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
  • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
  • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
  • G03F7/029—Inorganic compounds; Onium compounds; Organic compounds having hetero atoms other than oxygen, nitrogen or sulfur
• • H—ELECTRICITY
  • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
  • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
  • H05K3/00—Apparatus or processes for manufacturing printed circuits
  • H05K3/02—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding
  • H05K3/06—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding the conductive material being removed chemically or electrolytically, e.g. by photo-etch process
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F2/00—Processes of polymerisation
  • C08F2/46—Polymerisation initiated by wave energy or particle radiation
  • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
  • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
• • 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
  • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
  • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
  • G03F7/031—Organic compounds not covered by group G03F7/029
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
  • Y10S430/1053—Imaging affecting physical property or radiation sensitive material, or producing nonplanar or printing surface - process, composition, or product: radiation sensitive composition or product or process of making binder containing
  • Y10S430/1055—Radiation sensitive composition or product or process of making
  • Y10S430/106—Binder containing
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
  • Y10S430/1053—Imaging affecting physical property or radiation sensitive material, or producing nonplanar or printing surface - process, composition, or product: radiation sensitive composition or product or process of making binder containing
  • Y10S430/1055—Radiation sensitive composition or product or process of making
  • Y10S430/114—Initiator containing
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
  • Y10S430/1053—Imaging affecting physical property or radiation sensitive material, or producing nonplanar or printing surface - process, composition, or product: radiation sensitive composition or product or process of making binder containing
  • Y10S430/1055—Radiation sensitive composition or product or process of making
  • Y10S430/114—Initiator containing
  • Y10S430/115—Cationic or anionic

Definitions

• Photosensitive element method for forming resist pattern, and method for manufacturing printed wiring board
• the present invention relates to a photosensitive element, a method for forming a resist pattern, and a method for manufacturing a printed wiring board.
• a printed wiring board for example, after a photosensitive element is laminated on a copper-clad laminate and subjected to pattern exposure, portions other than the exposed portion are removed with a developing solution. Next, after a pattern is formed by performing an etching process or a plating process, the hardened portion is manufactured by a method of peeling and removing it from the substrate.
• mercury lamps have been mainly used as light sources for non-exposure.
• the light from the mercury lamp contains ultraviolet rays (light having a wavelength of 400 nm or less) that are harmful to the human body, and there has been a problem with work safety.
• ultraviolet rays light having a wavelength of 400 nm or less
• Non-Patent Document 1 a method has been proposed in which a plurality of mirrors are arranged, and the angle of each mirror is changed as necessary, thereby performing exposure by a direct drawing method in which the exposure light becomes image-like (eg, , Non-Patent Document 1).
• This exposure unit also emits light with a wavelength of 365 nm or less from a mercury lamp light source. 99.5 using filters. In some cases, a light cut by more than / 0 or a gallium nitride based semiconductor laser light source is used.
• Non-Patent Document 1 Electronics Packaging Technology June 2002 (p. 74-79)
• the conventional photosensitive element is designed to cope with the full wavelength exposure of a mercury lamp light source centered on light having a wavelength of 365 nm.
• the conventional photosensitive resin composition layer has a small optical density value (hereinafter referred to as “ ⁇ .D. Value”) with respect to light having a wavelength of 400 to 450 nm and cannot absorb light sufficiently.
• ⁇ .D. Value small optical density value
• the sensitivity of the conventional photosensitive resin composition is low and the resolution is insufficient.
• the formed resist has an inverted trapezoidal cross-sectional shape.
• the inverted trapezoidal shape refers to a state in which the cross-sectional shape of the resist is trapezoidal and the width of the resist pattern decreases from its surface toward the substrate interface.
• the present invention has been made in view of the above, and particularly has a superior sensitivity and resolution to exposure to light having a wavelength of 400 to 450 nm, and has a rectangular cross-sectional shape of a developed resist. It is another object of the present invention to provide a method for forming a resist pattern and a method for manufacturing a printed wiring board.
• the present invention provides a support, (A) a binder polymer provided on the support, and (B) a photopolymerizable compound having at least one polymerizable ethylenically unsaturated bond in a molecule. And (C) a photosensitive resin composition layer composed of a photosensitive resin composition containing a photopolymerization initiator, wherein the photosensitive resin composition comprises: As the component (C), the following general formula (I):
• R 7 and R 8 each independently represent a hydrogen atom, a halogen atom or a hydrocarbon group.
• the weight ratio of the thioxanthone compound with respect to 100 parts by weight of the total amount of the component (A) and the component (B) is P, and the thickness of the photosensitive resin composition layer is 100 parts by weight.
• R force which is the product of P and Q, where Q [/ m], and the following equation (1):
• the present invention relates to a photosensitive element satisfying the following conditions.
• the present invention also relates to the photosensitive element wherein the weight average molecular weight of the binder polymer (A) is 5,000 to 300,000.
• the present invention also relates to the photosensitive element (B), wherein the photopolymerizable compound comprises a bisphenol A-based (meth) acrylate compound as an essential component.
• the present invention essentially requires (B) a compound having one ethylenically unsaturated bond in a molecule and a compound having two or more ethylenically unsaturated bonds in a molecule. It relates to a photosensitive element as a component.
• the photopolymerization initiator includes a 2,4,5-triarylimidazole dimer.
• the photosensitive element includes a 2,4,5-triarylimidazole dimer.
• the present invention provides the photopolymerization initiator represented by the following general formula (II):
• X, R 11 and R 12 each independently represent a monovalent organic group, and h and i each independently represent an integer of 0-5. ]
• the present invention provides an acinolephosphine oxide compound represented by the general formula (II), wherein the compound is represented by the following general formula (III):
• R ′′, R 12 and R 13 each independently represent a monovalent organic group, and h, i and j each independently represent an integer of 0-5.
• a photosensitive element which is an acylphosphine oxide compound represented by the formula:
• the present invention relates to a photosensitive element in which R satisfies the condition of the following formula (2). 28.0 ⁇ R ⁇ 77.0
• the present invention also relates to a photosensitive element wherein R satisfies the condition of the following formula (3).
• the present invention provides a photosensitive element which is exposed to light having an area integrated intensity a at a wavelength of 400 nm to 450 nm in an oscillation spectrum of a light source of 10 times or more of an integrated area intensity b having a wavelength of 300 nm or more and less than 400 nm.
• a photosensitive element which is exposed to light having an area integrated intensity a at a wavelength of 400 nm to 450 nm in an oscillation spectrum of a light source of 10 times or more of an integrated area intensity b having a wavelength of 300 nm or more and less than 400 nm.
• the present invention also relates to a photosensitive element exposed to light having a wavelength of 400 to 415 nm.
• the present invention also relates to a light-sensitive element exposed by light emitted from a gallium nitride based semiconductor laser.
• the present invention also relates to a photosensitive element that is exposed by light emitted from a blue laser.
• the present invention also relates to a photosensitive element that is exposed to light having a wavelength of 365 nm or less emitted from a light source and cut by 90% or more.
• the present invention also relates to a photosensitive element which is exposed by a direct drawing method in which exposure light becomes image-like by arranging a plurality of mirrors and changing the angle of each mirror as necessary. .
• the present invention provides a laminating step of laminating a photosensitive resin composition layer of a photosensitive element on a circuit-forming substrate, and irradiating a predetermined portion of the photosensitive resin composition layer with light for exposure.
• the present invention relates to a method for forming a resist pattern, comprising at least an exposure step of forming a portion and a developing step of removing a portion other than the exposed portion of the photosensitive resin composition layer.
• the present invention also relates to a method for manufacturing a printed wiring board, which comprises etching or plating a circuit-forming substrate on which a resist pattern has been formed by the above-described method for forming a resist pattern.
• the photosensitive element, the method for forming a resist pattern and the method for manufacturing a printed wiring board of the present invention have excellent sensitivity and resolution particularly to exposure to light having a wavelength of 400 to 450 nm,
• the cross-sectional shape of the developed resist is rectangular.
• FIG. 1 is a schematic sectional view showing a preferred embodiment of a photosensitive element of the present invention.
• FIG. 2 is a schematic sectional view showing another preferred embodiment of the photosensitive element of the present invention.
• FIG. 3 is an oscillation spectrum diagram of a mercury lamp light source.
• FIG. 4 is an oscillation spectrum diagram of a mercury lamp light source using a filter.
• (meth) acrylic acid means acrylic acid and its corresponding methacrylic acid
• (meth) atalylate means atalylate and its corresponding methacrylate
• (meth) atalyloyl group means Atariloyl group and the corresponding methacryloyl group are meant.
• FIG. 1 is a schematic sectional view showing a preferred embodiment of the photosensitive element of the present invention.
• the photosensitive element 1 of the present invention includes at least a support 11 and a photosensitive resin composition layer 12 made of a photosensitive resin composition provided on the support 11.
• the photosensitive resin composition forming the photosensitive resin composition layer 12 includes (A) a binder polymer, and (B) a photopolymerizable polymer having at least one polymerizable ethylenically unsaturated bond in a molecule. It contains a compound and (C) a photopolymerization initiator.
• binder polymer (A) examples include an acrylic resin, a styrene resin, an epoxy resin, an amide resin, an amide epoxy resin, an alkyd resin, and a phenol resin. From the viewpoint of alkali developability, an acrylic resin is preferred. These can be used alone or in combination of two or more.
• the binder polymer (A) can be produced, for example, by subjecting a polymerizable monomer to radical polymerization.
• a polymerizable monomer examples include polymerizable styrene such as styrene, vinyl toluene, ⁇ -methylstyrene, ⁇ -methylstyrene, and ⁇ -ethylstyrene.
• Esters of butyl alcohols such as styrene derivatives, atalinoleamide, acrylonitrile, and butyl n- butyl ether; alkyl (meth) acrylates; dimethyl ethyl (meth) acrylate; and glycidyl (meth) acrylate Ester, 2,2,2-trifluoroethyl (meth) acrylate, 2, 2, 3, 3-tetrafluoropropyl (meth) acrylate, (meth) acrylic acid, hy-bromo (meth) acryl Acid, poly (meth) acrylic acid, / 3—furyl (meth) acrylic acid, / 3—styrino (meth) acrylic acid, maleic acid, maleic anhydride, monomethyl maleate, monoethyl maleate, mono maleate Monoesters of maleic acid such as isopropyl, fumaric acid, cinnamic acid, ⁇ _cyanoketic acid, itako
• alkyl (meth) acrylate examples include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, and (meth) acrylic acid. Pentyl, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and structural isomers thereof. These can be used alone or in combination of two or more.
• the binder polymer (ii) preferably contains a carboxyl group.
• a polymerizable monomer having a carboxy group and another polymerizable monomer are formed by radicals. It can be produced by polymerizing.
• methacrylic acid is preferred.
• the binder polymer contains styrene or a styrene derivative as a polymerizable monomer.
• the content be 3 to 30% by weight based on all copolymer components. Is more preferably 5 to 27% by weight. If the copolymerization ratio is less than 3 ⁇ 4% by weight, the adhesion tends to be inferior, and if it exceeds 30% by weight, the peeled pieces tend to be large and the peeling time tends to be long.
• the dispersity (weight average molecular weight / number average molecular weight) of the binder polymer (ii) is preferably 1.0 to 3.0, more preferably 1.0 to 2.0. Dispersion degree exceeds 3.0 Then, the adhesion and the resolution tend to decrease.
• the weight average molecular weight and the number average molecular weight in the present embodiment are values measured by gel permeation chromatography and converted by a calibration curve using standard polystyrene.
• the weight average molecular weight of the binder polymer (A) is preferably 5,000 to 300,000, and more preferably 40,000 to 150,000. When the weight average molecular weight is less than 50,000, the developer resistance of the photocured resist tends to decrease, and when it exceeds 300,000, the development time tends to be long.
• the acid value of the binder polymer (A) is preferably from 30 to 200 mgKOH / g, more preferably from 150 to 150 mgK ⁇ H / g.
• the acid value is less than 30 mgK ⁇ H / g, the development time tends to be long, and when the acid value exceeds 200 mgK ⁇ H / g, the developer resistance of the photocured resist tends to decrease.
• solvent development is performed as the developing step, it is preferable to prepare a small amount of a polymerizable monomer having a carboxy group.
• the binder polymer (A) may have a photosensitive group.
• binder binders can be used alone or in combination of two or more.
• examples of the binder binders include two or more binder binders composed of different copolymer components, two or more binder binders having different weight average molecular weights, and two or more binder binders having different dispersion degrees. And the like. Further, a polymer having a multi-mode molecular weight distribution described in JP-A-11-327137 can also be used.
• the photopolymerizable compound (B) having one or more polymerizable ethylenically unsaturated bonds in the molecule is, for example, obtained by reacting a polyhydric alcohol with a ⁇ -unsaturated carboxylic acid.
• Urethane monomers such as danigata, nourphenoxypolyethyleneoxy atalylate, phthalic acid compounds, taku) noanotan
• Power S These can be used alone or in combination of two or more. From the viewpoint of plating resistance and adhesion, it is preferable to use a bisphenol-based (meth) atalylate conjugate or a (meth) atalay conjugate having a urethane bond in the molecule as an essential component. Good.
• a photopolymerizable compound having one polymerizable ethylenically unsaturated bond in the molecule and a photopolymerizable compound having two or more polymerizable ethylenically unsaturated bonds in the molecule are used in combination. This is preferable because sensitivity and resolution can be improved.
• Compounds obtained by reacting the above polyhydric alcohol with j3-unsaturated carboxylic acid include, for example, polyethylene glycol di (meth) acrylate having 2 to 14 ethylene groups, and propylene. Polypropylene glycol di (meth) acrylate having 2-14 groups, polyethylene having 2-14 ethylene groups and 2-14 propylene groups.
• EO represents ethylene oxide
• the EO-modified compound has a block structure of an ethylene oxide group.
• PO represents propylene oxide
• the PO-modified compound has a block structure of a propylene oxide group.
• Examples of the bisphenol A-based (meth) atalylate compound include 2,2_bis (4_ (meth) atalylate compound
• Examples of the 2,2_bis (4 _ ((meth) ataryloxypolyethoxy) phenyl) propane include, for example, 2,2_bis (4 — (((meta) attalimethylxidiethoxy) phenyl) propane, 2,2— Bis (4-(((meth) atalyloxytriethoxy) phenyl) propane, 2,2_bis (4-(((meth) atari- mouth xitetraethoxy) pheninole) propane, 2, 2_bis (4_ (( (Meth) ataryloxypentaethoxy) phenyl) propane, 2,2-bis (4-((meth) ataryloxyhexaethoxy) phenyl) propane, 2,2_bis (4-(((meth) ataryloxyheptaethoxy) Cis) phenyl) propane, 2,2_bis (4-((meta) atari mouth xyloctaethoxy) phenyl) p mouth bread, 2,
• BPE-500 product name, manufactured by Shin-Nakamura Chemical Co., Ltd.
• Bis (4- (methacryloxypentadecaethoxy) phenyl) propane is commercially available as BPE_1300 (product name, manufactured by Shin-Nakamura Chemical Co., Ltd.).
• the number of oxide groups is preferably 4-20, more preferably 8-15. These can be used alone or in combination of two or more.
• Examples of the (meth) atalylate conjugate having a urethane bond in the molecule include a (meth) acrylic monomer having an OH group in the ⁇ -position and a diisocyanate compound (isophorone diisocyanate, 2, 6-toluene).
• Examples include methylene isocyanurate, EO-modified urethane di (meth) acrylate, EO, P ⁇ -modified urethane di (meth) acrylate.
• An example of the EO-modified urethane di (meth) acrylate is UA-11 (product name, manufactured by Shin-Nakamura Chemical Co., Ltd.).
• Examples of the EO, P ⁇ ⁇ modified urethane di (meth) acrylate include UA-13 (product name, manufactured by Shin-Nakamura Chemical Co., Ltd.). These can be used alone or in combination of two or more.
• nourphenoxypolyethyleneoxy attarylate examples include nourphenoxytetraethyleneoxy attarylate and nourphenoxypentaethyleneoxy attearliest.
• Nourphenoxyhexaethyleneoxy atalylate nourphenoxyheptaethylenoxy acrylate
• nourphenoxy octaethylene oxalate nourphenoxynona ethyleneoxy atalylate
• phthalic acid-based compound examples include, for example, ⁇ -chloro- ⁇ -hydroxypropyl- ⁇ '-(meth) atalyloyloxexetyl- ⁇ -phthalate, j3-hydroxyalkyl- / 3,-( Meta) At Georgiaoxyalkyl mono-phthalate and the like. These can be used alone or in combination of two or more.
• a thioxanthone-based compound represented by the general formula (I) is an essential component.
• the thioxanthone compound is used in an amount of P parts by weight based on 100 parts by weight in total of the component (A) and the component (B).
• R 2 , R 3 , R 7 and R 8 each independently represent a hydrogen atom, a halogen atom or a hydrocarbon group.
• the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and the like, and a chlorine atom is preferable.
• Preferred examples of the hydrocarbon group include a C13 alkyl group and a C13 alkenyl group.
• the alkyl group having 13 to 13 carbon atoms include a methyl group, an ethyl group, and a propyl group, and an ethyl group is preferable.
• Examples of the above alkenyl group having 13 to 13 carbon atoms include an ethyl group and a propenyl group.
• Examples of the thioxanthone compound include a compound in which R 2 and R 4 are both ethyl groups, a compound in which R 2 or R 4 is an isopropyl group, and a compound in which R 2 and R 4 are both chlorine atoms.
• a compound in which R 2 is a chlorine atom is more preferable, and a compound in which R 2 and R 4 are both ethyl groups is more preferable.
• R 2 and R 4 are both ethyl groups.
• the thioxanthone compound is added as a photopolymerization initiator, the storage stability under yellow light is improved.
• the blending amount P is determined by the product R of the photosensitive resin composition layer thickness Q [zm] and the product of the following formula (1).
• the obtained photosensitive element has excellent sensitivity and resolution, and the cross-sectional shape of the developed resist is rectangular.
• the above R is preferably 77.0 or less, more preferably 75.0 or less, still more preferably 72.0 or less, particularly preferably 69.6 or less. It is very preferable that the value be 68.4 or less.
• the above R is preferably 28.0 or more, more preferably 30.0 or more, still more preferably 31.2 or more, and particularly preferably 32.4 or more. preferable.
• the ⁇ .D. Value of the photosensitive resin composition layer for light having a wavelength of 400 to 450 nm is too small to sufficiently absorb light. If it exceeds 0, the above OD value is high and the sensitivity is high, but the light hardly reaches the bottom, so the curability of the bottom deteriorates, the cross-sectional shape of the developed resist becomes inverted trapezoidal, and the resolution becomes poor. It gets worse.
• ⁇ .D. ⁇ is 0.24-0.65, particularly for light having a wavelength of 405 nm, and 0.26-0. It is better than the power of being 62.
• the O.D. value is within the above range, the photosensitive element can obtain sufficient sensitivity and resolution, and the cross-sectional shape of the developed resist becomes rectangular. If the above ⁇ . D. value is less than 0.24, sufficient light for conducting the polymerization reaction cannot be absorbed, and thus the sensitivity tends to be low.
• the OD value exceeds 0.65, the sensitivity is high, but the Since the light hardly reaches the bottom, the curability of the bottom is deteriorated, and the cross-sectional shape of the resist after development tends to be an inverted trapezoid or the resolution is deteriorated.
• the photosensitive resin composition of the present invention may contain a photopolymerization initiator other than the thioxanthone-based compound.
• a photopolymerization initiator other than the thioxanthone-based compound.
• these are, for example, benzophenone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2-methyl- Aromatic ketones such as 1_ [4_ (methylthio) phenyl] _2_morpholino-propanone_1, quinones such as anolequinoleanthraquinone, benzoin ether compounds such as benzoin anolequinoleatenole, benzoin, alkylbenzoin, etc.
• Atarizine derivatives such as 7_bis (9,9,1-ataridinyl) heptane, N-phen-N-phenylglycine derivatives, and acylphosphine oxide compounds can be added. These can be used alone or in combination of two or more. Of these, 2,4,5-triarylimidazole dimers are preferred because they can improve the adhesion and sensitivity.
• the substituents of the aryl groups of the two 2,4,5-triarylimidazoles may be the same to give the target compound, or may give different asymmetric compounds.
• an acylphosphine oxide compound represented by the following general formula (II) is particularly preferred.
• X, R 11 and R 12 each independently represent a monovalent organic group, and h and i each independently represent an integer of 0-5.
• the monovalent organic group R 11 and R 12, a hydrocarbon group of the hydrocarbon group is preferably tool having a carbon number of one 20 is more preferred.
• hydrocarbon groups thus, an alkyl group having 115 carbon atoms is more preferable, and an alkyl group having 115 carbon atoms is more preferable.
• Examples of the monovalent organic group X include a substituted or unsubstituted hydrocarbon group, a carboxyl group, an alkoxy group, and a monovalent substituent obtained by combining these.
• Examples of the substituted or unsubstituted hydrocarbon group include a substituted or unsubstituted aryl group, a substituted or unsubstituted alkyl group, and a substituted or unsubstituted alkenyl group. Of these, a substituted or unsubstituted aryl group is preferred.
• Examples of the substituent in the strongly substituted or unsubstituted hydrocarbon group include an alkyl group, a carboxyl group, an alkoxy group and the like. Among them, an alkyl group having 115 carbon atoms, which is preferred by the alkyl group, is more preferable. preferable.
• an acylphosphine oxide compound represented by the following general formula (III) is preferable.
• R u , R 12 and R 13 each independently represent a monovalent organic group, and h, i and j each independently represent an integer of 0-5.
• the monovalent organic groups R ′′, R 12 and R 13 are more preferably hydrocarbon groups having 120 carbon atoms, preferably hydrocarbon groups.
• alkyl groups are preferable.
• An alkyl group having 1 to 20 carbon atoms is more preferable.
• An alkyl group having 1 to 5 carbon atoms is more preferable, and as a combination of h, i and j, h is 0, i is 0, j is preferably 3.
• acylphosphine oxide compound represented by the general formula (III) examples include 2,4,6_trimethylbenzoyldiphenylphosphine oxide and the like.
• the above R is selected from the range of 25.5 to 95.5. It may be done. In this case, the above R is preferably 90.0 or less, more preferably 75.0 or less, more preferably 72.0 or less, and even more preferably 69.6 or less. Especially preferred is 68.4 or less.
• the above R is preferably 30.0 or more, more preferably 31.2 or more, more preferably 32.4 or more, and still more preferably 32.5 or more. Particularly preferred.
• the content of the component (A) is preferably from 40 to 80 parts by weight based on 100 parts by weight of the total of the components (A) and (B), and more preferably from 45 to 70 parts by weight. More preferred to be.
• the content is less than 40 parts by weight, the photocured resist tends to become brittle, and the photosensitive element tends to be inferior when forming a photosensitive element, and when it exceeds 80 parts by weight, the sensitivity tends to be insufficient. There is.
• the content of the component (B) is preferably 20 to 60 parts by weight based on 100 parts by weight of the total of the components (A) and (B), and more preferably 30 to 55 parts by weight. More preferred to be. If the content is less than 20 parts by weight, the sensitivity tends to be insufficient, and if it exceeds 60 parts by weight, the resist tends to be brittle.
• the content of the component (C) is preferably from 0.1 to 20 parts by weight based on 100 parts by weight of the total of the components (A) and (B). — More preferably 10 parts by weight. If the content is less than 0.1 part by weight, the sensitivity tends to be insufficient.If the content is more than 20 parts by weight, the absorption on the surface of the composition during exposure increases and the photocuring inside becomes insufficient. Tend to be.
• the photosensitive resin composition according to the present invention may optionally contain, for example, a photopolymerizable compound (oxetane compound or the like) having at least one cationically polymerizable cyclic ether group in the molecule, a cationic polymerizable compound, or the like.
• dyes such as malachite green, photochromic agents such as tripromomethylphenylsulfone and leucocrystal violet, thermal coloring inhibitors, plasticizers such as p-toluenesulfonamide, pigments, fillers, defoamers, Flame retardant, stabilizer, adhesion Agents, leveling agents, release accelerators, antioxidants, fragrances, imaging agents, thermal cross-linking agents, etc., with respect to 100 parts by weight of the total amount of the components (A) and (B), respectively. — About 20 parts by weight can be contained. These can be used alone or in combination of two or more.
• the photosensitive resin composition may be used, for example, as required, for example, methanol, ethanol, acetate, methyl ethyl ketone, methyl sorb, ethyl sorb, toluene, N, N-dimethylmethonolenomamide. It can be dissolved in a solvent such as propylene glycol monomethyl ether or a mixed solvent thereof and applied as a solution having a solid content of about 30 to 60% by weight.
• a solvent such as propylene glycol monomethyl ether or a mixed solvent thereof
• the thickness of the photosensitive resin composition layer after drying is preferably 1 to 100 ⁇ m, more preferably 5 to 60 / im, and more preferably 10 to 50 ⁇ m. More preferably, ⁇ . If the film thickness is less than 1 ⁇ m , it tends to be difficult to apply industrially, and if it exceeds 100 ⁇ m, the effect of the present invention is reduced, and the adhesion and the resolution tend to be reduced.
• the photosensitive element 1 of the present invention includes a support 11, a photosensitive resin composition layer 12 formed on the support 11, and a photosensitive resin composition layer 12. It is sufficient to have at least
• a protective film 13 is further provided on the photosensitive resin composition layer 12 and on the surface opposite to the surface in contact with the support 11. It is good.
• the support (support film) 11 for example, a polymer film of polyethylene terephthalate, polypropylene, polyethylene, polyester, or the like can be used.
• the protective film for example, a polymer film such as polyethylene or polypropylene can be used.
• the thickness of the polymer film is preferably about 100 ⁇ m.
• the protective film 13 one having a smaller adhesive force between the photosensitive resin composition layer 12 and the protective film 13 than the adhesive force between the photosensitive resin composition layer 12 and the support 11 is preferable. She prefers a film of she-eye.
• a support having an intermediate layer such as a cushion layer, an adhesive layer, a light absorption layer, a gas barrier layer, or a protective layer on the polymer film may be used as the support.
• a photosensitive resin composition is applied on a support and dried. You can get S by doing
• the coating can be performed by a known method such as a roll coater, a comma coater, a dara via coater, an air knife coater, a die coater, and a bar coater. Drying can be performed at 70 to 150 ° C for about 5 to 30 minutes. Further, the amount of the residual organic solvent in the photosensitive resin composition layer is preferably 2% by weight or less from the viewpoint of preventing the diffusion of the organic solvent in the subsequent step.
• a protective film is further laminated as it is or on the surface of the photosensitive resin composition layer opposite to the surface in contact with the support to form a cylindrical core. It can be stored in rolls. In this case, it is preferable that the support is wound up so that it is the outermost side. It is preferable to install a moisture-proof end face separator on the end face of the roll-shaped photosensitive element roll wound around the core, from the viewpoint of edge fusion resistance, where it is preferable to install an end face separator in terms of end face protection. Further, as a packing method, it is preferable to wrap in a black sheet having low moisture permeability.
• Examples of the core include plastics such as polyethylene resin, polypropylene resin, polystyrene resin, polyvinyl chloride resin, and ABS resin (acrylonitrile butadiene styrene copolymer).
• plastics such as polyethylene resin, polypropylene resin, polystyrene resin, polyvinyl chloride resin, and ABS resin (acrylonitrile butadiene styrene copolymer).
• the method of forming a resist pattern using the photosensitive element includes a laminating step of laminating a photosensitive resin composition layer of the photosensitive element on a circuit-forming substrate, and a method of forming a layer of the photosensitive resin composition layer.
• the method includes at least an exposure step of irradiating a portion with light to form an exposed portion, and a developing step of removing a portion of the photosensitive resin composition layer other than the exposed portion.
• the method of laminating the photosensitive resin composition layer of the photosensitive element on the circuit-forming substrate in the laminating step includes, for example, after removing the protective film when the protective film is present, method of laminating Ri by the crimping pressure of the photosensitive resin composition layer 70- 130 ° 0. 1- 1 MPa about the circuit-forming board while heating to about C (1 one 1 Okgf Zcm 2 approximately) And the like.
• the above-mentioned lamination conditions are not particularly limited, and lamination can be performed under reduced pressure.
• the surface to be laminated is usually a metal surface, but is not particularly limited.
• Light is applied to a predetermined portion of the photosensitive resin composition layer on which the lamination in the exposure step is completed.
• the method for forming an exposed portion by irradiating a mask include a mask exposure method using a mask pattern, a laser direct writing exposure method, and an array of about 480,000 to 800,000 mirrors each having a size of 13 to 17 zm square.
• the photosensitive resin composition layer is irradiated with light after removing the support.
• Approximately 480,000 to 800,000 mirrors each having a size of 13-17 zm are arranged, and the angle of each mirror is changed as necessary, thereby performing exposure by a direct drawing method in which the exposure light becomes image-like.
• Methods include, for example, Texas Instruments' “Digital Light Processing” exposure method (DLP (Digital Light Processing)), Pentax's “Data 'Direct' Imaging” system, and BALL Conductor's “Maskless Lithography System ( Maskless Lithography System).
• the arranged mirrors that perform the core function of the direct writing method are called, for example, a “micromirror array”, a “two-dimensional display element”, a “DMD (Digital Mirror Device)”, and the like.
• a known light source that effectively emits ultraviolet light, visible light, or the like for example, a carbon arc lamp, a mercury vapor arc lamp, a high-pressure mercury lamp, a xenon lamp, an Ar ion laser, a semiconductor laser, or the like is used.
• a light source that emits a lot of light with a wavelength of 365 nm or less, such as a mercury lamp, is used as the exposure light use a filter with light of a wavelength of 365 nm or less90.
• a filter for cutting light having a wavelength of 365 nm or less for example, a sharp cut filter SCF-100S-39L manufactured by Sigma Koki Co., Ltd. can be used.
• a light source a gallium nitride based semiconductor laser and a blue laser are more preferable, and a gallium nitride based semiconductor laser and a blue laser are more preferable.
• the blue laser a gallium nitride blue laser is preferable.
• the laser light source is the exposure light
• Approximately 480,000-800,000 13-17 xm square mirrors are arranged, and the angle of each mirror is changed as necessary
• the method of performing exposure by the direct drawing method in which the exposure light becomes image-like is preferably performed by light having a wavelength of 400 to 450 ⁇ m, more preferably a light power S having a wavelength of 400 to 415 nm, and a wavelength of 400 to 410 nm. Light is particularly preferred.
• FIG. 3 is an oscillation spectrum diagram of a mercury lamp light source. When exposed as it is using a mercury lamp as a light source, the wavelength range of the light emitted is broad, as shown in Fig. 3. Light with a wavelength of less than 400nm, which is harmful to the human body and centered on light with a wavelength of 365nm (i-line). Irradiated.
• FIG. 4 is an oscillation spectrum diagram of a mercury lamp light source using a filter.
• a method for removing a portion other than the exposed portion of the photosensitive resin composition layer in the developing step for example, when a support is present on the photosensitive resin composition layer, And then developing by removing portions other than the exposed portions by wet development with a developer such as an alkaline aqueous solution, an aqueous developer, or an organic solvent, or dry development.
• a developer such as an alkaline aqueous solution, an aqueous developer, or an organic solvent, or dry development.
• a resist pattern is formed.
• the alkaline aqueous solution include a dilute solution of 0.1-5% by weight of sodium carbonate, a dilute solution of 0.1-5% by weight of potassium carbonate, a dilute solution of 0.1-5% by weight of sodium hydroxide, . 1-5% by weight of dilute sodium tetraborate solution.
• the pH of the alkaline aqueous solution is preferably in the range of 911, and the temperature is adjusted according to the developability of the photosensitive resin composition layer. Further, a surfactant, an antifoaming agent, an organic solvent, and the like may be mixed in the alkaline aqueous solution.
• Examples of the development method include a dipping method, a spray method, a brushing method, and a slapping method.
• the resist pattern may be further cured by heating at about 60 to 250 ° C. or exposing at about 0.2 to 10 j / cm 2 as necessary.
• the photosensitive element since the photosensitive element is used, good exposure and development can be performed, and a method of forming a resist pattern that is excellent in sensitivity and resolution and can obtain a desired resist shape can be performed. It becomes.
• the surface of the circuit-forming substrate is etched or plated using the resist pattern formed by the method of forming a resist pattern as a mask. Things.
• a cupric chloride solution, a ferric chloride solution, an alkaline etching solution or the like can be used.
• the plating method include copper plating, solder plating, nickel plating, and gold plating.
• the resist pattern can be removed, for example, with an aqueous solution that is more alkaline than the alkaline aqueous solution used for development.
• an aqueous solution that is more alkaline than the alkaline aqueous solution used for development for example, with an aqueous solution that is more alkaline than the alkaline aqueous solution used for development.
• the strong alkaline aqueous solution for example, an aqueous solution of 110% by weight of sodium hydroxide, an aqueous solution of 110% by weight of potassium hydroxide, or the like is used.
• the peeling method include an immersion method and a spray method.
• the printed wiring board on which the resist pattern is formed may be a multilayer printed wiring board having small diameter through holes.
• the above-mentioned method for manufacturing a printed wiring board uses the above-described method for forming a resist pattern.
• a printed wiring board having a high density and high power can be obtained with high throughput.
• the photosensitive element was obtained by uniformly applying the film on a tofilm (manufactured by Teijin Limited, product name: GS-16) and drying it with a hot air convection dryer at 100 ° C for 10 minutes.
• the thickness of the photosensitive resin composition layer was 24 xm.
• the OD value of the photosensitive resin composition layer with respect to the exposure wavelength was measured using a UV spectrophotometer (trade name: U-3310 spectrophotometer, manufactured by Hitachi, Ltd.).
• a photosensitive element consisting of a support film and a layer of the photosensitive resin composition is placed on the measurement side, a support film is placed on the reference side, and continuous measurement of light with a wavelength of 550-300 nm is performed in the absorbance mode. It was determined by reading the light and the value at 405 nm light.
• the copper surface of a copper-clad laminate (manufactured by Hitachi Chemical Co., Ltd., product name: MCL-E-67), which is a glass epoxy material with copper foil (thickness: 35 ⁇ m) laminated on both sides, It was polished using a polishing machine with a brush equivalent to # 600 (manufactured by Sankei Co., Ltd.), washed with water, and dried in an air stream.
• the photosensitive element obtained above was placed at 120 ° so that the photosensitive resin composition layer was in close contact with the surface of the copper-clad laminate.
• the layers were laminated under a pressure of 0.4 MPa at C.
• the polyethylene terephthalate surface had a density range of 0.000 to 2.00, a density step of 0.05, A photo tool with a 41-step tablet with a size of 20mm X 187mm, each step size 3 ⁇ 4mm X 12mm, and a line width / space width of 6 / 6—35 / 35 (unit: ⁇ ) as a negative for resolution evaluation
• a photo tool having a wiring pattern of is adhered, and a Sigma Koki Sharp Cut Filter SCF-100S-39L is placed on top of it to cut 99.5% or more of light with a wavelength of 365 nm or less.
• the number of remaining steps after development of the 41-step tablet was 14, 17, and 20 using a parallel light exposure machine (manufactured by Oak Manufacturing Co., Ltd., product name EXM-1201). Exposure was performed at different exposure doses. The sensitivity was defined as the exposure amount at which the number of remaining steps after development of the 41-step tablet was 17 steps.
• the measurement of the illuminance was performed on the light transmitted through the sharp cut filter using a UV illuminometer UIT-101 manufactured by Shio Electric Co., Ltd. to which a probe corresponding to a wavelength of 405 nm was applied, and the illuminance X exposure time was defined as the exposure amount.
• the resolution is such that the portion other than the exposed portion can be removed cleanly by the development process, and the line width between the generated line widths without meandering or chipping is the highest. It was evaluated by a small value. The smaller the value, the better the sensitivity and resolution evaluation.
• the cross-sectional shape of the developed resist was observed using a scanning electron microscope S-500A manufactured by Hitachi, Ltd.
• the cross-sectional shape of the resist is desirably close to a rectangle.
• Table 3 shows the data of the O.D. values, the sensitivity, the resolution, and the cross-sectional shape of the resist of the photosensitive elements of Examples 13 and 13 and Comparative Examples 1 and 2.
• the blending amount P [g] of 2,4-getylthioxanthone in the photosensitive resin composition, the thickness Q [ ⁇ m] of the photosensitive resin composition layer of the photosensitive element, The product R is also shown.
• Table 4 the components shown in Table 4 were mixed in the amounts shown in the table to obtain solutions of the photosensitive resin compositions of Examples 16 to 16 and Comparative Examples 3 and 4.
• Table 6 shows the amounts of 2,4-thioxanthone as the component (C).
• Component (A) was copolymerized at a weight ratio of 25/47/28.
• Table 7 shows the amount of oxanthon.
• Component (A) was copolymerized at a weight ratio of 25/47/28.
• the obtained solutions of the photosensitive resin compositions of Examples 417 and Comparative Examples 3-6 were applied to a 16 ⁇ m-thick polyethylene terephthalate film (manufactured by Teijin Limited, product name: GS-16).
• the photosensitive element was uniformly coated and dried with a hot air convection dryer at 100 ° C for 10 minutes to obtain a photosensitive element.
• the thickness of the photosensitive resin composition layer was 25 xm.
• the ⁇ D value of the photosensitive element composition layer in the obtained photosensitive element with respect to the exposure wavelength was measured in the same manner as in Example 1. Also, the sensitivity, resolution and resist shape were evaluated in the same manner as in Example 1 except that the obtained photosensitive element was used.
• the measurement of the illuminance of Examples 417 and Comparative Examples 3-6 was carried out by replacing the UV illuminometer UIT-101 manufactured by Shio Electric Co., Ltd. The measurement was carried out using a photodetector UVD-S405 in combination.
• Tables 6 and 7 show data on the OD value, sensitivity, resolution, and cross-sectional shape of the resist of the photosensitive elements of Examples 4 to 7 and Comparative Examples 3 to 6, respectively.
• the compounding amount P [g] of 2,4-getylthioxanthone in the photosensitive resin composition, the thickness Q [ ⁇ m] of the photosensitive resin composition layer of the photosensitive element, and the product R thereof are also shown.
• Example 4-17 in which the component (A) and the film thickness were changed with respect to Examples 13 to 13, the sensitivity and resolution were excellent, and the substantially rectangular shape was obtained. It was confirmed that the resist shape was obtained.
• the sensitivity was smaller than that of Examples 1-3, but this was due to the change in the measurement equipment used for measuring the illuminance and the amount of component (C) to be changed. It is considered to be.
• the photosensitive element of the present invention has excellent sensitivity and resolution particularly to exposure to light having a wavelength of 400 to 450 nm, and the cross-sectional shape of the developed resist is rectangular. Therefore, by using the photosensitive element of the present invention, a printed wiring board can be suitably manufactured.

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