measured values in methanol (MeOH).) Specific examples of phthalocyanine dyes include the following.

8

[6 ^] [00]

Ζί Ζ £ / 900Ζάΐ / 13ά 91 · S8S690 / .00Z OAV

Furthermore, the dye shown below can be illustrated.

Ten] (Dye 1)

[0058] [Chemical 13]

C ₂ H ₄ OCH ₃

Of these, dye 16 is particularly preferred.

[0060] Among these dyes, those having a counter ion of -BF are preferred from the viewpoint of storage stability.

 Four

 Good.

 Furthermore, the following dyes can be exemplified.

[0062] [Chemical 15]

¾H ₄ QCH ₃ un [Resolution]

PZLn 900Zdtl 3d vz S8S690 //. 00r OfA

] 069585

 26

 PCT / JP2006 / 324724

[OZ ^] [Z900]

mi oozd / iDd LZ S8S690 / .00Z OAV

]

<6Z S8S690 //. 00Z ΟΛ ^

CIO, CH ₃

C2H4OC2H OC2H6 C2H4OC2H OC2H6

] 24724

Specific examples of preferred photothermal conversion materials on the market include KA-10, CY-17, CY-5, CY-4, CY-2, CY-20, and CY30 as well as IRG- in the “KAYASORB” series. 002 (above, Nippon Kayaku Co., Ltd.); YKR-4010, YKR-3030, YK R-3070, YKR2900, SIR—159, PA—1005, SIR—128, YKR—2080 and PA—1006 (above, Yamamoto Kasei Co., Ltd.); "PROJECT" 825LDI, "PROJECT" 8 30NP, S174963, S174270 (above Avecia Limited); NK—2014, NK—2 911, NK—2912, NK—4432, NK—4474, NK—4489, NK—4680, NK—4 776, NK—5020 , NK-5036 and NK-5042, NK-1342, NK-1977, NK

— 1886, NK— 1819, NK— 1331, NK— 1837, NK— 863, NK— 3213, NK

— 88, NK—3989, NK—1204, NK—723, NK—3984 (above, manufactured by Hayashibara Biological Research Institute); IR2T, IR3T (above, manufactured by Showa Denko KK); “EXCOLOR” 801K, IR-1, IR-2, "TX-EX-801B" and "TX-EX-805K" (Nippon Shokubai Co., Ltd.); CIR-1080 (Nihon Caritz Corp.); IR98011 , IR980301, IR980401, IR980402, IR980405, IR980406 and IR980504 (YAMADA CHEMICAL Co., Ltd.); and "EPOLIGHT" V-149, V-129, V-63, 111-184, III 192, IV 62B, IV-67, VI-19, VI-148 (manufactured by EPOLIN, INC.) And the like can be mentioned, but are not limited thereto.

 [0073] When the photothermal conversion substance is used, the content of the photothermal conversion substance in the positive resist composition is preferably 0. 0, based on the total amount of the component (A), the component (B) and the component (C). The content may be 5 to 40% by mass, more preferably 1 to 35% by mass.

 [0074] The type of the photothermal conversion substance and the blending amount thereof are also in themselves! Are selected so that desired characteristics as a positive resist can be obtained in combination with the components (A) and (C). Therefore, it is set so that desired sensitivity and resolution can be obtained in the intensity of active energy rays such as laser light used for exposure.

[0075] The acid generator as the component (C) can generate an acid that acts on the bull polymer (A) by exposure to impart solubility to the developer, or is exposed by exposure. It is possible to generate an acid that acts on the vinyl polymer (A) by the action of heat generated from the photothermal conversion substance (B) and imparts solubility to the developer. For example, acid generation occurs in resist compositions such as organic sulfate salts, benzothiazolium salts, ammonium salts, phosphonium salts, etc., and photosensitive compositions. What is contained as an agent can be used. Furthermore, among the acid generators contained in various positive resist compositions, those capable of generating an acid under the heat generation of the photothermal conversion substance mentioned above can be used. [0076] Examples of such an acid generator include diazoum, phospho-um, sulfo-um, and odo-um, and fluorine ion, chlorine ion, bromine ion, iodine ion, perchlorate ion. Inorganic acid ions such as phosphate ion, hexafluorophosphate ion, hexafluoroantimonate ion, hexafluorostannate ion, phosphate ion, borofluoride ion, tetrafluoroborate ion, etc. -ON,, cyano cyanate, benzene sulfonate, naphthalene sulfonate, naphthalene sulfonate, p toluene sulfonate, alkyl sulfonate, benzene carboxylate, Organic acid ions such as alkyl carboxylate ions, trihaloalkyl carboxylate ions, alkyl sulfate ions, trihaloalkyl sulfate ions, nicotinate ions, , Salts with organic metal complex ions such as bisphenol dithiol, thiocatechol chelate, thiobisphenolate chelate, bisdiol OC-diketone, etc .; organic halogen compounds; orthoquinone diazidesulfuryl chloride; oxazole Derivatives; Triazine derivatives; Disulfone derivatives; Sulfonate derivatives; Diazosulfone derivatives; Aromatic sulfone derivatives; Organometallics;

 [0077] As the oxazole derivative and the triazine derivative, an oxazole derivative represented by the following general formula (PAG1) substituted with a trihalomethyl group and an S-triazine derivative represented by the general formula (PAG2) are preferable U, Can be cited as a thing.

 [0078] [Chemical 26]

Junichi N

R ²⁰¹ V ^C , G (Y) ₃

(PA61) (PA62) wherein R ^{2C) 1} is a substituted or unsubstituted aryl group, substituted or unsubstituted alkenyl group, R ^2G2 is a substituted or unsubstituted aryl group, substituted or unsubstituted alkenyl group Represents a substituted or unsubstituted alkyl group, C (Y). Y is chlorine atom or bromine atom

 Three

Indicates. [0079] Examples of the substituent of each of the above groups include, for example, a hydroxyl group, for example, an alkoxy group such as a methoxy group, an ethoxy group, a propoxy group, and a butoxy group, for example, a halogen atom such as chlorine, bromine, and fluorine, and a cyan group. Dialkylamino groups such as dimethylamino groups and jetylamino groups, silyl groups such as trimethylsilyl groups, triethylsilyl groups, tert-butyldimethylsilyl groups, substituted silyl groups such as triphenylsilyl groups, such as siloxy of tert-butyldimethylsiloxy groups Group, sulfonic acid group, alkylcarboxoxy group, alkylamide group, alkylsulfonamide group, alkoxycarbyl group, alkylamino group, alkyl-powered rubamoyl group, alkylsulfamoyl group, alkoxy group, aryloxy group, Aryloxycarbonyl group, alkylthio group, a Alkylthio group, alkyl group, aryl group, carboxyl group, halogen atom (for example, chlorine atom, bromine atom, fluorine atom), trifluoroacetyl group, cyano group, acyl group (for example, acetyl group, propiool group, trifluoro group) An acetyl group), an acyloxy group (for example, acetooxy group, propionyloxy group, trifluoroacetoxy group, etc.), an alkyl sulfonyl group, an aryl sulfonyl group, a cyan group, a nitro group and the like are preferable.

 [0080] Specific examples include, but are not limited to, the following compounds:

[0081] [Chemical 27]

 (PAG2-7)

 (PAG2-5) (PAG2-6)

OaC

(PAG2-8) () As the odonium salt and sulfoyuum salt, the odonium salt represented by the following general formula (PAG3) and the sulfo-um salt represented by the general formula (PAG4) are preferred. Raising It can be done.

 [0082] [Chemical 28]

Here, Ar ¹ and Ar ² each independently represents a substituted or unsubstituted aryl group.

R ^2G3 , R ^2G4 and R ²⁵ each independently represents a substituted or unsubstituted alkyl group or aryl group.

 [0083] Examples of the substituent for each of the above groups include, for example, a hydroxyl group, for example, a methoxy group, an ethoxy group, a propoxy group, a butoxy group and other alkoxy groups, for example, a halogen atom such as chlorine, bromine and fluorine, and a cyan group. Dialkylamino groups such as dimethylamino groups and jetylamino groups, silyl groups such as trimethylsilyl groups, triethylsilyl groups, tert-butyldimethylsilyl groups, substituted silyl groups such as triphenylsilyl groups, such as siloxy of tert-butyldimethylsiloxy groups Group, sulfonic acid group, alkylcarboxoxy group, alkylamide group, alkylsulfonamide group, alkoxycarbyl group, alkylamino group, alkyl-powered rubamoyl group, alkylsulfamoyl group, alkoxy group, aryloxy group, Aryloxycarbonyl group, alkylthio group, a Alkylthio group, alkyl group, aryl group, carboxyl group, halogen atom (for example, chlorine atom, bromine atom, fluorine atom, etc.), trifluoroacetyl group, cyano group, isyl group (for example, acetyl group, propiool group, trifluoro group) An acetyl group), an acyloxy group (for example, acetooxy group, propionyloxy group, trifluoroacetoxy group, etc.), an alkylsulfol group, an arylsulfol group, a cyano group, a nitro group and the like are preferable.

[0084] Z- is Taia - illustrates the on, for example BF-, AsF-, PF-, SbF-, SiF 2_, CIO-, C

 4 6 6 6 6 4

Perfluoroalkane sulfonates such as F SO—, toluene sulfonates

3 3

, Dodecylbenzene sulfonate cation, pentafluorobenzene sulfonate sulfonate Substituted polybenzene aromatic sulfonates such as substituted benzene sulfonates, naphthalene 1-sulfonates, anthraquinone sulfonates, and the like, and sulfonate group-containing dyes. However, it is not limited to these.

[0085] ^{Two of} R ^2G3 , R ^2G4 , R ^{2G5 and ΑΛ} Ar ² may be bonded via a single bond or a substituent. Specific examples include the following compounds, but are not limited thereto.

[0086] [Chemical 29]

§ SS0O

Bu represents a tert-butyl group.

CH ₃ CH;

CH ^ / ^-CH 3 (PAG3-25)

/ O 3 / -3ε900ί1 £ S8S690 / -00ZAV

0600

() szsvd- s /: O 3 / -3ε1 £ AV

PAG4-37

The above formula salts represented by the general formulas (PAG3) and (PAG4) are known, for example, «JW Knapczyketal, J. Am. Chem. Soc., 91, 145 (1969), AL Maycoketal, J. Org Chem., 35, 2532, (1970), E. Goethasetal, Bull. Soc. Chem. Belg., 73, 546, (1964), HM Leicester, J. Am. Chem. Soc., 51, 3587 (192 9), JV Crivelloet al, J. Polym. Chem. Ed., 18, 2677 (1980), U.S. Pat.Nos. 2,807,648 and 4,247,473, JP-A-53-101,331 It can be synthesized by the method described in the above.

 Furthermore, the following compounds can be mentioned as preferred thermal acid generators.

 [0094] [Chemical 36]

Preferable examples of the disulfone derivative and the imide sulfonate derivative include a disulfone derivative represented by the following general formula (PAG5) and an imide sulfonate derivative represented by the general formula (PAG6).

[Chemical 37]

In the formula, Ar ³ and Ar ⁴ each independently represent a substituted or unsubstituted aryl group. R ^2G6 represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group. A represents a substituted or unsubstituted alkylene group, a substituted or unsubstituted alkylene group, or a substituted or unsubstituted arylene group.

 [0096] Examples of the substituent for each of the above groups include, for example, a hydroxyl group, for example, a methoxy group, an ethoxy group, a propoxy group, a butoxy group and other alkoxy groups, for example, a halogen atom such as chlorine, bromine and fluorine, and a cyan group. A dialkylamino group such as a dimethylamino group or a jetylamino group, a silyl group such as a trimethylsilyl group, a triethylsilyl group, a tert-butyldimethylsilyl group, a substituted silyl group such as a triphenylsilyl group, such as a siloxy of a t-butyldimethylsiloxy group Group, sulfonic acid group, alkylcarboxoxy group, alkylamide group, alkylsulfonamide group, alkoxycarbyl group, alkylamino group, alkylcarbamoyl group, alkylsulfamoyl group, alkoxy group, aryloxy group , Aryloxycarbonyl group, alkylthio group, aryl Alkylthio group, alkyl group, aryl group, carboxy group, halogen atom (eg, chlorine atom, bromine atom, fluorine atom, etc.), trifluoroacetyl group, cyano group, isyl group (eg, acetyl group, propionyl group, trifluoroacetyl group) Etc.), an acyloxy group (for example, acetooxy group, propio-loxy group, trifluoroacetoxy group, etc.), alkylsulfol group, aryl-sulfol group, cyano group, nitro group and the like are preferable.

 [0097] Specific examples include forces including the following compounds, but are not limited to these.

[0098] [Chemical 38] //: / O 3 / -3ε900ί1 £ S8S690 / -00ZAV 27

[§ [] 66600 3 /-/ s90 / 0z13d 6 S8S690 / L00Z OAV

靈] [Star 0 R one

As the diazodisulfone derivative, a diazodisulfone derivative represented by the following general formula (PAG7) is preferably mentioned.

[Chemical 41]

 (PAG7)

In the formula, R may have a linear, branched or cyclic alkyl group, or a substituent. Represents an aryl group. Specific examples include the following compounds, but are not limited thereto.

 [Chemical 42]

 Preferred examples of the sulfonate derivative include compounds represented by the following formula (I).

[Chemical 43]

In formula (I), Y to Y are each independently a hydrogen atom, an alkyl group, an aryl group, or a halogen atom.

 14

 , An alkoxy group or a group having OSOR. However, at least one of Υ ~ Υ

 2 1 4

Is a group having OSO R. At least two of Υ to Υ are bonded to each other to form a ring structure

 2 1 4

You may make it. R represents an alkyl group, an aryl group or a camphor residue. X represents —Ο—, —S—, 1 ΝΗ—, 1 NR —, or 1 CH (R) —. Where R is an alkyl group

 61 η 61 m 61

M and n each represents 0, 1 or 2. However, m + n = 2. Y to Y alkyl

 The 14 group is preferably an alkyl group having 1 to 30 carbon atoms, and is, for example, a linear or branched group such as a methyl group, an ethyl group, a propyl group, a η butyl group, a sec butyl group, or a tert butyl group. And a cyclic alkyl group such as a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, an adamantyl group, a norbornyl group, a carboxy group, and the like. You may have. Y to Y aryl groups are preferably charcoal

 14

An aryl group having a prime number of 6 to 14, and examples thereof include a phenyl group, a tolyl group, and a naphthyl group, and these may further have a substituent.

 Examples of the halogen atoms of Υ to Υ include, for example, chlorine atom, bromine atom, fluorine atom, iodine

14

Elementary atoms can be mentioned. As the alkoxy group of Υ to Υ, for example, preferably

 14

Examples thereof include an alkoxy group having 1 to 5 carbon atoms, such as a methoxy group, an ethoxy group, a propoxy group, and a butoxy group. These may further have a substituent. Υ ~ less Υ

 At least two of them may be bonded to each other to form a ring structure, but it is preferred that two adjacent to each other form an aromatic ring. The ring may contain a hetero atom or an oxo group. Further, it may be further substituted. The group having OSOR of Υ to Υ is represented by -OSO R

1 4 2 2 group or an organic group having a group represented by OSO R as a substituent. Examples of the organic group having one OSOR as a substituent include alkyl as Y to Y.

 2 1 4

 And groups in which —OSOR® is substituted on a group, aryl group, or alkoxy group.

 2

 [0105] The alkyl group of R is preferably an alkyl group having 1 to 30 carbon atoms, and is, for example, a linear group such as a methyl group, an ethyl group, a propyl group, a η-butyl group, a sec-butyl group, a tert-butyl group, or the like. Examples thereof include branched alkyl groups, and cyclic alkyl groups such as cyclopropyl group, cyclopentyl group, cyclohexyl group, adamantyl group, norbornyl group, and boron group. These are further substituted. It may have a group. The aryl group of R is preferably an aryl group having 6 to 14 carbon atoms, and examples thereof include a phenyl group, a tolyl group, a naphthyl group, etc. These may further have a substituent. Good.

 [0106] X represents 1 O, 1 S, 1 NH, 1 NR — or 1 CHn (R) m —. here,

 61 61

 R 1 represents an alkyl group, and m and n each represents 0, 1 or 2. Where m + n = 2

61

 . R61 is preferably an alkyl group having 1 to 30 carbon atoms, for example, a linear or branched alkyl group such as a methyl group, an ethyl group, a propyl group, an n-butyl group, a sec butyl group, or a tert butyl group. And a cyclic alkyl group such as a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, an adamantyl group, a norbornyl group, and a vicinal group. These have a substituent. May be.

[0107] Y and Y are preferably bonded to each other to have a structure of the following formula (Π)

 1 2

[0108] [Chemical 44]

In the above formula (Π), X is — O—, — S—, — NH— NR or CH

Show. Y and Y are each independently a hydrogen atom, an alkyl group, an aryl group, a halogen atom, A group having an alkoxy group or OSO R is shown. Where R is an alkyl group, aryl

 2

 Indicates a group or camphor residue. R represents an alkyl group, and m and n are 0, 1 or 2 respectively.

 61

 Represents. However, m + n = 2. R to R are each independently a hydrogen atom, an alkyl group, or

 14

 Has a alkoxy group, a halogen atom, a hydroxyl group, a nitro group, a cyano group, an aryl group, an aryloxy group, an alkoxycarbonyl group, an acyl group, an acyloxy group or an OSOR

 2 groups are shown.

 [0109] However, at least one of R to R, Y, and Y is a group having —OSO R. Y—O

 1 4 3 4 2 3

A group having SOR is preferable.

 2

 [0110] Therefore, among the compounds of the above formula (I), the compound represented by the following formula (IV) is more preferred to be a compound represented by (ΠΙ).

[0111] [Chemical 45]

[0112] [Chem 46]

In formula (III) and formula (IV), the definitions of Y, Y, Y, R, and X are the same as those in formula (1) and formula (Π). R to R are each independently a hydrogen atom, alkyl group, alkoxy group, halogen atom, hydroxyl group

14

 , A nitro group, a cyano group, an aryl group, an aryloxy group, an alkoxycarbonyl group, an acyl group, an acyloxy group or a group having OSOR. The alkyl group of R to R is

 2 1 4

 Preferably, it is an alkyl group having 1 to 30 carbon atoms, for example, a linear or branched alkyl group such as a methyl group, an ethyl group, a propyl group, an n-butyl group, a sec butyl group, a tert butyl group, and the like. The ability to cite cyclic alkyl groups such as cyclopropyl group, cyclopentyl group, cyclohexyl group, adamantyl group, norbornyl group, and carboxy group. good. The aryl group of R to R is preferably 6 to 6 carbon atoms

 14

 Examples of the 14 aryl groups include a phenyl group, a tolyl group, and a naphthyl group, which may further have a substituent.

[0113] Examples of the halogen atom represented by R to R include a chlorine atom, a bromine atom, a fluorine atom, and iodine.

 14

 Elementary atoms can be mentioned. As the R to R alkoxy group, for example, preferably

 14

 Examples thereof include an alkoxy group having 1 to 5 carbon atoms, such as a methoxy group, an ethoxy group, a propoxy group, and a butoxy group. These may further have a substituent.

[0114] The group having OSO R of R to R is a group represented by OSO R or a substituent.

 1 4 2 2

 As an organic group having a group represented by OSO R. OSO R as a substituent

 Examples of the organic group having 2 2 include, for example, alkyl groups, alkoxy groups, and hydroxyl groups as R to R

 14

 , A nitro group, a cyano group, an aryl group, an aryloxy group, an alkoxycarbonyl group, an acyl group or an acyloxy group substituted with —OSOR. R ~ R

 At least two of 2 1 4 may be bonded to each other to form a ring structure.

[0115] When Y to Y, R, X, and R to R further have a substituent, for example, an aryl group (for example,

 1 4 1 4

 Phenyl group), a nitro group, a halogen atom, a carboxyl group, a hydroxyl group, an amino group, a cyano group, an alkoxy group (preferably having a carbon number of 1 to 5) and the like. As the aryl group and arylene group, an alkyl group (preferably having 1 to 5 carbon atoms) can be further exemplified.

 [0116] Preferred specific examples of the compound of formula (I) are shown below, but the present invention is not limited thereto.

[0117] [Chemical 47]

The acid generators represented by formula (I) can be used singly or in combination of two or more.

In addition, acid generators include bis (4 tert butylphenyl) ododonium p-toluene sulphonate, 4-methoxyphenol ferrophenol camphors sulphonate, bis (4 — Tert-butylphenol) Jodonium camphor sulfonate, diphenyl-diphenyl p-toluenesulfonate, bis (4-tert-butylphenol) odo-umperfluorobutyl sulfonate, bis (4-tert-butylphenol) R) Jodonium cyclohexylsulfamate, succinimidyl ρ-toluenesulfonato, naphthalimidylcamphorsulfonate, 2-[(tribromomethyl) sulfol] pyridine, tribromomethylphenolsulfone, etc. preferable. One of these or two or more can be used as necessary.

 [0119] Still further, as an acid generator, 4-methylphenol [4- (1-methylethyl) phenol] dononium tetrakis (pentafluorophenol) borate (trade name RHODORSIL— 2074), 2-[(tribromomethyl) sulfol] pyridine (BSP), a, a, α-tribromomethylphenol sulfone (BMPS), represented by the following general formula (1)

 [0120] [Chemical 48]

(In the formula, R represents an alkyl group having 1 to 4 carbon atoms. X represents a halogen atom. Q may have one condensed benzene ring, and an atomic group for forming a pyridine ring. A "represents a halogen ion, an inorganic acid ion or an organic acid ion.)

The cyclic imidazolium salt represented by the general formula (1) is represented by, for example, N-methyl-2- (trimethylammonium sulfo) pyridium-methylsulfate , N ethyl 2- (trimethylmethyl) -pyridium-ethylsulfate, N-methyl 2-trichloromethylsulfyl-methylsulfate, N-methyl-2 -(Tributyl-methyl-sulfuryl) pyridium-bromide, N-methyl-2- (tribromomethylsulfol) pyridyl-mu-hexafluorophosphatate, N-methyl-2-methyl (trimethyl-methyl-sulfo- ) Pyridi-um 'tetrafluoroborate, N-methyl-2- (trib-mouthed momethylsulfol) pyridium-acetate or N-methyl-2- (trib-mouthed methylsulfuryl) pyridi-um' Methanes A Honato like.), The following general formula (2) [0121] [Chemical 49]

A compound represented by

 The following general formula (3)-(5)

 [Chemical 50]

(Trade names NAI-100, NAI-101, NAI-105), etc.

[0123] In the first invention, the content of the acid generator as the component (C) in the positive resist composition is preferably based on the total amount of the components (A) and (C). It can be 5 to 20% by mass, more preferably 1 to 15% by mass.

 [0124] In the second invention, the content of the acid generator as the component (C) in the positive resist composition is based on the total amount of the components (A), (B) and (C). The content may be preferably 0.5 to 20% by mass, more preferably 1 to 15% by mass.

[0125] The type of the acid generator and the amount of the acid generator itself are also present! /, Is a combination of (A) or a combination of the components (A) and (B). It is selected so as to obtain characteristics for substrate production, and the intensity of active energy rays such as laser light used for exposure is selected. To set the desired sensitivity and resolution.

 [0126] In the first invention, it is preferable to further add a photosensitizer (D) to the positive resist composition. That is, a better effect can be obtained by using the suitable acid generator and photosensitizer mentioned above in combination. Conventionally known photosensitizing dyes can be used as the photosensitizer. For example, thixanthene, xanthene, ketone, thiopyrylium salt, base styryl, merocyanine, 3-substituted coumarin, 3, 4 substituted coumarin, cyanine, atalidine, thiazine, phenothiazine, anthracene, Examples include coronene, benzanthracene, perylene, ketocoumarin, coumarin, and borate pigments. These can be used alone or in combination of two or more. Examples of the borate photosensitizing dye include, for example, JP-A-5-241338, JP-A-7-5685, JP-A-7-225474, JP-A-8-6245, and JP-A-7-219223. And those described in JP-A-11-116612, JP-A-11-100408, JP-A-10-273504, and the like. In particular, 9, 10 dibutoxyanthracene (DBA) and coumarin photosensitizers (particularly coumarin photosensitizers shown below) are preferred.

 [0127] Examples of coumarin photosensitizers include coumarin derivatives represented by the following general formulas.

 [0128] [Chemical 51]

(In the above formula, R, R, R and R are each independently an alkyl group having 1 to 3 carbon atoms,

 1 2 3 4

 X represents a 5-membered heterocyclic group which may have a condensed ring. )

[Chemical 52]

(In the above formula, R represents an acyl group, an alkoxy carbo group, or an aryloxy group carbonyl group.)

[0130] [Chemical 53]

(In the above formula, R and R are each independently a hydrogen atom, a C to C alkyl group, R

 1 2 1 3 3 is an alkyl group which may be branched, an alkyl group having an oxygen atom in the carbon chain, or an alkyl group substituted with a halogen, hydroxyl group, cyclohexyl group or phenyl group, X is carbon And a heterocyclic group having 5 to 13 total hetero atoms or —CO—Υ, Υ is C to C

 16 represents a substituted or unsubstituted alkyl group, alkoxy group, etc.)

 [0131] [Chemical 54]

(In the above formula, R and R are each independently a hydrogen atom, a C to C alkyl group, R

1 2 1 3; is an alkyl group which may be branched, an alkyl group having an oxygen atom in the carbon chain, or a halogen atom. , Hydroxyl group, cyclohexyl group or alkyl group substituted with a phenyl group, X is a heterocyclic group having 5 to 13 carbon and hetero atoms in total, or —CO—Y, and Υ is C to C

 16 represents a substituted or unsubstituted alkyl group, alkoxy group, etc.)

 [Chemical 55]

(In the above formula, R, R, R and R each independently represents an alkyl group, of which

 1 2 3 4

 At least one represents an alkyl group having an oxygen atom in the carbon chain).

[0133] An acid may be further added to the positive resist compositions of the first and second inventions. By adding an appropriate amount of this acid, characteristics such as photosensitivity can be improved by synergistic action with the acid generator, and resolution and sensitivity can be further improved. Acids that can be used for this purpose include inorganic acids such as hydrochloric acid, nitric acid, sulfuric acid, and phosphoric acid, carboxylic acids such as acetic acid, oxalic acid, tartaric acid, and benzoic acid, sulfonic acids, sulfinic acids, and phenols. Examples thereof include organic acids such as imides, oximes, and aromatic sulfonamides. One or more of these selected acids can be added depending on the purpose. Of these, p-toluenesulfonic acid is particularly preferred. The acid is preferably selected from the range of 0.001 to 1 monole, more preferably 0.5 to 0.5 monole per mole of acid generator. .

 [0134] Further, in the positive resist composition, in addition to the above-mentioned components, one or more selected ones or two or more selected for adhesion improvers, metal chelate inhibitors, surface conditioners, etc. are used for the purpose. Can be added accordingly. In addition, add a UV absorber to prevent decomposition of the acid generator in the bright room.

[0135] The positive resist composition may be made into a liquid composition by adding a solvent! Examples of the solvent include hydrocarbon solvents such as water, hexane, toluene, and xylene, ether solvents such as dioxane and tetrahydrofuran, acetone, methyl ethyl ketone, and methyl isobutyl. Examples include ketone solvents such as ketones, and acetate solvents such as ethyl acetate and propylene glycol methyl ether acetate. One or more of these may be used depending on the application of the positive resist composition. Can be used in combination. For example, in the case of film formation by coating, the solvent can be used in an amount such that the solid content is preferably about 1 to 50% by mass, more preferably about 2 to 20% by mass. Depending on the type of solvent, a component for maintaining a liquid state may be added. For example, it is possible to obtain a liquid composition as an emulsion by adding necessary components to water or a solvent mainly composed of water using an emulsifier.

 [0136] On the other hand, if necessary, the liquid composition obtained using a solvent can be formed into a film on a substrate and used as a dry film.

[0137] The positive resist composition is made into a liquid form using a solvent as described above, applied onto a substrate to form a film, and an active energy ray such as a laser beam having a wavelength required for patterning is formed on the positive resist composition. A predetermined resist pattern can be obtained by irradiating a position corresponding to the pattern and further developing.

 [0138] As the substrate on which the positive resist composition is formed, a substrate conventionally used for a circuit board such as a printed wiring board can be used. The surface of the substrate may be subjected to a surface treatment for further improving the adhesion of the positive resist composition to the substrate, if necessary. As such a surface treatment, a treatment with a silane coupling agent can be mentioned as a suitable one.

 [0139] As a method of forming a photosensitive layer using a positive resist composition on a substrate, a predetermined amount is applied as a liquid composition on the substrate so as to obtain a desired layer thickness after drying. Examples thereof include a method of obtaining a photosensitive layer by evaporating a solvent, and a method of applying a dry film on a substrate for forming a dry film to form a dry film, and laminating it on the substrate on which the photosensitive layer is to be formed. For coating on the substrate, spin coating, blade coating, spray coating, wire bar coating, date bubbling, air knife coating, roller coating, curtain coating, or the like can be used. The thickness of the photosensitive layer is set according to the characteristics required for circuit board manufacture.

[0140] The photosensitive layer provided on the substrate is exposed to active energy rays including the photosensitive wavelength. It can be performed by an exposure apparatus capable of shooting. In addition, pattern-shaped exposure to the photosensitive layer is, for example, exposure through a mask having a light transmitting portion corresponding to a desired pattern, or a method of directly irradiating a predetermined portion of the photosensitive layer on the substrate with active energy rays. For example, a normal exposure method can be used. When a laser device is used, either a pulse irradiation type or a continuous irradiation type may be used.

 [0141] When using an array-type light source such as a light-emitting diode array, or when controlling the exposure of light sources such as halogen lamps, metal lamps, ride lamps, and tungsten lamps with optical shutter materials such as liquid crystal and PLZT, Digital exposure according to the image signal can be performed. In this case, direct writing can be performed without using a mask material. However, since this method requires a new optical shutter material in addition to the light source, it is preferable to use a laser as the light source for digital exposure.

 [0142] When laser light is used as the light source, it is possible to squeeze the light into a beam and perform latent image recording by scanning exposure according to image data. Further, if a laser is used as the light source, the exposure area can be reduced. It is easy to narrow down to a very small size and high-resolution image recording becomes possible.

 [0143] When the laser device is used for exposure, the wavelength of the irradiated laser beam is not particularly limited. If it is arranged, 266nm, 351nm, 355nm, 405nm, 436nm, 650nm, 610nm, 760nm Alternatively, a laser device that emits laser light having a wavelength of 830 nm can be used. Laser light sources used in the present invention are generally well-known solid lasers such as ruby laser, YAG laser, and glass laser; He—Ne laser, Ar ion laser, Kr ion laser, CO laser, CO laser Laser, He—Cd laser,

 2

 Gas laser such as N laser and excimer laser; InGaP laser, AlGaAs laser

2

 One by one, GaAsP laser, InGaAs laser, InAsP laser, CdSnP laser,

 2

 Examples thereof include semiconductor lasers such as GaSb lasers; chemical lasers and dye lasers. The laser device is not particularly limited, but a semiconductor laser that can be miniaturized is useful. The output of the irradiator uses the desired sensitivity based on the composition and layer thickness of the photosensitive layer, for example, an output that provides effective resolution in bright room processing, and uses a high-power laser up to about 20 W it can.

[0144] In the second invention, the light intensity of the light source for irradiation is 1. OX 10 ² mjZs' cm ^{2 or more} In addition, preferably, it may be 1.0 × 10 ³ mjZs ′ cm ² or more.

[0145] As the developer for removing the exposed portion from the substrate after the exposure, an alkali developer capable of dissolving the portion in which the acid acts on the structural unit having a polymerizable ethylenically unsaturated bond and an alkali-soluble group is used. be able to. Examples of alkali components used in the developer include sodium silicate, potassium silicate, lithium silicate, ammonium silicate, sodium metasilicate, potassium metasilicate, sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, Inorganic, such as sodium bicarbonate, potassium carbonate, dibasic sodium phosphate, tribasic sodium phosphate, dibasic ammonium phosphate, tertiary phosphate ammonium, sodium borate, potassium borate, ammonium borate Alkali salt, monomethylamine, dimethylamine, trimethylamine, monoethylamine, jetylamine, triethylamine, monoisopropylamine, dipropylamine, monobutylamine, monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diii Organic amine compounds such as propanol § Min and the like. Of these, alkali metal silicates such as sodium metasilicate are preferred. An organic solvent such as various surfactants (a ionic surfactant, a nonionic surfactant, and an amphoteric surfactant) and alcohol can be added to the developer as necessary. Further, the content of the alkali component in the developer can be set to a force that can be selected depending on the composition of the positive resist composition, for example, about 0.1 to 5% by mass.

 Example

 [0146] Reference example of production method of polymer (I) and its raw material

 The weight average molecular weight (Mw) of the polymer in the reference example was measured by gel permeation chromatography under the following conditions.

[0147] Column: TSKgel Super HM-M (2), HM-H (1) [all manufactured by Tosoh Corporation] were connected in series.

 Column retention temperature: 40 ° C

 Detector: RI

 Developing solvent: Tetrahydrofuran (flow rate 0.5mlZ min)

Reference material: Polystyrene. [0148] Reference Example 1: Monomer synthesis

50 g of methacrylic acid, 42 g of ethyl vinyl ether and 0.4 g of phosphoric acid were added and reacted at room temperature for 3 hours. The conversion rate of methacrylic acid was 82%, and the selectivity to 1-methacrylic acid methacrylate was ₈₅ %. After neutralizing the reaction solution with 5% aqueous sodium carbonate solution, the organic layer obtained by liquid separation was concentrated under reduced pressure to obtain 1 ethoxyethyl methacrylate.

74g was obtained.

[0149] Hereinafter, the ¹ H-NMR ^ vector of the target product will be described.

 Yeah! NMR spectrum (400MHz)

 Measuring equipment: JEOL GSX- 400

 Measuring solvent: heavy black mouth form

 δ: 6. 16— 6. 14 (m, 1H), 6.00 (q, J = 5.4Hz, 1H), 5. 60 — 5.59 (m, 1H), 3. 73 (dq, J = 9. 5, 7. 1Hz, 1H), 3.56 (dq, J = 9. 6, 7. 1Hz, 1H), 1.95 — 1.94 (m, 3H), 1.44 (d, J = 5.1 Hz, 3H), 1.22 (t, J = 7.1 Hz, 3H).

 [0150] Reference Example 2: Production of vinyl polymer (Q— 1)

 Into a flask equipped with a dripping device, a stirring device, a thermometer, a cooling tube and a nitrogen gas introduction tube, cyclohexanone 200. Og was charged, heated to 80 ° C, and stirred in a nitrogen atmosphere while methacrylic acid was stirred. 1 A solution in which 40 g of ethoxyethyl, 160 g of butyl methacrylate and 16 g of 2,2′-azobis-2 methylbutyryl-tolyl (AMBN) were uniformly dissolved was dropped by applying power for 2 hours from a dropping device. After completion of dropping, 3 times every 30 minutes, add a mixed solution of AMBNZ propylene glycol monomethyl ether acetate = 0.2 g / l. 8 g, and mature at 80 ° C for 3.5 hours to polymerize The reaction was terminated. The obtained polymer solution was a vinyl polymer (Q-1) having a solid content of 53% by mass and a weight average molecular weight of 13,000.

 [0151] Example A1

 Bull polymer (Q-1) 100 parts by weight, photoacid generator (NAI 105, manufactured by Midori Chemical Co., Ltd., trade name) 5 parts are dissolved in cyclohexanone to give a photosensitive solution with a solid content of 28%. Obtained. The resulting photosensitive solution was applied to a copper-clad laminate with a bar coater so that the dry coating film was 10 m, and heated at 80 ° C. for 10 minutes to prepare a substrate with a resist film.

[0152] Ultraviolet mercury lamp with 400mjZcm ² intensity through this substrate with positive pattern mask , Heated at 110 ° C. for 10 minutes, and developed with 1.0% aqueous sodium carbonate solution. Next, etching was performed with a salty cupric aqueous solution at about 40 ° C., and peeling was performed with a 3% aqueous solution of caustic soda to obtain a printed wiring board. The obtained resist pattern was evaluated. As a result, it was confirmed that the resolution of LineZSpace was possible.

 [0153] Example A2

Bullet polymer (Q—1) 100 parts by weight, photoacid generator (NAI-105, manufactured by Midori Chemical Co., Ltd., trade name) 5 parts is dissolved in cyclohexanone, and a photosensitive solution with a solid content of 28%. Got. The resulting photosensitive solution was applied to a polyethylene terephthalate film with a bar coater so that the dry coating film was 10 m, and heated at 80 ° C. for 10 minutes to prepare a dry film. This dry film is formed on the surface of the insulating resin with a metal thin film, such as a Cu thin film, formed by sputtering, electroless plating, etc., and then attached using a dry film laminator, and the polyethylene terephthalate film is peeled off. A substrate with a resist film was obtained. This substrate was irradiated with a 400 mjZcm ² intensity ultraviolet mercury lamp through a positive pattern mask, heated at 110 ° C. for 10 minutes, and developed using a 1.0% aqueous sodium carbonate solution. The results are shown in Table 1. Next, the exposed metal thin film was thickened with a metal to be a wiring, for example, a Cu metal, by a semi-additive method. After that, peeling with 3% caustic soda solution was performed, and as a result, it was confirmed that 5 μm LineZSpace could be resolved.

 [0154] Example A3

Bullet polymer (Q—1) 100 parts by weight, photoacid generator (NAI-105, manufactured by Midori Chemical Co., Ltd., trade name) 5 parts dissolved in cyclohexanone to a photosensitive solution with a solid content of 28% Got. The resulting photosensitive solution was applied to a polyethylene terephthalate film with a bar coater so that the dry coating film was 10 m, and heated at 80 ° C. for 10 minutes to prepare a dry film. This dry film is formed on the surface of the insulating resin with a metal thin film, such as a Cu thin film, formed by sputtering, electroless plating, etc., and then attached using a dry film laminator, and the polyethylene terephthalate film is peeled off A substrate with a resist film was obtained. This substrate was irradiated with an ultraviolet mercury lamp having a strength of 400 mjZcm ² through a positive pattern mask, heated at 110 ° C. for 10 minutes, and developed using a 1.0% aqueous sodium carbonate solution. The results are shown in Table 1. Next, the exposed metal thin film is subjected to a metal that becomes a wiring by a semi-additive method, for example, C u Thickened metal. The entire substrate was irradiated with a 400miZcm ² intensity ultraviolet mercury lamp and heated at 110 ° C for 10 minutes, and then stripped with a 3% aqueous solution of sodium hydroxide. As a result, 5 m LineZSpace could be resolved. confirmed.

 [0155] Example A4

Bullet polymer (Q—1) 100 parts by weight, photoacid generator (NAI-105, manufactured by Midori Chemical Co., Ltd., trade name) 5 parts dissolved in cyclohexanone to a photosensitive solution with a solid content of 28% Got. The resulting photosensitive solution was applied to a polyethylene terephthalate film with a bar coater so that the dry coating film was 10 m, and heated at 80 ° C. for 10 minutes to prepare a dry film. This dry film is formed on the surface of the insulating resin with a metal thin film, such as a Cu thin film, formed by sputtering, electroless plating, etc., and then attached using a dry film laminator, and the polyethylene terephthalate film is still attached. A substrate with a resist film was obtained. The substrate was irradiated with an ultraviolet mercury lamp having a strength of 400 miZcm ² through a positive pattern mask, heated at 110 ° C. for 10 minutes, and developed with a 1.0% aqueous sodium carbonate solution. The results are shown in Table 1. Next, the exposed metal thin film was thickened with a metal to be a wiring, for example, Cu metal, by a semi-additive method. After that, peeling with 3% caustic soda solution was performed, and as a result, it was confirmed that 5 m Line / Space resolution was possible.

 [0156] Example A5

Bullet polymer (Q—1) 100 parts by weight, photoacid generator (NAI-105, manufactured by Midori Chemical Co., Ltd., trade name) 5 parts is dissolved in cyclohexanone, and a photosensitive solution with a solid content of 28%. Got. The resulting photosensitive solution was applied to a polyethylene terephthalate film with a bar coater so that the dry coating film was 10 m, and heated at 80 ° C. for 10 minutes to prepare a dry film. This dry film is formed on the surface of the insulating resin with a metal thin film, for example, a Cu thin film formed by sputtering, electroless plating, etc., and then attached using a dry film laminator, and the polyethylene terephthalate film is still attached. A substrate with a resist film was obtained. This substrate was irradiated with an ultraviolet mercury lamp having a strength of 400 miZcm ² through a positive pattern mask, the polyethylene terephthalate film was peeled off, heated at 110 ° C. for 10 minutes, and developed using a 1.0% aqueous sodium carbonate solution. The results are shown in Table 1. Next, the exposed metal thin film was thickened with a metal to be a wiring, for example, Cu metal, by a semi-additive method. 3% after that Peeling was performed with a caustic soda solution, and as a result, it was confirmed that 5 m Line / Space resolution was possible.

[0157] Examples A6 to A10

Bull polymer (Q— 1) 100 parts by weight, photoacid generator [(4 Methylphenol [4 (1-Methylethyl) phenol] Jodonium tetrakis (pentafluorophenol) borate (Product name! ¾10001 ^ 11 ^ -2074)] 7 parts, photosensitizer 9, 10 3 parts dibutoxyanthracene (DBA) was dissolved in cyclohexanone to prepare a 28% solids sensitizing solution, and, except that the exposure intensity of the ultraviolet ray to 500MjZcm ^2, respectively, in the same manner as in example A1 to A5, to produce a printed wiring board was evaluated. as a result, allows resolution of 5 m LineZSpace It was confirmed that there was.

 [0158] Examples A11 to A15

Vinyl polymer (Q-1) 100 parts by mass, acid generator [compound represented by the following formula] 5 parts, photosensitizer 9, 10 dibutoxyanthracene (DBA) 3 parts dissolved in cyclohexanone A printed wiring board was produced and evaluated in the same manner as in Examples A1 to A5, except that a photosensitive solution having a solid content of 28% was prepared and the exposure intensity of ultraviolet rays was changed to 600 n3j / cm ^2. did. As a result, it was confirmed that Line / Space resolution was possible.

 [0159] [Chemical 56]

Comparative example

Bulle polymer (Q-1) Only 100 parts by mass was dissolved in cyclohexanone to prepare a photosensitive solution having a solid content of 28%. The resulting photosensitive solution was applied to a copper-clad laminate with a bar coater so that the dry coating thickness was 10 m, and heated at 80 ° C. for 10 minutes to produce a substrate with a resist film. When this substrate was exposed to 5 OOmiZcm ² of excimer lamp light with a wavelength of 172 nm through a metal pattern mask and developed, the resist film peeled off in the developer, and after development The resist film thickness has decreased.

 Example B1

 Vinyl polymer (Q-1) 100 parts by mass, 20 parts by mass of the cyanine dye shown below, 10 parts by mass of the acid generator shown below, 0.5 part by mass of paratoluenesulfonic acid in methyl ethyl ketone Was added so as to be 3% by mass to obtain a liquid composition.

[0160] [Chemical 57]

This liquid composition was applied on a glass substrate so that the dry film thickness was 0. m, and dried at room temperature to form a photosensitive layer. This photosensitive layer was irradiated with laser under the following conditions.

 • Resolution: 6400dpi

 • Laser output (total): 5W

 • Laser wavelength for drawing: 830nm

 • Laser scanning speed: 6000mmZ seconds

 After exposure, develop with 1.5% NaCO aqueous solution (25 ° C, 1 minute), wash and dry,

 twenty three

 The obtained resist pattern was evaluated. As a result, it was confirmed that 10 mLine / Space could be resolved.

[0161] Example B2

 Vinyl polymer (Q-1) 100 parts by mass, 20 parts by mass of the cyanine dye shown below and 10 parts by mass of the acid generator shown below were added to methyl ethyl ketone so that the solid content was 3% by mass. Thus, a liquid composition was obtained.

[0162] [Chemical 58]

This liquid composition was applied on a glass substrate so that the dry film thickness was 0. m, and dried at room temperature to form a photosensitive layer. This photosensitive layer was subjected to laser irradiation, development and washing / drying under the same conditions as in Example B1, and the resulting resist pattern was evaluated. As a result, it was confirmed that 10 m LineZSpace could be resolved.

[0163] Example B3

 100 parts by mass of vinyl polymer (Q-1), 20 parts by mass of the cyanine dye shown below, and 10 parts by mass of the acid generator shown below were added in methyl ethyl ketone so that the solid content would be 3% by mass. Thus, a liquid composition was obtained.

[0164] [Chemical 59]

This liquid composition was applied on a glass substrate so that the dry film thickness was 0. m, and dried at room temperature to form a photosensitive layer. This photosensitive layer was subjected to laser irradiation, development and washing / drying under the same conditions as in Example B1, and the resulting resist pattern was evaluated. As a result, it was confirmed that 10 m LineZSpace could be resolved.

[0165] Example B4

Vinyl polymer (Q-1) 100 parts by mass, 20 parts by mass of the cyanine dye shown below and 10 parts by mass of the acid generator shown below were added to methyl ethyl ketone so that the solid content was 3% by mass. Thus, a liquid composition was obtained. [0166] [Chemical 60]

This liquid composition was applied on a glass substrate so that the dry film thickness was 0. m, and dried at room temperature to form a photosensitive layer. This photosensitive layer was subjected to laser irradiation, development and washing / drying under the same conditions as in Example B1, and the resulting resist pattern was evaluated. As a result, it was confirmed that 10 m LineZSpace could be resolved.

[0167] Example B5

 Vinyl polymer (Q-1) 100 parts by weight, 20 parts by weight of cyanine dye shown below, 10 parts by weight of acid generator shown below, 0.5 part by weight of paratoluenesulfonic acid in methyl ethyl ketone Was added so as to be 3% by mass to obtain a liquid composition.

[0168] [Chemical 61]

This liquid composition was applied on a glass substrate so that the dry film thickness was 0. m, and dried at room temperature to form a photosensitive layer. This photosensitive layer was subjected to laser irradiation, development and washing / drying under the same conditions as in Example B1, and the resulting resist pattern was evaluated. As a result, it was confirmed that 10 m LineZSpace could be resolved.

[0169] Example B6

Vinyl polymer (Q-1) 100 parts by mass, cyanine dye 20 parts by mass shown below, 10 parts by mass of the acid generator shown and 0.5 parts by mass of paratoluenesulfonic acid were added to methyl ethyl ketone so that the solid content was 3% by mass to obtain a liquid composition.

[0170] [Chemical 62]

 Fanosani This liquid composition was applied onto a glass substrate so that the dry film thickness was 0.:m, and dried at room temperature to form a photosensitive layer. This photosensitive layer was subjected to laser irradiation, development and washing / drying under the same conditions as in Example B1, and the resulting resist pattern was evaluated. As a result, it was confirmed that 10 m LineZSpace could be resolved.

[0171] Example B7

 Vinyl polymer (Q-1) 100 parts by mass, 20 parts by mass of the cyanine dye shown below and 10 parts by mass of the acid generator shown below were added to methyl ethyl ketone so that the solid content was 3% by mass. Thus, a liquid composition was obtained.

[0172] [Chemical 63]

This liquid composition was applied on a glass substrate so that the dry film thickness was 0. m, and dried at room temperature to form a photosensitive layer. This photosensitive layer was subjected to laser irradiation, development and washing / drying under the same conditions as in Example B1, and the resulting resist pattern was evaluated. As a result, it was confirmed that 10 m LineZSpace could be resolved. [0173] Example B8

 Vinyl polymer (Q-1) 100 parts by mass, 20 parts by mass of the cyanine dye shown below and 10 parts by mass of the acid generator shown below were added to methyl ethyl ketone so that the solid content was 3% by mass. Thus, a liquid composition was obtained.

[0174] [Chemical 64]

SOjCBrg

This liquid composition was applied on a glass substrate so that the dry film thickness was 0. m, and dried at room temperature to form a photosensitive layer. This photosensitive layer was subjected to laser irradiation, development and washing / drying under the same conditions as in Example B1, and the resulting resist pattern was evaluated. As a result, it was confirmed that 10 m LineZSpace could be resolved.

[0175] Example B9

 Vinyl polymer (Q-1) 100 parts by mass, 20 parts by mass of the cyanine dye shown below, and 10 parts by mass of the acid generator shown below were added to methyl ethyl ketone so that the solid content was 3% by mass. Thus, a liquid composition was obtained.

[0176] [Chemical 65]

This liquid composition was applied on a glass substrate so that the dry film thickness was 0 .: m, and at room temperature. A photosensitive layer was formed by drying. This photosensitive layer was subjected to laser irradiation, development and washing / drying under the same conditions as in Example B1, and the resulting resist pattern was evaluated. As a result, it was confirmed that 10 m LineZSpace could be resolved.

 [0177] Example B10

 Vinyl polymer (Q-1) 100 parts by mass, 20 parts by mass of the cyanine dye shown below, 10 parts by mass of the acid generator shown below, 0.5 part by mass of paratoluenesulfonic acid in methyl ethyl ketone Was added so as to be 3% by mass to obtain a liquid composition.

 [0178] [Chemical 66]

This liquid composition was applied on a glass substrate so that the dry film thickness was 0. m, and dried at room temperature to form a photosensitive layer. This photosensitive layer was subjected to laser irradiation, development and washing / drying under the same conditions as in Example B1, and the resulting resist pattern was evaluated. As a result, it was confirmed that 10 m LineZSpace could be resolved.

[0179] Example B11

 Vinyl polymer (Q-1) 100 parts by mass, 20 parts by mass of the cyanine dye shown below, 10 parts by mass of the acid generator shown below, 0.5 part by mass of paratoluenesulfonic acid in methyl ethyl ketone Was added so as to be 3% by mass to obtain a liquid composition.

[0180] [Chemical 67]

This liquid composition was applied on a glass substrate so that the dry film thickness was 0. m, and dried at room temperature to form a photosensitive layer. This photosensitive layer was subjected to laser irradiation, development and washing / drying under the same conditions as in Example B1, and the resulting resist pattern was evaluated. As a result, it was confirmed that 10 m LineZSpace could be resolved.

[0181] Example B12

 Vinyl polymer (Q-1) 100 parts by mass, 20 parts by mass of the cyanine dye shown below, 10 parts by mass of the acid generator shown below, 0.5 part by mass of paratoluenesulfonic acid in methyl ethyl ketone Was added so as to be 3% by mass to obtain a liquid composition.

[0182] [Chemical 68]

This liquid composition was applied on a glass substrate so that the dry film thickness was 0. m, and dried at room temperature to form a photosensitive layer. This photosensitive layer was subjected to laser irradiation, development and washing / drying under the same conditions as in Example B1, and the resulting resist pattern was evaluated. As a result, it was confirmed that 10 m LineZSpace could be resolved.

 [0183] Example B 13

 Vinyl polymer (Q-1) 100 parts by weight, cyanine dye 20 parts by weight shown below, acid generator 10 parts by weight shown below, paratoluenesulfonic acid 0.5 parts by weight, UV absorber 1.5 parts by weight Was added to methyl ethyl ketone so that the solid content was 3% by mass to obtain a liquid composition.

[0184] [Chemical 69]

 υ ¾ shelf This liquid composition was applied on a glass substrate so that the dry film thickness was 0 .: m, and dried at room temperature to form a photosensitive layer. This photosensitive layer was subjected to laser irradiation, development and washing / drying under the same conditions as in Example B1, and the resulting resist pattern was evaluated. As a result, it was confirmed that 10 m LineZSpace could be resolved.

[0185] Examples B14 to: B26

 Using the liquid compositions (positive resist compositions) of Examples B1 to B13, resist patterns were formed and evaluated in the same manner except that the laser wavelength was changed to 830 nm force and 405 nm. As a result, it was confirmed that 0.2 μΐΆ LineZSpace can be resolved.

[0186] Examples B27 to: B39

 Using the liquid compositions (positive resist compositions) of Examples B1 to B13, resist patterns were formed and evaluated in the same manner except that the laser wavelength was changed from 830 nm to 35 lnm. As a result, it was confirmed that 0.1 m Line / Space resolution was possible.

Claims

 The scope of the claims

 [1] A positive resist composition for a circuit board, comprising a bulle polymer having a monomer unit having an alkali-soluble group blocked with an alkyl bur ether.

 [2] The positive resist composition for circuit boards according to claim 1, further comprising an acid generator.

 3. The positive resist composition for a circuit board according to claim 2, wherein the acid generator is an acid generator that generates an acid by active energy rays.

[4] The positive resist composition for a circuit board according to [3], further comprising a photosensitizer.

[5] The positive resist composition for a circuit board according to [1], wherein the alkali-soluble group is a carboxyl group.

[6] The vinyl polymer has the following general formula (1)

 [Chemical 1]

 (1)

6. The circuit according to claim 5, which is a vinyl polymer having a structural unit represented by the formula (wherein R ¹ represents a hydrogen atom or a lower alkyl group, and R ² represents a substituted or unsubstituted alkyl group). A positive resist composition for a substrate.

 Forming a layer of a positive resist yarn and a composite on the substrate; irradiating a predetermined portion of the layer with an active energy line; removing the irradiated portion on the substrate by alkali development; and Forming a pattern of the positive resist composition according to the circuit pattern on the circuit board,

2. The method of manufacturing a circuit board, wherein the positive resist composition is the positive resist composition according to claim 1. [8] The maximum absorption wavelength of the positive energy composition is 10 nm, the lZn wavelength of the maximum absorption wavelength, and the wavelength n times the maximum absorption wavelength (n represents an integer of 1 or more) The method for manufacturing a circuit board according to claim 7, comprising at least a wavelength of

[9] The method for manufacturing a circuit board according to [8], wherein the maximum absorption wavelength is in a range of 200 to 900 nm.

 [10] A positive dry film for a circuit board comprising a bulle polymer having a monomer unit having an alkali-soluble group blocked with an alkyl bur ether.

11. The positive dry film for a circuit board according to claim 10, further comprising an acid generator.

12. The positive dry film for a circuit board according to claim 11, wherein the acid generator is an acid generator that generates an acid by active energy rays.

13. The positive dry film for a circuit board according to claim 12, further comprising a photosensitizer.

[14] The substrate-type dry film for circuit board according to [10], wherein the allylic soluble group is a carboxyl group.

[15] The vinyl polymer has the following general formula (1)

 [Chemical 2]

15. The circuit according to claim 14, wherein the circuit is a vinyl polymer having a structural unit represented by the formula (wherein R ¹ represents a hydrogen atom or a lower alkyl group, and R ² represents a substituted or unsubstituted alkyl group). Positive dry film for substrates.

A step of laminating a positive dry film on a substrate, and a predetermined portion of the positive dry film; Irradiating active energy rays to the substrate, and removing the irradiated portion from the substrate by alkali development to form a pattern of the positive dry film in accordance with the circuit pattern on the substrate. In the method for manufacturing a substrate,

 The method for producing a circuit board, which is the positive dry film according to claim 10.

 [17] The maximum energy absorption wavelength of the positive energy composition 10 nm, the wavelength of lZn of the maximum absorption wavelength, and the wavelength n times the maximum absorption wavelength (n represents an integer of 1 or more) 17. The method for manufacturing a circuit board according to claim 16, wherein the circuit board includes at least a wavelength of the following.

 18. The method for manufacturing a circuit board according to claim 17, wherein the maximum absorption wavelength is in a range of 200 to 900 nm.

 [19] (A) a vinyl polymer having a monomer unit having an alkali-soluble group blocked with an alkyl butyl ether;

 (B) a photothermal conversion substance that generates heat by active energy rays;

 (C) an acid generator that generates acid by heat;

 A positive resist composition for circuit boards, comprising:

[20] The substrate type resist composition for circuit boards according to [19], wherein the alkali-soluble group is a carboxyl group.

[21] The vinyl polymer is represented by the following general formula (1):

 [Chemical 3]

(1) 21. The circuit according to claim 20, wherein R ¹ represents a hydrogen atom or a lower alkyl group, and R ² represents a substituted or unsubstituted alkyl group. A positive resist composition for a substrate.

[22] A step of forming a layer of a positive resist composition on a substrate, a step of irradiating a predetermined portion of the layer with an active energy line, and removing an irradiated portion on the substrate by alkali development, Forming a pattern of the positive resist composition corresponding to the circuit pattern on the substrate, and a method of manufacturing a circuit board,

 20. A method of manufacturing a circuit board, comprising: the positive resist composition according to claim 19.

[23] The active energy ray has a maximum absorption wavelength ± 10 nm of the photothermal conversion substance, a lZn wavelength of the maximum absorption wavelength, and a wavelength n times the maximum absorption wavelength (n represents an integer of 1 or more). 23. The method for manufacturing a circuit board according to claim 22, wherein the circuit board includes at least one of the wavelengths.

 24. The method for manufacturing a circuit board according to claim 23, wherein the maximum absorption wavelength is in a range of 200 to 900 nm.

 [25] (A) a vinyl polymer having a monomer unit having an alkali-soluble group blocked with an alkyl butyl ether;

 (B) a photothermal conversion substance that generates heat by active energy rays;

 (C) an acid generator that generates acid by heat;

 A positive dry film for circuit boards, comprising:

26. The substrate dry film for circuit board according to claim 25, wherein the alkali-soluble group is a carboxyl group.

[27] The vinyl polymer has the following general formula (1)

[Chemical 4]

 (1)

27. The circuit according to claim 26, wherein the circuit is a vinyl polymer having a structural unit represented by (wherein R ¹ represents a hydrogen atom or a lower alkyl group, and R ² represents a substituted or unsubstituted alkyl group). Positive dry film for substrates.

[28] A step of laminating a positive dry film on a substrate, a step of irradiating a predetermined portion of the positive dry film with active energy rays, and removing the irradiated portion from the substrate by alkali development, Forming a pattern of the positive dry film according to the circuit pattern on the substrate,

 26. A method for producing a circuit board, wherein the positive dry film force is the positive dry film according to claim 25.

[29] The active energy ray has a maximum absorption wavelength ± 10 nm of the photothermal conversion substance, a lZn wavelength of the maximum absorption wavelength, and a wavelength n times the maximum absorption wavelength (n represents an integer of 1 or more). 30. The method for producing a circuit board according to claim 28, comprising at least any of the wavelengths.

 30. The method for manufacturing a circuit board according to claim 29, wherein the maximum absorption wavelength is in a range of 200 to 900 nm.