WO2007069585A1 - Composition de réserve positive pour carte de circuit imprimé et film sec positif pour carte de circuit imprimé et procédé servant à produire une carte de circuit imprimé en utilisant ceux-ci - Google Patents

Composition de réserve positive pour carte de circuit imprimé et film sec positif pour carte de circuit imprimé et procédé servant à produire une carte de circuit imprimé en utilisant ceux-ci Download PDF

Info

Publication number
WO2007069585A1
WO2007069585A1 PCT/JP2006/324724 JP2006324724W WO2007069585A1 WO 2007069585 A1 WO2007069585 A1 WO 2007069585A1 JP 2006324724 W JP2006324724 W JP 2006324724W WO 2007069585 A1 WO2007069585 A1 WO 2007069585A1
Authority
WO
WIPO (PCT)
Prior art keywords
group
circuit board
positive
dry film
substrate
Prior art date
Application number
PCT/JP2006/324724
Other languages
English (en)
Japanese (ja)
Inventor
Genji Imai
Toshikazu Murayama
Harufumi Hagino
Original Assignee
Kansai Paint Co., Ltd.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from JP2005359234A external-priority patent/JP2007163772A/ja
Priority claimed from JP2005359156A external-priority patent/JP2007163767A/ja
Application filed by Kansai Paint Co., Ltd. filed Critical Kansai Paint Co., Ltd.
Publication of WO2007069585A1 publication Critical patent/WO2007069585A1/fr

Links

Classifications

    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
    • G03F7/0392—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition

Definitions

  • Circuit board positive resist composition circuit board positive dry film, and circuit board manufacturing method using the same
  • 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.
  • a photosensitive resist or a photosensitive dry film can be used for forming the wiring pattern of the circuit board.
  • 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.
  • JP-A-2001-22067 discloses a (co) polymer, carboxyl group of p-hydroxy mono- ⁇ -methylstyrene compound and, if necessary, other unsaturated monomer copolymerizable with the compound.
  • 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.
  • 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.
  • 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.
  • 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.
  • the positive resist composition for a circuit board and the positive dry film for a circuit board according to the second invention are:
  • an acid generator that generates an acid by heat (hereinafter sometimes simply referred to as “acid generator”).
  • 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.
  • 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.
  • the positive resist composition and the positive dry film of the first invention preferably contain an acid generator.
  • an 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.
  • an acid generator [(C) component] and a photosensitizer [( D) component] 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.
  • 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)).
  • component (A) an alkyl ether
  • 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.
  • 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.
  • 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.
  • a circuit board having a desired pattern of wiring can be obtained.
  • the conductor is made of copper, the conductor can be etched with an acidic etchant such as cupric chloride or an ammonia etchant.
  • 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.
  • a conductor portion copper or the like
  • 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.
  • 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.
  • 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.
  • 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.
  • the maximum absorption wavelength ( ⁇ max) of the photothermal conversion material is 10 nm, its lZn wavelength ( ⁇ maxZn) and
  • An active energy ray including any one of wavelengths selected from ⁇ times wavelength ( ⁇ ⁇ ⁇ 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.
  • 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 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).
  • the positive resist composition of the second aspect of the present invention and the positive dry film comprising the resist composition include the following (A) It contains at least each component of (C).
  • 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)).
  • block alkyl butyl ether (I) an alkyl butyl ether
  • V, u) are blocked using! /,
  • 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.
  • an alkyl butyl ether (I) for blocking, and further, this block is formed by the action of an acid.
  • 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.
  • R 1 represents a hydrogen atom or a lower alkyl group
  • 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.
  • 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.
  • an alkyl group having 1 to 6 carbon atoms is preferable, and an alkyl group having 1 to 3 carbon atoms is more preferable.
  • 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.
  • 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
  • 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.
  • 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):
  • 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.
  • 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.
  • those having a structure represented by the following general formula (4) are preferable as long as they can block the group.
  • R 2 is defined in the same manner as in general formula (1).
  • 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.
  • 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.
  • 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.
  • alkyl butyl ether (I) for blocking
  • the monomer unit is contained in the polymer, so that another type of alkenyl ether is used as a blocking agent.
  • the sensitivity is excellent.
  • 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.
  • copolymer various forms such as a random copolymer and a block copolymer can be 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.
  • 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
  • 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.
  • 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
  • (meth) acrylic acid means acrylic acid and methacrylic acid, and other (meth) acrylic acid derivatives have the same meaning.
  • a vinyl polymer that can be used as the component (A) can be obtained.
  • the polymerization can be performed according to a known method.
  • a reaction solvent may be used.
  • the reaction solvent is not particularly limited as long as it is inert to the reaction.
  • the polymerization initiator has different power depending on the polymerization mode.
  • chain transfer agent examples include thio ⁇ naphthol, thiophenol, ⁇ butyl mercaptan, ethyl thioglycolate, mercapto'ethanol, isopropyl 'mercaptan, tert-butyl mercaptan, diphenyl' disulfide, jetyl di
  • chain transfer agent examples include thioglycolate, jetyl disulfide and the like, and the amount used is preferably 0.01 to 5% by mass in the total raw materials.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • ⁇ max maximum absorption wavelength
  • 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.
  • 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.
  • cyanine dyes include the following.
  • phthalocyanine dyes include the following.
  • dye 16 is particularly 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • each of the above groups examples 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.
  • 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
  • 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.
  • 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.
  • 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 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.), trifluoroacet
  • Z- is Taia - illustrates the on, for example BF-, AsF-, PF-, SbF-, SiF 2_, CIO-, C
  • Perfluoroalkane sulfonates such as F SO—, toluene sulfonates
  • 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.
  • R 2G3 , R 2G4 , R 2G5 and ⁇ Ar 2 may be bonded via a single bond or a substituent.
  • Specific examples include the following compounds, but are not limited thereto.
  • Bu represents a tert-butyl group.
  • 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).
  • 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.
  • 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 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, bro
  • a diazodisulfone derivative represented by the following general formula (PAG7) is preferably mentioned.
  • 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.
  • Preferred examples of the sulfonate derivative include compounds represented by the following formula (I).
  • Y to Y are each independently a hydrogen atom, an alkyl group, an aryl group, or a halogen atom.
  • R represents an alkyl group, an aryl group or a camphor residue.
  • X represents — ⁇ —, —S—, 1 ⁇ —, 1 NR —, or 1 CH (R) —. Where R is an alkyl group
  • 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 ⁇ butyl group, a sec butyl group, or a tert butyl group.
  • 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
  • halogen atoms of ⁇ to ⁇ include, for example, chlorine atom, bromine atom, fluorine atom, iodine
  • 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. ⁇ ⁇ less ⁇
  • 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 ⁇ to ⁇ is represented by -OSO R
  • organic group having a group represented by OSO R examples include alkyl as Y to Y.
  • 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 ⁇ -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.
  • X represents 1 O, 1 S, 1 NH, 1 NR — or 1 CHn (R) m —.
  • 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.
  • 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.
  • Y and Y are preferably bonded to each other to have a structure of the following formula ( ⁇ )
  • X is — O—, — S—, — NH— NR or CH
  • 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
  • R represents an alkyl group, and m and n are 0, 1 or 2 respectively.
  • R to R are each independently a hydrogen atom, an alkyl group, or
  • R to R, Y, and Y is a group having —OSO R. Y—O
  • a group having SOR is preferable.
  • the compound represented by the following formula (IV) is more preferred to be a compound represented by ( ⁇ ).
  • R to R are each independently a hydrogen atom, alkyl group, alkoxy group, halogen atom, hydroxyl group
  • the alkyl group of R to R is
  • 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.
  • 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.
  • the aryl group of R to R is preferably 6 to 6 carbon atoms
  • Examples of the 14 aryl groups include a phenyl group, a tolyl group, and a naphthyl group, which may further have a substituent.
  • Examples of the halogen atom represented by R to R include a chlorine atom, a bromine atom, a fluorine atom, and iodine.
  • R to R alkoxy group for example, preferably
  • 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.
  • the group having OSO R of R to R is a group represented by OSO R or a substituent.
  • organic group having 2 2 examples include, for example, alkyl groups, alkoxy groups, and hydroxyl groups as R to R
  • At least two of 2 1 4 may be bonded to each other to form a ring structure.
  • 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.
  • an alkyl group preferably having 1 to 5 carbon atoms
  • the acid generators represented by formula (I) can be used singly or in combination of two or more.
  • 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 ⁇ -toluenesulfonato, naphthalimidylcamphorsulfonate, 2-[(tribromomethyl) sulfol] pyridine, tribromomethylphenolsulfone, etc. preferable.
  • One of these or two or more can be used as necessary.
  • 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
  • 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.
  • 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.
  • 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.
  • 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.
  • Examples include coronene, benzanthracene, perylene, ketocoumarin, coumarin, and borate pigments. These can be used alone or in combination of two or more.
  • borate photosensitizing dye examples 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.
  • DBA dibutoxyanthracene
  • coumarin photosensitizers particularly coumarin photosensitizers shown below
  • Examples of coumarin photosensitizers include coumarin derivatives represented by the following general formulas.
  • R, R, R and R are each independently an alkyl group having 1 to 3 carbon atoms
  • X represents a 5-membered heterocyclic group which may have a condensed ring.
  • R represents an acyl group, an alkoxy carbo group, or an aryloxy group carbonyl group.
  • 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— ⁇ , ⁇ is C to C
  • 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 ⁇ is C to C
  • R, R, R and R each independently represents an alkyl group, of which
  • At least one represents an alkyl group having an oxygen atom in the carbon chain).
  • An acid may be further added to the positive resist compositions of the first and second inventions.
  • 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. .
  • 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.
  • the positive resist composition may be made into a liquid composition by adding a solvent!
  • 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.
  • ketone solvents such as ketones
  • 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.
  • the solvent in the case of film formation by coating, 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.
  • a component for maintaining a liquid state may be added.
  • the liquid composition obtained using a solvent can be formed into a film on a substrate and used as a dry film.
  • 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.
  • 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.
  • a surface treatment a treatment with a silane coupling agent can be mentioned as a suitable one.
  • 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.
  • spin coating, blade coating, spray coating, wire bar coating, date bubbling, air knife coating, roller coating, curtain coating, or the like can be used for coating on the substrate.
  • the thickness of the photosensitive layer is set according to the characteristics required for circuit board manufacture.
  • 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.
  • 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.
  • a normal exposure method can be used.
  • a pulse irradiation type or a continuous irradiation type may be used.
  • 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,
  • Gas laser such as N laser and excimer laser; InGaP laser, AlGaAs laser
  • GaAsP laser One by one, GaAsP laser, InGaAs laser, InAsP laser, CdSnP laser,
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • the weight average molecular weight (Mw) of the polymer in the reference example was measured by gel permeation chromatography under the following conditions.
  • 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.
  • 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 ⁇ m LineZSpace could be resolved.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • the obtained resist pattern was evaluated. As a result, it was confirmed that 10 mLine / Space could be resolved.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • Example B8 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.

Landscapes

  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • General Physics & Mathematics (AREA)
  • Materials For Photolithography (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

L'invention concerne une composition de réserve positive pour carte de circuit imprimé et un film sec positif pour carte de circuit imprimé, caractérisés en ce qu'ils contiennent un polymère vinylique ayant des unités monomères ayant un groupe soluble dans les alcalis, bloqué avec un éther d'alkyle et de vinyle. En outre, l'invention concerne un procédé servant à produire une carte de circuit imprimé en utilisant ceux-ci.
PCT/JP2006/324724 2005-12-13 2006-12-12 Composition de réserve positive pour carte de circuit imprimé et film sec positif pour carte de circuit imprimé et procédé servant à produire une carte de circuit imprimé en utilisant ceux-ci WO2007069585A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP2005-359234 2005-12-13
JP2005359234A JP2007163772A (ja) 2005-12-13 2005-12-13 回路基板用ポジ型レジスト組成物、回路基板用ポジ型ドライフィルム、及び、それを用いた回路基板の製造方法
JP2005359156A JP2007163767A (ja) 2005-12-13 2005-12-13 回路基板用ポジ型レジスト組成物、回路基板用ポジ型ドライフィルム、及び、それを用いた回路基板の製造方法
JP2005-359156 2005-12-13

Publications (1)

Publication Number Publication Date
WO2007069585A1 true WO2007069585A1 (fr) 2007-06-21

Family

ID=38162893

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2006/324724 WO2007069585A1 (fr) 2005-12-13 2006-12-12 Composition de réserve positive pour carte de circuit imprimé et film sec positif pour carte de circuit imprimé et procédé servant à produire une carte de circuit imprimé en utilisant ceux-ci

Country Status (2)

Country Link
TW (1) TW200736837A (fr)
WO (1) WO2007069585A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2016057612A (ja) * 2014-09-08 2016-04-21 信越化学工業株式会社 化学増幅ポジ型レジストドライフィルム並びにドライフィルム積層体及びその製造方法

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6267951B2 (ja) 2013-12-18 2018-01-24 富士フイルム株式会社 感光性転写材料、パターン形成方法およびエッチング方法
TWI648298B (zh) 2018-02-08 2019-01-21 財團法人工業技術研究院 共聚物與樹脂組合物

Citations (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH05506106A (ja) * 1990-04-10 1993-09-02 イー・アイ・デユポン・ドウ・ヌムール・アンド・カンパニー ポジティブワーキングレジスト組成物および乾燥フィルムフォトレジストにおけるそれらの使用
JPH06308733A (ja) * 1993-04-23 1994-11-04 Kansai Paint Co Ltd 感光性組成物及びパターンの製造方法
JPH11286535A (ja) * 1998-02-03 1999-10-19 Taiyo Ink Mfg Ltd 感光性・熱硬化性樹脂組成物及びそれを用いた樹脂絶縁パターンの形成方法
WO2003006407A1 (fr) * 2001-07-13 2003-01-23 Kyowa Yuka Co., Ltd. Procédé de production de composé d'éther
JP2004045448A (ja) * 2002-07-04 2004-02-12 Shin Etsu Chem Co Ltd レジスト材料及びパターン形成方法
JP2004053617A (ja) * 2001-07-09 2004-02-19 Mitsui Chemicals Inc ポジ型感光性レジスト組成物およびその用途
JP2004054106A (ja) * 2002-07-23 2004-02-19 Mitsubishi Chemicals Corp ポジ型感光性組成物、ポジ型感光性画像形成材及びそれを用いたポジ画像形成方法
WO2004081065A1 (fr) * 2003-03-10 2004-09-23 Mitsui Chemicals, Inc. Copolymere sensible a l'acide et son utilisation
JP2005091433A (ja) * 2003-09-12 2005-04-07 Mitsui Chemicals Inc ポジ型感光性樹脂組成物、およびその用途
JP2006003861A (ja) * 2004-05-19 2006-01-05 Mitsui Chemicals Inc ポジ型感光性レジスト組成物およびその製造方法
WO2006009258A1 (fr) * 2004-07-22 2006-01-26 Kansai Paint Co., Ltd. Composition de résine positive de type activation à rayons proches de l’infrarouge
JP2006178423A (ja) * 2004-11-25 2006-07-06 Kyowa Hakko Chemical Co Ltd 化学増幅ポジ型レジスト組成物
WO2006115117A1 (fr) * 2005-04-20 2006-11-02 Kansai Paint Co., Ltd. Composition de reserve positive pour un disque de support d'enregistrement, et procede pour produire un disque de support d'enregistrement et procede pour produire une matrice respectivement en utilisant une telle composition de reserve positive

Patent Citations (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH05506106A (ja) * 1990-04-10 1993-09-02 イー・アイ・デユポン・ドウ・ヌムール・アンド・カンパニー ポジティブワーキングレジスト組成物および乾燥フィルムフォトレジストにおけるそれらの使用
JPH06308733A (ja) * 1993-04-23 1994-11-04 Kansai Paint Co Ltd 感光性組成物及びパターンの製造方法
JPH11286535A (ja) * 1998-02-03 1999-10-19 Taiyo Ink Mfg Ltd 感光性・熱硬化性樹脂組成物及びそれを用いた樹脂絶縁パターンの形成方法
JP2004053617A (ja) * 2001-07-09 2004-02-19 Mitsui Chemicals Inc ポジ型感光性レジスト組成物およびその用途
WO2003006407A1 (fr) * 2001-07-13 2003-01-23 Kyowa Yuka Co., Ltd. Procédé de production de composé d'éther
JP2004045448A (ja) * 2002-07-04 2004-02-12 Shin Etsu Chem Co Ltd レジスト材料及びパターン形成方法
JP2004054106A (ja) * 2002-07-23 2004-02-19 Mitsubishi Chemicals Corp ポジ型感光性組成物、ポジ型感光性画像形成材及びそれを用いたポジ画像形成方法
WO2004081065A1 (fr) * 2003-03-10 2004-09-23 Mitsui Chemicals, Inc. Copolymere sensible a l'acide et son utilisation
JP2005091433A (ja) * 2003-09-12 2005-04-07 Mitsui Chemicals Inc ポジ型感光性樹脂組成物、およびその用途
JP2006003861A (ja) * 2004-05-19 2006-01-05 Mitsui Chemicals Inc ポジ型感光性レジスト組成物およびその製造方法
WO2006009258A1 (fr) * 2004-07-22 2006-01-26 Kansai Paint Co., Ltd. Composition de résine positive de type activation à rayons proches de l’infrarouge
JP2006178423A (ja) * 2004-11-25 2006-07-06 Kyowa Hakko Chemical Co Ltd 化学増幅ポジ型レジスト組成物
WO2006115117A1 (fr) * 2005-04-20 2006-11-02 Kansai Paint Co., Ltd. Composition de reserve positive pour un disque de support d'enregistrement, et procede pour produire un disque de support d'enregistrement et procede pour produire une matrice respectivement en utilisant une telle composition de reserve positive

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2016057612A (ja) * 2014-09-08 2016-04-21 信越化学工業株式会社 化学増幅ポジ型レジストドライフィルム並びにドライフィルム積層体及びその製造方法
US10007181B2 (en) 2014-09-08 2018-06-26 Shin-Etsu Chemical Co., Ltd. Chemically amplified positive resist dry film, dry film laminate and method of preparing laminate

Also Published As

Publication number Publication date
TW200736837A (en) 2007-10-01

Similar Documents

Publication Publication Date Title
TWI825018B (zh) 感光化射線性或感放射線性樹脂組成物、抗蝕劑膜、圖案形成方法及電子元件的製造方法
US5397680A (en) Positive photoresist having improved processing properties
US20180329297A1 (en) Curable composition and cured article using same
WO2002082185A1 (fr) Generateurs photoacides a utiliser dans des compositions de photoresine
KR19990072757A (ko) 포토레지스트조성물및이를포함하는방법및제품
JP2007163772A (ja) 回路基板用ポジ型レジスト組成物、回路基板用ポジ型ドライフィルム、及び、それを用いた回路基板の製造方法
WO2007123062A1 (fr) Élément photosensible, procédé de traçage d'un motif d'enduit protecteur, et procédé de production d'une carte de circuit imprimé
JP6550048B2 (ja) 光開始剤及びその感光性組成物
WO2009147913A1 (fr) Composition de résine photosensible, élément photosensible, procédé de fabrication d'un motif de résist et procédé de fabrication de carte de circuit imprimé
JP6887394B2 (ja) スルホニウム塩、光酸発生剤、それを含む組成物、及び、デバイスの製造方法
JP2011093856A (ja) 組成物、レジスト膜、パターン形成方法、及びインクジェット記録方法
WO2006115117A1 (fr) Composition de reserve positive pour un disque de support d'enregistrement, et procede pour produire un disque de support d'enregistrement et procede pour produire une matrice respectivement en utilisant une telle composition de reserve positive
US20200199261A1 (en) Highly sensitive oxime ester photopolymerization initiator and photopolymerizable composition including the same
US5229254A (en) Positive-working radiation-sensitive mixtures, and radiation-sensitive recording materials produced with these mixtures
JP2004334060A (ja) 化学増幅型レジスト用光酸発生剤及びそれを含有するレジスト材料並びにパターン形成方法
JP7444791B2 (ja) スルホニウム塩、光酸発生剤、硬化性組成物およびレジスト組成物
JP4096857B2 (ja) 青紫色レーザー感光性画像形成材料、青紫色レーザー感光性画像形成材及び画像形成方法
JPWO2009119784A1 (ja) 環状化合物、環状化合物の製造方法、環状化合物からなるフォトレジスト基材、フォトレジスト組成物、微細加工方法、半導体装置及び装置
TWI782107B (zh) 光酸產生劑、硬化性組成物、硬化體、光阻組成物以及抗蝕劑圖案的製作方法
WO2006009258A1 (fr) Composition de résine positive de type activation à rayons proches de l’infrarouge
WO2007069585A1 (fr) Composition de réserve positive pour carte de circuit imprimé et film sec positif pour carte de circuit imprimé et procédé servant à produire une carte de circuit imprimé en utilisant ceux-ci
TWI425313B (zh) A photosensitive resin composition, a photosensitive member, a method for forming a resist pattern, and a method for manufacturing a printed wiring board
JP7117900B2 (ja) 化学増幅型レジスト用光ルイス酸発生剤、および化学増幅型レジスト組成物
KR100714811B1 (ko) 산감응성 공중합체 및 그 용도
JP2009242756A (ja) 感光性樹脂組成物、高分子化合物、パターンの製造法および電子デバイス

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application
NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 06834479

Country of ref document: EP

Kind code of ref document: A1