WO2015178462A1 - Composition de résine photosensible et procédé de formation de tracé de circuit - Google Patents

Composition de résine photosensible et procédé de formation de tracé de circuit Download PDF

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Publication number
WO2015178462A1
WO2015178462A1 PCT/JP2015/064644 JP2015064644W WO2015178462A1 WO 2015178462 A1 WO2015178462 A1 WO 2015178462A1 JP 2015064644 W JP2015064644 W JP 2015064644W WO 2015178462 A1 WO2015178462 A1 WO 2015178462A1
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Prior art keywords
photosensitive resin
resin composition
compound
mass
exposure
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PCT/JP2015/064644
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English (en)
Japanese (ja)
Inventor
一也 内藤
隆之 松田
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旭化成イーマテリアルズ株式会社
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Application filed by 旭化成イーマテリアルズ株式会社 filed Critical 旭化成イーマテリアルズ株式会社
Priority to KR1020167027956A priority Critical patent/KR20160131084A/ko
Priority to JP2016521151A priority patent/JPWO2015178462A1/ja
Priority to KR1020197022465A priority patent/KR20190092622A/ko
Priority to CN202010587896.3A priority patent/CN111694218B/zh
Priority to CN201580025748.XA priority patent/CN106462068B/zh
Priority to KR1020217025400A priority patent/KR20210102494A/ko
Priority to KR1020227036070A priority patent/KR20220148301A/ko
Publication of WO2015178462A1 publication Critical patent/WO2015178462A1/fr

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    • 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
    • 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
    • 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
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10—Esters
    • C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
    • C08F222/106—Esters of polycondensation macromers
    • C08F222/1063—Esters of polycondensation macromers of alcohol terminated polyethers
    • 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
    • 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
    • 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
    • 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
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
    • 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
    • G03F7/20—Exposure; Apparatus therefor
    • G03F7/2051—Exposure without an original mask, e.g. using a programmed deflection of a point source, by scanning, by drawing with a light beam, using an addressed light or corpuscular source
    • G03F7/2053—Exposure without an original mask, e.g. using a programmed deflection of a point source, by scanning, by drawing with a light beam, using an addressed light or corpuscular source using a laser
    • G03F7/2055—Exposure without an original mask, e.g. using a programmed deflection of a point source, by scanning, by drawing with a light beam, using an addressed light or corpuscular source using a laser for the production of printing plates; Exposure of liquid photohardening compositions
    • 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
    • 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
    • H05K3/22—Secondary treatment of printed circuits
    • H05K3/28—Applying non-metallic protective coatings
    • H05K3/285—Permanent coating compositions
    • H05K3/287—Photosensitive compositions

Definitions

  • the present invention relates to a photosensitive resin composition that can be developed with an alkaline aqueous solution, and a circuit pattern forming method using the photosensitive resin composition. More specifically, the present invention relates to metal foil precision processing such as printed wiring board manufacturing, flexible printed wiring board manufacturing, IC chip mounting lead frame manufacturing, metal mask manufacturing, etc .; BGA (ball grid array), CSP (chip) Manufacturing of semiconductor packages such as size packages) Manufacturing of tape substrates typified by TAB (Tape Automated Bonding) and COF (Chip On Film: a semiconductor IC mounted on a film-like fine wiring board); Manufacturing of semiconductor bumps A photosensitive resin composition that provides a resist pattern suitable for the production of members such as ITO electrodes, address electrodes, and electromagnetic wave shields in the field of flat panel displays, and a circuit pattern forming method using the photosensitive resin composition.
  • metal foil precision processing such as printed wiring board manufacturing, flexible printed wiring board manufacturing, IC chip mounting lead frame manufacturing, metal mask manufacturing, etc .
  • BGA ball grid array
  • the photosensitive resin composition used for the photolithography method is classified into a negative composition and a positive composition.
  • the photolithography method using the negative photosensitive resin composition is performed, for example, as follows: A negative photosensitive resin composition is applied onto the substrate, and pattern exposure is performed to polymerize and cure the exposed portion of the photosensitive resin composition. Next, the unexposed portion is removed with a developing solution to form a resist pattern on the substrate. Furthermore, after a conductor pattern is formed by performing etching or plating treatment, the conductor pattern is formed on the substrate by peeling and removing the resist pattern from the substrate.
  • photosensitive resin layer a layer comprising a support and a photosensitive resin composition (hereinafter referred to as “photosensitive resin layer”), and if necessary, a protective layer. Any method of laminating the photosensitive resin layer on the substrate using the sequentially laminated photosensitive resin laminate is used. In the production of a printed wiring board, the latter method is often used.
  • the protective layer is peeled from the photosensitive resin laminate.
  • the photosensitive resin layer and the support are laminated on a substrate such as a copper clad laminate so that the substrate, the photosensitive resin layer, and the support are in this order.
  • the photosensitive resin layer is exposed through a photomask having a desired wiring pattern, and the exposed portion is polymerized and cured.
  • the support is peeled off. And a resist pattern is formed on a board
  • the protective layer include a polyethylene film;
  • the support include a polyethylene terephthalate film;
  • the developer include an aqueous solution having weak alkalinity; Each is preferably used.
  • the step of dissolving or dispersing and removing the photosensitive resin layer in the unexposed portion with the above developer is called a development step.
  • a development step Each time this development process is repeated, the amount of unexposed portion of the photosensitive resin composition dissolved in the developer increases. Therefore, when the development process is repeated, the foamability of the developer tends to increase. This foaming property of the developer significantly reduces the working efficiency in the development process.
  • etching process or a pattern plating process is performed using the resist pattern formed through the above development process as a protective mask.
  • the resist pattern is peeled from the substrate to manufacture a substrate having a conductor pattern (that is, a printed wiring board).
  • Patent Documents 1 and 2 describe a photosensitive resin composition containing a specific alkali-soluble polymer, a monomer, and a photopolymerizable initiator. It is described that high sensitivity and high resolution are realized.
  • Patent Document 3 reports means for using polyalkylene alcohol as an additive of the photosensitive resin composition in order to suppress the foamability of the developer.
  • the finished line width of a conductor line after etching (for example, a copper line) can be stably produced.
  • the resist width after development is stable.
  • a minute bottoming phenomenon often referred to as “resist bottom” is observed at the bottom of the resist after development (see FIG. 1).
  • the presence of the resist skirt is a factor in varying the width of the conductor line after etching.
  • the presence of the resist skirt greatly affects the adhesion of the obtained conductor pattern to the substrate in the manufacturing method in which the conductor pattern is formed by pattern plating.
  • DI exposure is an exposure method by scanning a laser spot.
  • the irradiation intensity of the laser spot follows a Gaussian distribution. For this reason, regions with low exposure amounts (weak exposure regions) are generated at both ends of the exposure pattern.
  • the cured resist in the weakly exposed region is partially dissolved in the subsequent development process because the resistance to the developer is lowered.
  • the dissolution residue at this time settles and deposits on the bottom of the resist, and it is considered that a resist skirt is generated.
  • This weak exposure area is a problem peculiar to DI using spot multiple exposure. More importantly, since the width of the faint light region is determined as a fixed value, the problem becomes more apparent as the design line width becomes narrower.
  • Each exposure machine manufacturer is working on improving the laser spot diameter and the resolution between spots in order to improve the resolution. However, the current situation is that the performance of the exposure machine has not kept pace with the demanded specifications of printed circuit boards.
  • Patent Document 3 Japanese Patent Laid-Open No. 2012-159651. Has been.
  • Patent Document 3 since the density of the monomer is reduced by the addition of the antifoaming agent, the efficiency of photopolymerization by exposure tends to decrease and the sensitivity tends to decrease.
  • the present invention uses a photosensitive resin composition for direct imaging, which is excellent in stability of a conductor line width after etching, adhesion of a conductor line after plating, or both, and the photosensitive resin composition. It is an object to provide a method for forming a circuit pattern.
  • the present inventors have intensively studied and repeated experiments. As a result, the inventors have found that the above-described problems can be solved by the following technical means, and have completed the present invention.
  • the present invention discloses the following embodiments.
  • a photosensitive resin composition comprising: Forming a photosensitive resin layer having a thickness of 25 ⁇ m comprising the photosensitive resin composition on the substrate surface; The resist base width of the resist pattern obtained by performing exposure and development under the condition that the position of the focal point at the time of exposure is shifted from the substrate surface to the inside of the substrate by 200 ⁇ m in the thickness direction of the substrate is 0.01 ⁇ m to 3.5 ⁇ m, and The photosensitive resin composition, which is used for direct imaging exposure.
  • a photosensitive resin layer having a thickness of 25 ⁇ m made of the photosensitive resin composition is formed on the substrate surface, exposed using a stove 21-step tablet as a mask, and then developed, so that the maximum number of remaining film steps is 6.
  • P ⁇ Q / where Q is the average number of ethylenic double bonds in the compound (C) and P is the reaction rate of ethylenic double bonds in the compound (C) after the exposure.
  • a photosensitive resin layer having a thickness of 25 ⁇ m made of the photosensitive resin composition is formed on the substrate surface, exposed using a stove 21-step step tablet as a mask, and then developed.
  • P ′ is the reaction rate of ethylenic double bonds in the compound (C) after the exposure.
  • the compound (C) is represented by the following general formula (IV): ⁇ Wherein n 1 , n 2 , n 3 , and n 4 each independently represents an integer of 1 to 25, and n 1 + n 2 + n 3 + n 4 is an integer of 9 to 60, R 1 , R 2 , R 3 , and R 4 each independently represents an alkyl group, R 5 , R 6 , R 7 , and R 8 each independently represent an alkylene group, and when there are a plurality of R 5 , R 6 , R 7 , and R 8 , respectively, the plurality of R 5 , R 6 , R 7 and R 8 may be the same as or different from each other.
  • the photosensitive resin composition according to any one of [1] to [6], comprising a compound represented by the formula:
  • a photosensitive resin composition comprising: The photosensitive resin composition, wherein the compound (C) includes a compound having three or more methacryloyl groups in one molecule.
  • a photosensitive resin layer having a thickness of 25 ⁇ m made of the photosensitive resin composition is formed on the substrate surface, exposed using a stove 21-step tablet as a mask, and then developed, so that the maximum number of remaining film steps is 6.
  • P ⁇ Q / where Q is the average number of ethylenic double bonds in the compound (C) and P is the reaction rate of ethylenic double bonds in the compound (C) after the exposure.
  • a photosensitive resin layer having a thickness of 25 ⁇ m formed of the photosensitive resin composition is formed on the substrate surface, exposed using a stove 21-step tablet as a mask, and then developed, so that the maximum number of remaining film steps is 6.
  • P ′ is the reaction rate of ethylenic double bonds in the compound (C) after the exposure.
  • the photosensitive resin composition as described in [14] or [15] whose Q / 100 value is 0.3 or more.
  • the compound (C) is represented by the following general formula (IV): ⁇ Wherein n 1 , n 2 , n 3 , and n 4 each independently represents an integer of 1 to 25, and n 1 + n 2 + n 3 + n 4 is an integer of 9 to 60, R 1 , R 2 , R 3 , and R 4 each independently represents an alkyl group, R 5 , R 6 , R 7 , and R 8 each independently represent an alkylene group, and when there are a plurality of R 5 , R 6 , R 7 , and R 8 , respectively, the plurality of R 5 , R 6 , R 7 and R 8 may be the same or different from each other.
  • the photosensitive resin composition according to any one of [14] to [17], comprising a compound represented by the formula:
  • a step of forming a layer of the photosensitive resin composition according to any one of [1] to [26] on a substrate A method for forming a circuit pattern, comprising: a step of exposing and developing the layer of the photosensitive resin composition to form a resist pattern; and a step of etching or plating the substrate on which the resist pattern is formed. . [28] The method according to [27], wherein the exposure is performed by direct imaging exposure.
  • the present invention suppresses the generation of resist skirts, thereby improving the width of a conductor line (for example, a copper line) after etching and the adhesion of a conductor line after plating, and forming a circuit pattern by a direct imaging method. It is possible to provide a photosensitive resin composition that can be suitably applied to the present invention, and a method for forming a circuit pattern using the photosensitive resin composition.
  • FIG. 1 is a schematic cross-sectional view for explaining the definition of the resist skirt width.
  • Photosensitive resin composition One embodiment is: (A) Alkali-soluble polymer: 40 to 80% by mass, (B) Photopolymerization initiator: 0.1 to 20% by mass, (C) Compound having ethylenic double bond: 5 to 50% by mass, A photosensitive resin composition comprising: Forming a photosensitive resin layer having a thickness of 25 ⁇ m comprising the photosensitive resin composition on the substrate surface; The resist base width of the resist pattern obtained by performing exposure and development under the condition that the position of the focal point at the time of exposure is shifted from the substrate surface to the inside of the substrate by 200 ⁇ m in the thickness direction of the substrate is 0.01 ⁇ m to 3.5 ⁇ m, and Provided is the photosensitive resin composition (photosensitive resin composition for direct imaging exposure), which is used for direct imaging exposure.
  • a photosensitive resin composition comprising: The (C) compound includes a compound having 3 or more methacryloyl groups in one molecule, and provides the photosensitive resin composition.
  • the photosensitive resin composition for direct imaging exposure of the present disclosure is a composition in which a resist pattern obtained by exposure and development under the above conditions gives the specific resist skirt width.
  • a photosensitive resin layer made of a photosensitive resin composition having a thickness of 25 ⁇ m is formed on the substrate surface, and exposure and development are performed under the condition that the focal position during exposure is shifted from the substrate surface to the inside of the substrate by 200 ⁇ m in the thickness direction of the substrate.
  • the resist skirt width of the resist pattern obtained by performing the process of 0.01 ⁇ m to 3.5 ⁇ m is a requirement that contributes to reducing the variation in the width of the conductor line after etching and improving the adhesion of the conductor line after plating It is.
  • a resist skirt width of 0.01 ⁇ m or more is advantageous from the viewpoint of improving the adhesion of the cured resist; this value of 3.5 ⁇ m or less reduces variations in conductor line width after etching. It is advantageous from the viewpoint of improving the adhesion of the conductor line after plating.
  • the resist skirt width is preferably 0.02 ⁇ m or more, more preferably 0.03 ⁇ m or more, preferably 2.5 ⁇ m or less, more preferably 2.0 ⁇ m or less, still more preferably 1.5 ⁇ m or less, and particularly preferably 1. 2 ⁇ m or less, most preferably 1 ⁇ m or less. More specific procedures for the exposure and development described above follow the method described in the section of [Example] or a method understood by those skilled in the art to be equivalent thereto.
  • the specific resist skirt width described above can be realized by using the components (A) to (C) in specific ratios, and by means (for example, but not limited to) exemplified below. Understood. Hereinafter, each component contained in the photosensitive resin composition of this Embodiment is demonstrated in order.
  • the (A) alkali-soluble polymer in the present embodiment is a polymer that can be dissolved in an alkaline aqueous solution.
  • a vinyl polymer containing a carboxy group is exemplified, and a copolymer of monomers selected from (meth) acrylic acid, (meth) acrylic acid ester, (meth) acrylonitrile, (meth) acrylamide and the like is preferable.
  • the alkali-soluble polymer preferably contains a carboxyl group and has an acid equivalent of 100 to 600. The acid equivalent refers to the mass in grams of an alkali-soluble polymer having 1 equivalent of a carboxyl group therein.
  • the acid equivalent is measured by a potentiometric titration method using a 0.1 mol / L sodium hydroxide aqueous solution using a titration device (for example, Hiranuma Automatic Titration Device (COM-555) manufactured by Hiranuma Sangyo Co., Ltd.). it can.
  • a titration device for example, Hiranuma Automatic Titration Device (COM-555) manufactured by Hiranuma Sangyo Co., Ltd.
  • COM-555 Hiranuma Automatic Titration Device manufactured by Hiranuma Sangyo Co., Ltd.
  • the weight average molecular weight of the alkali-soluble polymer is preferably 5,000 or more and 500,000 or less.
  • a weight average molecular weight of 5,000 or more is preferable from the viewpoint of the properties of the development aggregate, and from the viewpoint of the properties of the unexposed film such as edge fuse properties and cut chip properties in the photosensitive resin laminate, Setting the weight average molecular weight to 500,000 or less is preferable from the viewpoint of improving the solubility in a developer.
  • the edge fuse property is a property that suppresses the phenomenon that the photosensitive resin composition layer protrudes from the end face of the roll when the photosensitive resin laminate is wound into a roll.
  • the cut chip property is a property that suppresses a phenomenon that a chip flies when an unexposed film is cut with a cutter. If the cut chip property is poor, the scattered chips adhere to, for example, the upper surface of the photosensitive resin laminate, and the chip is transferred to a mask in a subsequent exposure process, causing defects.
  • the weight average molecular weight of the alkali-soluble polymer is more preferably from 5,000 to 300,000, still more preferably from 10,000 to 200,000.
  • the alkali-soluble polymer preferably has an aromatic hydrocarbon group.
  • An aromatic hydrocarbon group can be introduced into the (A) alkali-soluble polymer by using an aromatic vinyl compound, a (meth) acrylate compound having a benzyl group, or the like as a part of the monomer used in the synthesis.
  • the alkali-soluble polymer can be obtained by copolymerizing one or more monomers from the following two types of monomers.
  • the first monomer is a carboxylic acid or acid anhydride having one polymerizable unsaturated group in the molecule. Examples include (meth) acrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, maleic anhydride, maleic acid half ester, and the like.
  • (meth) acrylic acid is preferable.
  • (meth) acryl means acryl or methacryl.
  • the copolymerization ratio of the first monomer in the alkali-soluble polymer can be easily calculated from the desired acid equivalent value in the alkali-soluble polymer.
  • the copolymerization ratio of the first monomer in the alkali-soluble polymer is preferably 10 to 50% by mass based on the total mass of all monomer components. Setting the copolymerization ratio to 10% by mass or more is preferable from the viewpoint of developing good developability and controlling the edge fuse property. Setting the copolymerization ratio to 50% by mass or less is preferable from the viewpoint of improving the resolution and suppressing the generation of the resist tail, and in these viewpoints, 30% by mass or less is more preferable, and 25% by mass. % Or less is more preferable, and 20% by mass or less is particularly preferable.
  • the second monomer is non-acidic and has at least one polymerizable unsaturated group in the molecule.
  • aromatic vinyl compound examples include styrene and styrene derivatives.
  • methyl (meth) acrylate, n-butyl (meth) acrylate, styrene, styrene derivatives, and benzyl (meth) acrylate are preferred as the second monomer.
  • styrene, a styrene derivative, and benzyl (meth) acrylate are particularly preferable from the viewpoints of improved resolution, improved adhesion, good development aggregation (small amount of aggregate), and etching resistance.
  • the copolymer component in the alkali-soluble polymer aromatic monomers such as aromatic vinyl compounds and (meth) acrylate compounds having a benzyl group can be used.
  • the copolymerization ratio of the aromatic monomer compound in the alkali-soluble polymer is preferably 20 to 85% by mass based on the total mass of all monomer components. Setting the copolymerization ratio to 20% by mass or more is preferable from the viewpoints of improving resolution and adhesion, suppressing the generation of aggregates during development, and improving etching resistance, and is 25% by mass or more. More preferably, it is more preferably 30% by mass or more, and particularly preferably 40% by mass or more.
  • the copolymerization ratio to 85% by mass or less is preferable from the viewpoint of developing appropriate developability.
  • an aromatic vinyl compound is more preferable
  • the copolymerization ratio in the alkali-soluble polymer is 20 to 70% by mass based on the total mass of all monomer components. preferable.
  • Setting the copolymerization ratio to 20% by mass or more is preferable from the viewpoint of improving resolution, improving adhesion, developing cohesiveness, etching resistance, etc., and more preferably 25% by mass or more. 30% by mass or more, more preferably 40% by mass or more.
  • Setting the copolymerization ratio to 70% by mass or less is preferable from the viewpoint of expressing appropriate developability and cured film flexibility, and more preferably 60% by mass or less.
  • the copolymerization ratio of the aromatic vinyl compound is more preferably 20 to 50% by mass, and particularly preferably 20 to 30% by mass.
  • examples of the aromatic vinyl compound include styrene and styrene derivatives.
  • examples of the styrene derivative include oxystyrene, hydroxystyrene, acetoxystyrene, alkyl styrene, halogenoalkyl styrene and the like.
  • the alkali-soluble polymer is preferably a copolymer of a monomer mixture containing styrene or a styrene derivative, methyl (meth) acrylate, and (meth) acrylic acid as a copolymerization monomer.
  • the copolymerization ratio of the aromatic vinyl compound is preferably 40 to 60% by mass based on the total mass of all monomer components.
  • the copolymerization monomer preferably contains styrene or a styrene derivative and methyl (meth) acrylate and / or (meth) acrylic acid.
  • the weight average value Tg total of Tg of the alkali-soluble polymer (A) in the photosensitive resin composition can be in the range of 30 to 125 ° C., preferably 50 to 110 ° C. Yes, more preferably 50 to 105 ° C, and still more preferably 50 to 90 ° C. Setting the weight average value of Tg to 30 ° C. or higher is preferable from the viewpoint of controlling the edge fuse property, and setting it to 110 ° C. or lower is preferable from the viewpoint of suppressing the occurrence of the resist tail.
  • W i is the solid mass of each alkali-soluble polymer
  • Tg i is the glass transition temperature determined by the Fox equation for each of the alkali-soluble polymer
  • W total is the total value of the solid mass of each alkali-soluble polymer.
  • the glass transition temperature Tg i for each of the alkali-soluble polymer when determined by the Fox equation it is necessary to Tg of a homopolymer made of comonomers to form each alkali-soluble polymer.
  • the mechanism by which the resist skirt in DI exposure is suppressed by using the (A) alkali-soluble polymer having the above composition is considered as follows.
  • the present invention is not limited to the following theory.
  • DI exposure weak exposure areas occur on both sides of the exposure pattern.
  • the reaction rate of the resist in the weakly exposed region is lowered.
  • the hardened resist in the region has a lower resistance to the developer and is partially dissolved in the subsequent development process. It is presumed that a resist bottom is generated when the dissolution residue at this time settles and accumulates at the bottom of the resist. Therefore, in order to suppress the occurrence of the resist tail, it is considered that the monomer in the resist needs to be efficiently cured even in the weakly exposed region.
  • the monomer reaction rate is affected by the diffusion rate between the monomers, and the diffusion rate is considered to be governed by the free volume in the resist. From the above, by designing the composition and structure of (A) the alkali-soluble polymer so that the free volume in the resist is increased, the reaction rate of the monomer can be improved and the resist tail in the weakly exposed region can be suppressed. it is conceivable that.
  • the glass transition temperature Tg is used as an index of free volume.
  • Tg is the temperature at which the proportion of free volume in the total volume of the polymer begins to increase. Therefore, it is considered that the free volume increases in proportion to the temperature difference from Tg at temperatures above Tg. Under the same temperature condition, the higher the Tg of the substance, the smaller the free volume, and the lower the Tg, the larger the free volume. Therefore, it is considered that a resist composition having a high Tg tends to reduce the monomer reaction rate and thus generates a resist skirt, and a resist composition having a low Tg suppresses the generation of the resist skirt.
  • the weight average value Tg total of Tg of the alkali-soluble polymer (A) is low, but it is preferable that Tg total is high considering the control of edge fuse property.
  • Tg total is high considering the control of edge fuse property.
  • the blending amount of the (A) alkali-soluble polymer in the photosensitive resin composition is 40 to 80% by mass when the total solid content mass of the photosensitive resin composition is 100% by mass.
  • the content is preferably in the range, more preferably 50 to 70% by mass. Setting the blending amount to 40% by mass or more is advantageous from the viewpoint of controlling the edge fuse property, while setting the blending amount to 80% by mass or less is advantageous from the viewpoint of controlling the development time. is there.
  • (B) the photopolymerization initiator various substances that can be used as the photopolymerization initiator of the photosensitive resin can be used.
  • the (B) photopolymerization initiator in the present embodiment for example, one or more selected from the group consisting of acridine compounds, N-aryl- ⁇ -amino acid compounds, and triarylimidazole dimers are used. Can do.
  • the acridine-based compound is preferable from the viewpoint of developing high sensitivity, and from the viewpoint of achieving both high sensitivity and suppression of occurrence of the bottom of the resist;
  • the triarylimidazole dimer is preferable from the viewpoint of more reliably suppressing the occurrence of the bottom of the resist.
  • acridine compound examples include 1,7-bis (9,9′-acridinyl) heptane, 9-phenylacridine, 9-methylacridine, 9-ethylacridine, 9-chloroethylacridine, 9-methoxyacridine, 9 -Ethoxy acridine, 9- (4-methylphenyl) acridine, 9- (4-ethylphenyl) acridine, 9- (4-n-propylphenyl) acridine, 9- (4-n-butylphenyl) acridine, 9- (4-tert-butylphenyl) acridine, 9- (4-methoxyphenyl) acridine, 9- (4-ethoxyphenyl) acridine, 9- (4- (4-acetylphenyl) acridine, 9- (4-dimethylaminophenyl) acridine 9-
  • N-aryl- ⁇ -amino acid compounds examples include N-phenylglycine, N-methyl-N-phenylglycine, and N-ethyl-N-phenylglycine.
  • N-phenylglycine is preferable because of its high sensitizing effect.
  • triarylimidazole dimer examples include 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer and 2- (o-chlorophenyl) -4,5-di (methoxyphenyl) imidazole dimer.
  • the acridine compound is more sensitive than the triarylimidazole dimer compound. Furthermore, when a urethane compound is used as the compound having (C) an ethylenic double bond, it is preferable in combination with this in that both foamability and development aggregation are suppressed. N-phenylglycine and its derivatives are preferable in terms of improving sensitivity. In particular, when N-phenylglycine or a derivative thereof is used in combination with an acridine compound, it is preferable in that the occurrence of resist tails can be more reliably suppressed.
  • the photopolymerization initiator is It is preferable to include one or more selected from the group consisting of acridine compounds, N-phenylglycine, and N-phenylglycine derivatives.
  • acridine compound the following formula (I): 9-phenylacridine represented by the following general formula (II): (Wherein R 1 represents an alkylene group having 1 to 12 carbon atoms) It is preferable that 1 or more types selected from the group which consists of a compound represented by these are included. These compounds are advantageous from the viewpoint of improving sensitivity in DI exposure. It is advantageous from the viewpoint of solubility that the carbon number of R 1 in the general formula (II) is 1 to 12. More preferably, R 1 has 4 to 10 carbon atoms.
  • the acridine compound it is preferable to use 9-phenylacridine represented by the above formula (I).
  • photopolymerization initiator (B) in the present embodiment only one or more selected from the group consisting of acridine compounds, N-phenylglycine or derivatives thereof, and triarylimidazole dimers may be used. However, it may further contain a photopolymerization initiator other than these.
  • (B) As a further example of the photopolymerization initiator, for example, Benzophenone, N, N′-tetramethyl-4,4′-dimethylaminobenzophenone (Michler ketone), N, N′-tetraethyl-4,4′-diaminobenzophenone, 4-methoxy-4′-dimethylaminobenzophenone, 2- Aromatic ketones such as benzyl-2-dimethylamino-1- (4-monofornophenyl) -butanone-1,2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propanone-1; 2-ethylanthraquinone, phenanthrenequinone, 2-tert-butylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, 2,3-benzanthraquinone, 2-phenylanthraquinone
  • the blending amount of the photopolymerization initiator (B) in the photosensitive resin composition is 0.1 to 20% by mass when the total solid mass of the photosensitive resin composition is 100% by mass.
  • Making the blending amount 0.1% by mass or more is based on the viewpoint of obtaining an exposure pattern having a sufficient remaining film ratio after development, while making the blending amount 20% by mass or less. Is based on the viewpoint of sufficiently transmitting light to the bottom surface of the resist to obtain high resolution, and the viewpoint of suppressing development aggregation in the developer.
  • a preferable range of the blending amount is 0.3 to 10% by mass.
  • the blending amount of the acridine compound is preferably 0.01% by mass to 5% by mass with respect to the total solid mass of the photosensitive resin composition.
  • the blending amount of 0.01% by mass or more is preferable from the viewpoint of obtaining good sensitivity.
  • the blending amount is more preferably 0.1% by mass or more, and particularly preferably 0.2% by mass or more.
  • the blending amount is more preferably 3% by mass or less, and particularly preferably 2% by mass or less.
  • the content of the N-aryl- ⁇ -amino acid compound is 0. 001 mass% to 5 mass% is preferable. Setting the amount to 0.001% by mass or more is preferable from the viewpoint of obtaining good sensitivity. In particular, when this N-aryl- ⁇ -amino acid compound is used in combination with an acridine compound, it is preferable in that the occurrence of resist tails can be more reliably suppressed.
  • the blending amount is more preferably 0.01% by mass or more, further preferably 0.05% by mass or more, and particularly preferably 0.1% by mass or more.
  • the blending amount is more preferably 1% by mass or less, and particularly preferably 0.5% by mass or less.
  • the content of the triarylimidazole dimer is from 0.1% by mass to the total solid mass of the photosensitive resin composition. It is preferable that it is 15 mass%.
  • the blending amount of 0.1% by mass or more is preferable from the viewpoint of obtaining good sensitivity.
  • the blending amount is more preferably 1% by mass or more, and particularly preferably 3% by mass or more.
  • the blending amount is 15% by mass or less from the viewpoint of obtaining high resolution and suppressing aggregation in the developer.
  • the blending amount is more preferably 10% by mass or less, and particularly preferably 6% by mass or less.
  • the photosensitive resin composition contains the compound which has (C) ethylenic double bond.
  • a preferred example of this compound is a compound (polyfunctional monomer) having a tri- or higher functional methacrylate group (three or more methacryloyl groups in one molecule) and a molecular weight of 500 g / mol to 5,000 g / mol. Is mentioned.
  • (C) As a compound the compound which has a tetrafunctional or more methacrylate group (4 or more methacryloyl group in 1 molecule) is more preferable.
  • the mechanism by which the resist tail in DI exposure is suppressed by using the compound (C) is considered as follows.
  • the present invention is not limited to the following theory. As described above, in the DI exposure, weak exposure areas are generated on both sides of the exposure pattern. Then, it is presumed that when the reaction rate of the resist existing in this region is lowered, the resistance to the developer is lowered and a resist tail is generated. Therefore, in order to suppress the occurrence of the resist tail, it is necessary to increase the cross-linking density by increasing the reaction rate of the compound (C) and improve the developer resistance even in the weakly exposed region. In order for the resist to crosslink, after one double bond in one polyfunctional monomer reacts, another unreacted double bond in the same monomer needs to react further. Therefore, the crosslinking density increases as the compound (C) has many double bonds and the fewer unreacted double bonds remaining after exposure.
  • the polyfunctional monomer in which the double bond has reacted even once is incorporated into the high molecular weight growing polymer chain. Therefore, in order for two or more double bonds in the polyfunctional monomer molecule to react, the double bond hanging from the growing polymer chain needs to react with another monomer or the growing polymer. This reaction is disadvantageous because of its great steric hindrance. In order to reduce the steric hindrance of the reaction and promote the reaction, it is necessary to increase the length of the molecular chain between the double bonds in the compound (C). Therefore, the one where the molecular weight of (C) compound is larger is preferable. On the other hand, when the molecular weight is excessively high, the reaction rate of the double bond of the compound (C) is improved, but the amount of the double bond in the composition is lowered. Therefore, also in this case, the crosslinking density is lowered.
  • the compound (C) in the present embodiment has an optimum molecular weight and a range of the number of functional groups.
  • the molecular weight of the compound is preferably 500 g / mol to 5,000 g / mol, more preferably 600 g / mol to 4,000 g / mol, and still more preferably 700 g / mol to 3,000 g / mol. is there.
  • the number of functional groups in the compound is preferably 3 or more, more preferably 4 or more, from the viewpoint of improving the crosslinking density, improving the resolution and adhesion, and suppressing the generation of the resist tail. It is. From the viewpoint of controlling the edge fuse property, trifunctional or more is preferable, and tetrafunctional or more is more preferable. Moreover, from a viewpoint of peeling characteristics, 10 functional or less is preferable, 6 functional or less is more preferable, 5 functional or less is further more preferable, and 4 functional or less is especially preferable. Therefore, tetrafunctionality is most preferable in order to exhibit all of improvement in resolution, suppression of occurrence of resist skirt, control of edge fuse property, and peeling characteristics at a high level.
  • a methacrylate monomer having low hydrolyzability is effective.
  • the methacrylate monomer is excellent in terms of improving resolution and adhesion, suppressing the occurrence of resist tails, and controlling edge fuse properties.
  • the photosensitive resin composition (C) is a compound having an ethylenic double bond represented by the following general formula (III): ⁇ Wherein n 1 , n 2 and n 3 are each independently an integer of 1 to 25, provided that n 1 + n 2 + n 3 is an integer of 3 to 75, R 1 , R 2 , and R 3 are each independently an alkyl group. ⁇ Is preferably included.
  • the value of n 1 + n 2 + n 3 is preferably 3 or more and 50 or less. It is preferable that n 1 + n 2 + n 3 is 3 or more from the viewpoint of suppressing the generation of the resist skirt, from the viewpoint of imparting flexibility to the cured film, and from the viewpoint of improving the tent film puncture resistance. It is preferable that 1 + n 2 + n 3 is 50 or less from the viewpoint of obtaining high resolution and adhesion, and good peeling characteristics. A more preferable range of n 1 + n 2 + n 3 is 6 or more and 40 or less, and a more preferable range is 9 or more and 30 or less.
  • Specific examples of the compound represented by the general formula (III) include Trimethacrylate having an average of 3 moles of ethylene oxide added to the end of the hydroxyl group of trimethylolpropane; Trimethacrylate having an average of 9 moles of ethylene oxide added to the terminal of the hydroxyl group of trimethylolpropane; Trimethacrylate obtained by adding an average of 15 moles of ethylene oxide to the terminal of the hydroxyl group of trimethylolpropane; Examples include trimethacrylate obtained by adding an average of 30 moles of ethylene oxide to the terminal of the hydroxyl group of trimethylolpropane.
  • the photosensitive resin composition has the following general formula (IV) as a compound having (C) an ethylenic double bond: ⁇ Wherein n 1 , n 2 , n 3 , and n 4 each independently represents an integer of 1 to 25, and n 1 + n 2 + n 3 + n 4 is an integer of 4 to 100, R 1 , R 2 , R 3 , and R 4 each independently represents an alkyl group, R 5 , R 6 , R 7 , and R 8 each independently represent an alkylene group, and when there are a plurality of R 5 , R 6 , R 7 , and R 8 , respectively, the plurality of R 5 , R 6 , R 7 and R 8 may be the same or different from each other.
  • ⁇ Is preferably included. It is preferable that the compound represented by these is included.
  • n 1 + n 2 + n 3 + n 4 is preferably 9 or more and 60 or less. It is preferable that n 1 + n 2 + n 3 + n 4 is 9 or more from the viewpoint of suppressing the occurrence of the resist skirt, improving the tent film puncture resistance, and imparting flexibility to the cured film, It is preferable to set n 1 + n 2 + n 3 + n 4 to 60 or less from the viewpoints of improving resolution and adhesion, obtaining good peeling characteristics, and controlling edge fuse properties.
  • n 1 + n 2 + n 3 + n 4 is 9 or more and 40 or less
  • a further preferable range is 15 or more and 40 or less
  • a particularly preferable range is 15 or more and 28 or less.
  • R 5 , R 6 , R 7 and R 8 in the general formula (IV) can each be 1,2-ethylene group, 1,2-propylene group, butylene group, etc. From the viewpoint of imparting flexibility, improving the tent film puncture resistance, suppressing the development aggregation property, and increasing the reactivity of the ethylenic double bond, a 1,2-ethylene group is preferable.
  • the compound represented by the general formula (IV) is preferably the following general formula (V): [Wherein, n 1 , n 2 , n 3 and n 4 are each independently an integer of 1 to 25, provided that n 1 + n 2 + n 3 + n 4 is an integer of 4 to 100 and R 1 , R 2 , R 3 , and R 4 are each independently an alkyl group. ⁇ It is a compound represented. The preferred range of n 1 + n 2 + n 3 + n 4 is the same as described above.
  • Specific examples of the compound represented by the general formula (IV) include, for example, Tetramethacrylate having an average of 9 moles of ethylene oxide added to the end of the hydroxyl group of pentaerythritol, Tetramethacrylate having an average of 12 moles of ethylene oxide added to the end of the hydroxyl group of pentaerythritol, Tetramethacrylate having an average of 15 moles of ethylene oxide added to the end of the hydroxyl group of pentaerythritol, Tetramethacrylate having an average of 20 moles of ethylene oxide added to the end of the hydroxyl group of pentaerythritol, Tetramethacrylate having an average of 28 moles of ethylene oxide added to the terminal of the hydroxyl group of pentaerythritol, Examples include tetramethacrylate in which an average of 35 mol of ethylene oxide is added to the terminal of the hydroxyl group of pentaerythritol.
  • the photosensitive resin composition has the following general formula (VI) as a compound having (C) an ethylenic double bond: ⁇ Wherein R 3 and R 4 are each independently a hydrogen atom or a methyl group; n 9 and n 11 are each independently an integer from 0 to 20 and n 9 + n 11 is an integer from 0 to 20; n 8 and n 10 are each independently an integer from 1 to 20 and n 8 + n 10 is an integer from 2 to 20; The sequence of repeating units of — (C 2 H 4 O) — and — (C 3 H 6 O) — may be random or block, and — (C 2 H 4 O) — and — ( Any of C 3 H 6 O) — may be bonded to the bisphenol structure. ⁇ Is preferably included.
  • n 8 + n 9 + n 10 + n 11 is preferably 2 or more and 40 or less.
  • Setting n 8 + n 9 + n 10 + n 11 to 2 or more is preferable from the viewpoint of obtaining flexibility of the cured film, while setting n 8 + n 9 + n 10 + n 11 to 40 or less results in improved resolution. From the viewpoint of obtaining.
  • a more preferable range of n 8 + n 9 + n 10 + n 11 is 4 or more and 20 or less, and a more preferable range is 6 or more and 12 or less.
  • n 8 + n 9 + n 10 + n 11 is 16 or more and 40 or less, and a more preferable range is 30 or more and 40 or less. It is more preferable that n 9 + n 11 is an integer of 1 to 20, and n 8 + n 10 is an integer of 2 to 20.
  • Specific examples of the compound represented by the general formula (VI) include, for example, Dimethacrylate of ethylene glycol with an average of 2 moles of ethylene oxide added to both ends of bisphenol A, Dimethacrylate of ethylene glycol with an average of 5 moles of ethylene oxide added to both ends of bisphenol A, Dimethyl methacrylate of alkylene glycol in which an average of 6 moles of ethylene oxide and an average of 2 moles of propylene oxide are added to both ends of bisphenol A, An alkylene glycol dimethacrylate in which an alkylene glycol dimethacrylate having an average of 15 moles of ethylene oxide and an average of 2 moles of propylene oxide added to both ends of bisphenol A is used.
  • the photosensitive resin composition includes only the compound represented by each of the above general formulas (III), (IV), and (VI) as the compound (C) having an ethylenic double bond.
  • other (C) compounds may be further contained.
  • a photopolymerizable ethylenically unsaturated compound can be used as the other (C) compound. Examples of such photopolymerizable ethylenically unsaturated compounds include compounds having one ethylenic double bond, compounds having two ethylenic double bonds, and having three or more ethylenic double bonds. A compound can be illustrated.
  • Examples of the compound having one ethylenic double bond include a compound obtained by adding (meth) acrylic acid to one terminal of a polyalkylene oxide; Examples thereof include a compound in which (meth) acrylic acid is added to one end of a polyalkylene oxide and the other end is alkyl etherified or allyl etherified.
  • Examples of the compound having two ethylenic double bonds in the molecule include compounds having (meth) acryloyl groups at both ends of the alkylene oxide chain; A compound having a (meth) acryloyl group at both ends of an alkylene oxide chain in which an ethylene oxide unit and a propylene oxide unit are randomly, alternately or block-bonded; A compound having (meth) acryloyl groups at both ends of alkylene oxide-modified bisphenol A; Etc. Of these, compounds having (meth) acryloyl groups at both ends of bisphenol A modified with alkylene oxide are preferred from the viewpoint of resolution and adhesion.
  • alkylene oxide modification examples include ethylene oxide modification, propylene oxide modification, butylene oxide modification, pentylene oxide modification, and hexylene oxide modification.
  • a compound having a (meth) acryloyl group at both ends of bisphenol A modified with ethylene oxide is more preferable.
  • the compound having 3 or more ethylenic double bonds in the molecule is, for example, A compound having 3 mol or more of a group capable of adding an alkylene oxide group in the molecule as a central skeleton is used, and an alkyleneoxy group such as an ethyleneoxy group, a propyleneoxy group, or a butyleneoxy group is added to the compound. It can be obtained by making the obtained alcohol (meth) acrylate.
  • examples of the compound capable of becoming a central skeleton include glycerin, trimethylolpropane, pentaerythritol, dipentaerythritol, and a compound having an isocyanurate ring.
  • compounds having three or more ethylenic double bonds in the molecule include, for example, polypropylene glycol di (meth) acrylate, polyethylene glycol (meth) acrylate, 2-di (P-hydroxyphenyl) propane (meta ) Acrylate, glycerol tri (meth) acrylate trimethylol tri (meth) acrylate, polyoxypropyltrimethylolpropane tri (meth) acrylate, polyoxyethyltrimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, di Pentaerythritol penta (meth) acrylate, trimethylpropanetriglycidyl ether tri (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, nonylpheno Such as polyethylene-glycol (meth) acrylate.
  • Other (C) compounds may be used alone or in combination of
  • the compounding amount of the compound (C) having an ethylenic double bond in the photosensitive resin composition is 5 to 50% by mass when the total solid mass of the photosensitive resin composition is 100% by mass. Setting the blending amount to 5% by mass or more is based on the viewpoint of improving sensitivity, resolution, and adhesion, while setting the blending amount to 50% by mass or less suppresses edge fuses. It is based on a viewpoint and the viewpoint which suppresses the peeling delay of a cured resist. The blending amount is more preferably 25 to 45% by mass. (C) When the compound having an ethylenic double bond includes the compound represented by the above formula (III), the compounding amount of the compound is when the total solid content of the photosensitive resin composition is 100% by mass.
  • the compounding amount of the compound is when the total solid content of the photosensitive resin composition is 100% by mass. It is preferably 2% by mass or more and 40% by mass or less, more preferably 5% by mass or more and 30% by mass or less, and still more preferably 10% by mass or more and 20% by mass or less.
  • the compounding amount of the compound is when the total solid content of the photosensitive resin composition is 100% by mass. It is preferably 2% by mass or more and 40% by mass or less, more preferably 5% by mass or more and 30% by mass or less, and still more preferably 10% by mass or more and 20% by mass or less.
  • the photosensitive resin composition according to the present invention may contain one or more selected from leuco dyes, fluoran dyes, and coloring substances.
  • the exposed portion develops color. Therefore, it is preferable in terms of visibility.
  • an inspection machine reads an alignment marker for exposure, it is advantageous in that the contrast between the exposed part and the unexposed part becomes large and can be easily recognized.
  • the leuco dye examples include tris (4-dimethylaminophenyl) methane [leucocrystal violet], bis (4-dimethylaminophenyl) phenylmethane [leucomalachite green], and the like.
  • leuco crystal violet as the leuco dye from the viewpoint of good contrast.
  • the content of the leuco dye in the photosensitive resin composition is preferably 0.1 to 10% by mass when the total solid mass of the photosensitive resin composition is 100% by mass. Setting the content to 0.1% by mass or more is preferable from the viewpoint of improving the contrast between the exposed portion and the unexposed portion. This content is more preferably 0.2% by mass or more, and still more preferably 0.3% by mass or more.
  • the content is more preferably 5% by mass or less, and further preferably 1% by mass or less.
  • the coloring substance examples include fuchsin, phthalocyanine green, auramine base, paramadienta, crystal violet, methyl orange, Nile blue 2B, Victoria blue, malachite green (manufactured by Hodogaya Chemical Co., Ltd., Eisen (registered trademark) MALACHITE GREEN), basic And Blue 20 and Diamond Green (Hodogaya Chemical Co., Ltd., Eisen (registered trademark) DIAMOND GREEN GH).
  • the content of the coloring substance in the photosensitive resin composition is preferably 0.001% by mass to 1% by mass when the total solid content of the photosensitive resin composition is 100% by mass. Setting the content to 0.001% by mass or more is preferable from the viewpoint of improving handleability, while setting the content to 1% by mass or less is preferable from the viewpoint of maintaining storage stability.
  • halogen compounds include amyl bromide, isoamyl bromide, isobutylene bromide, ethylene bromide, diphenylmethyl bromide, benzyl bromide, methylene bromide, tribromomethylphenyl sulfone, carbon tetrabromide, tris (2 , 3-dibromopropyl) phosphate, trichloroacetamide, amyl iodide, isobutyl iodide, 1,1,1-trichloro-2,2-bis (p-chlorophenyl) ethane, chlorinated triazine compounds and the like.
  • Tribromomethylphenyl sulfone is particularly preferable.
  • Halogen compounds such as tribromomethylphenylsulfone are highly effective when used in combination with acridine compounds, improving resolution, improving adhesion, improving sensitivity, improving contrast, improving tent film puncture resistance, It is preferable from the viewpoint of suppressing the occurrence of the bottom of the resist and improving the etching resistance.
  • content of the halogen compound in the photosensitive resin composition is 0.01 mass% when the total solid content mass of the photosensitive resin composition is 100 mass%.
  • the content is more preferably 0.1% by mass or more, still more preferably 0.3% by mass or more, and particularly preferably 0.5% by mass or more.
  • this content is 3 mass% or less from the viewpoint of maintaining the storage stability of the hue in the photosensitive layer and from the viewpoint of suppressing the generation of aggregates during development.
  • This content is more preferably 2% by mass or less, and further preferably 1.5% by mass or less.
  • the photosensitive resin composition in order to improve the thermal stability and storage stability of the photosensitive resin composition, is a group consisting of radical polymerization inhibitors, benzotriazoles, and carboxybenzotriazoles. You may further contain the 1 or more types of compound chosen from these.
  • radical polymerization inhibitor examples include p-methoxyphenol, hydroquinone, pyrogallol, naphthylamine, tert-butylcatechol, biphenol, cuprous chloride, 2,6-di-tert-butyl-p-cresol, 2,2 ′.
  • benzotriazoles include 1,2,3-benzotriazole, 1-chloro-1,2,3-benzotriazole, bis (N-2-ethylhexyl) aminomethylene-1,2,3-benzotriazole, Examples thereof include bis (N-2-ethylhexyl) aminomethylene-1,2,3-tolyltriazole, bis (N-2-hydroxyethyl) aminomethylene-1,2,3-benzotriazole, and the like.
  • carboxybenzotriazoles include 4-carboxy-1,2,3-benzotriazole, 5-carboxy-1,2,3-benzotriazole, and N- (N, N-di-2-ethylhexyl) aminomethylene. Examples thereof include carboxybenzotriazole, N- (N, N-di-2-hydroxyethyl) aminomethylenecarboxybenzotriazole, N- (N, N-di-2-ethylhexyl) aminoethylenecarboxybenzotriazole and the like.
  • the total content of the radical polymerization inhibitor, the benzotriazoles, and the carboxybenzotriazoles is preferably 0.00 as the total of these contents when the total solid mass of the photosensitive resin composition is 100% by mass.
  • the content is 01 to 3% by mass, and more preferably 0.05 to 1% by mass. Setting the content to 0.01% by mass or more is preferable from the viewpoint of imparting storage stability to the photosensitive resin composition, while setting the content to 3% by mass or less improves sensitivity. It is preferable from the viewpoint of maintaining and suppressing decolorization of the dye.
  • the photosensitive resin composition of this Embodiment may contain a plasticizer as needed.
  • the plasticizer include polyethylene glycol, polypropylene glycol, polyoxypropylene polyoxyethylene ether, polyoxyethylene monomethyl ether, polyoxypropylene monomethyl ether, polyoxyethylene polyoxypropylene monomethyl ether, polyoxyethylene monoethyl ether, polyoxyethylene monomethyl ether, Glycol esters such as oxypropylene monoethyl ether and polyoxyethylene polyoxypropylene monoethyl ether; Phthalates such as diethyl phthalate; o-toluenesulfonic acid amide, p-toluenesulfonic acid amide, tributyl citrate, triethyl citrate, acetyl triethyl citrate, acetyl tri-n-propyl acetyl citrate, tri-n-butyl acetyl citrate and the like; Prop
  • the content of the plasticizer in the photosensitive resin composition is preferably 1 to 50% by mass, more preferably 1 to 30% by mass, when the total solid content of the photosensitive resin composition is 100% by mass. It is. Setting the content to 1% by mass or more is preferable from the viewpoint of suppressing development time delay and imparting flexibility to the cured film, while setting the content to 50% by mass or less is insufficiently cured. And from the viewpoint of suppressing edge fuses.
  • the photosensitive resin composition can be dissolved in a solvent and used as a solution.
  • a solvent to be used for example, Ketones represented by methyl ethyl ketone (MEK); Examples include alcohols typified by methanol, ethanol, and isopropanol.
  • MEK methyl ethyl ketone
  • the solvent is preferably added to the photosensitive resin composition so that the viscosity of the solution of the photosensitive resin composition applied on the support film is 500 to 4,000 mPa ⁇ s at 25 ° C.
  • a photosensitive resin layer having a thickness of 25 ⁇ m made of the photosensitive resin composition is formed on the substrate surface, exposed using a stove 21 step tablet as a mask, and then developed.
  • P ⁇ Q / where Q is the average number of ethylenic double bonds in the compound (C) and P is the reaction rate of ethylenic double bonds in the compound (C) after the exposure. It is preferable that the value of 100 is 0.7 or more.
  • the value of P ⁇ Q / 100 is more preferably 1.0 or more, more preferably 1.5 or more, and 1.7 or more. Is more preferably 2.0 or more, and most preferably 2.5 or more.
  • the value of P ⁇ Q / 100 is more preferably 5.0 or less, and 4.0 or less. More preferably, it is particularly preferably 3.5 or less.
  • a photosensitive resin layer having a thickness of 25 ⁇ m made of the photosensitive resin composition of the present embodiment was formed on the substrate surface, exposed using a stove 21 step tablet as a mask, and then developed.
  • P ′ ⁇ where Q is the average number of ethylenic double bonds in the compound (C) and P ′ is the reaction rate of ethylenic double bonds in the compound (C) after the exposure. It is preferable that the value of Q / 100 is 0.3 or more.
  • the exposure amount at this time is a value considering the exposure amount in the weak exposure region.
  • the value of P ′ ⁇ Q / 100 is More preferably 0.5 or more, more preferably 0.7 or more, still more preferably 1.0 or more, still more preferably 1.3 or more, and 1.6 or more Particularly preferred is 1.9 or more, most preferred; It is more preferably 5.0 or less, further preferably 3.0 or less, and particularly preferably 2.5 or less.
  • the value of P ⁇ Q / 100 is the exposure condition by a direct drawing exposure machine using h line. Measured below.
  • the value of P ⁇ Q / 100 is an exposure by a direct drawing exposure machine using i line. Measured under conditions. The value of P ′ ⁇ Q / 100 is measured under exposure conditions using an exposure machine of an ultra high pressure mercury lamp.
  • a photosensitive resin laminate can be formed using the photosensitive resin composition of the present disclosure.
  • this photosensitive resin laminated body has a support film and the photosensitive resin layer which consists of the said photosensitive resin composition laminated
  • the photosensitive resin laminate may have a protective layer on the surface opposite to the support film.
  • the support film is preferably a transparent film that transmits light emitted from the exposure light source.
  • a support film for example, a polyethylene terephthalate film, a polyvinyl alcohol film, a polyvinyl chloride film, a vinyl chloride copolymer film, a polyvinylidene chloride film, a vinylidene chloride copolymer film, a polymethyl methacrylate copolymer film.
  • Examples include polystyrene film, polyacrylonitrile film, styrene copolymer film, polyamide film, and cellulose derivative film. These films can be stretched if necessary.
  • the haze of the support film is preferably 5 or less.
  • a thinner support film is advantageous in terms of image forming properties and economic efficiency, but it is preferably 10 to 30 ⁇ m in view of the function of maintaining strength.
  • An important characteristic of the protective layer used in the photosensitive resin laminate is to have an appropriate adhesion. That is, it is preferable that the adhesive force of the protective layer to the photosensitive resin layer is sufficiently smaller than the adhesive force of the support film to the photosensitive resin layer, and the protective layer can be easily peeled from the photosensitive resin laminate.
  • the protective layer for example, a polyethylene film, a polypropylene film, a film having excellent peelability disclosed in JP-A-59-202457 can be used.
  • the thickness of the protective layer is preferably 10 to 100 ⁇ m, more preferably 10 to 50 ⁇ m.
  • the thickness of the photosensitive resin layer in the photosensitive resin laminate varies depending on the application, but is preferably 5 to 100 ⁇ m, more preferably 7 to 60 ⁇ m. The thinner the photosensitive resin layer, the higher the resolution, and the thicker the film, the better the film strength.
  • the photosensitive resin laminate can be produced by sequentially laminating a photosensitive resin layer and, if necessary, a protective layer on a support film.
  • a known method can be employed.
  • the photosensitive resin composition used for the photosensitive resin layer is mixed with a solvent that dissolves them to form a uniform coating solution.
  • the coating liquid can be applied on the support film using a bar coater or a roll coater, and then dried to laminate a photosensitive resin layer made of a photosensitive resin composition on the support film.
  • a photosensitive resin laminate can be produced by laminating a protective layer on the photosensitive resin layer.
  • ⁇ Circuit pattern forming method> Another embodiment of the present invention is: A step of forming the above-described layer of the photosensitive resin composition of the present disclosure on a substrate (lamination step); A step of exposing and developing the layer of the photosensitive resin composition to form a resist pattern (exposure step and developing step), and a step of etching or plating the substrate on which the resist pattern is formed (etching step or plating step) ) A method of forming a circuit pattern is provided. It is preferable to further include a peeling step for peeling the resist pattern from the laminate after the series of steps described above.
  • the layer of the photosensitive resin composition is formed using the above-described photosensitive resin laminate.
  • an example of a method for forming a circuit pattern using a photosensitive resin laminate and a copper-clad laminate as a substrate will be described.
  • Lamination process It is the process of sticking on board
  • substrates such as a copper clad laminated board and a flexible substrate, for example using a hot roll laminator, peeling off the protective layer of the photosensitive resin composition.
  • Exposure step In the layer of the photosensitive resin composition formed on the substrate, A step of performing exposure through the mask film in a state in which a mask film having a desired wiring pattern is adhered; It is a step of exposing a desired wiring pattern by a direct imaging exposure method, or a step of exposing by an exposure method of projecting an image of a photomask through a lens.
  • the advantages of the photosensitive resin composition according to the present embodiment are more significantly manifested in the direct imaging exposure method by direct drawing of the wiring pattern or the exposure method of projecting the image of the photomask through the lens. In the exposure process, it is preferable to employ a direct imaging exposure method because it is particularly noticeable in the method.
  • the support on the photosensitive resin layer is peeled off, and then the unexposed portion is developed and removed using an alkaline aqueous developer to form a resist pattern on the substrate.
  • an alkaline aqueous solution an aqueous solution of Na 2 CO 3 or K 2 CO 3 can be used.
  • the alkaline aqueous solution is appropriately selected according to the characteristics of the photosensitive resin layer, but it is preferable to use an aqueous Na 2 CO 3 solution having a concentration of about 0.2 to 2% by mass and a temperature of about 20 to 40 ° C.
  • a resist pattern can be obtained through each of the above steps.
  • these steps may be followed by a heating step at about 100 ° C. to 300 ° C.
  • a hot-air, infrared, or far-infrared heating furnace can be used.
  • a conductor pattern is manufactured by etching or plating the substrate surface exposed by development (for example, the copper surface of a copper-clad laminate).
  • an etching process it is a process of forming a desired circuit pattern by spraying an etching solution from above on the resist pattern formed through the above-described process and etching the copper surface not covered with the resist pattern.
  • the etching method include acid etching and alkali etching, and the etching is performed by a method suitable for the photosensitive resin laminate to be used.
  • the laminate is treated with an aqueous solution having alkalinity stronger than the developer, and the resist pattern is stripped from the substrate.
  • an aqueous solution having alkalinity stronger than the developer there is no restriction
  • An aqueous solution of NaOH or KOH having a concentration of about 2 to 5% by mass and a temperature of about 40 to 70 ° C. is generally used.
  • a small amount of a water-soluble solvent may be added to the stripping solution.
  • ⁇ Board surface preparation> A 0.4 mm thick copper clad laminate in which a rolled copper foil having a thickness of 35 ⁇ m was laminated was used as an evaluation substrate for image quality, resist skirt width, etching property, and peeling time.
  • the substrate was treated with CPE-900 (registered trademark, manufactured by Hishoe Chemical Co., Ltd.), then surface-washed with 10% by mass H 2 SO 4 and rinsed with pure water before use. did.
  • ⁇ Laminate> Laminating at a roll temperature of 105 ° C with a hot roll laminator (Asahi Kasei Co., Ltd., AL-700) on a copper clad laminate that has been leveled and preheated to 60 ° C while peeling the polyethylene film of the photosensitive resin laminate. By doing this, the laminated body for various evaluation was obtained.
  • the air pressure was 0.35 MPa, and the laminating speed was 1.5 m / min. Evaluations other than those specified in the evaluation method described later were performed on samples prepared under the conditions described in the items of various evaluation methods using the laminated body after lamination. General operating methods for exposure, development, etching, and peeling are described below.
  • ⁇ Exposure> For exposures other than “(x) P ′ ⁇ Q / 100” to be described later, a direct drawing exposure machine (manufactured by Hitachi Via Mechanics, DE-1DH, light source: GaN blue-violet diode (main wavelength 405 ⁇ 5 nm)) Using a stove 21 step tablet or a predetermined mask pattern for DI exposure, exposure was performed under the condition of an illuminance of 80 mW / cm 2 . This exposure was carried out with an exposure amount at which the maximum number of remaining film stages was 6 when exposed and developed using the stove 21-step tablet as a mask.
  • the position of the focal point during exposure was shifted from the substrate surface to the inside of the substrate by 200 ⁇ m in the thickness direction of the substrate.
  • a cupric chloride etching solution adjusted to 50 ° C. using a salt copper etching apparatus (manufactured by Tokyo Chemical Industry Co., Ltd., salt copper etching apparatus) By spraying for 1.3 times the minimum etching time, a portion of the copper foil not covered with the resist pattern on the copper clad laminate was dissolved and removed.
  • the cupric chloride etching solution is a solution having a cupric chloride concentration of 250 g / L and a hydrochloric acid concentration of 3 mol / L.
  • the minimum etching time is the time required until the copper foil on the substrate is completely dissolved and removed.
  • ⁇ When the exposure amount at which the maximum number of remaining film steps is 6 is less than 20 mJ / cm 2 ⁇ (Poor): The exposure amount at which the maximum number of remaining film steps is 6 is 20 mJ / cm 2 or more In the case of Examples 20 to 44 and Comparative Examples 9 to 12, the exposure values at which the maximum number of remaining film steps is 6 are listed in Table 1. In applications assumed by these examples, it can be evaluated that the sensitivity is good when the exposure amount is 70 mJ or less, preferably 40 mJ or less, more preferably 30 mJ or less, and still more preferably. Is 20 mJ or less.
  • the values of the minimum mask line width are shown in Table 1. In applications assumed by these embodiments, it can be evaluated that the resolution (1) is good when the minimum mask line width is 60 ⁇ m or less, preferably 35 ⁇ m or less, more preferably 25 ⁇ m or less. More preferably, it is 20 ⁇ m or less, and particularly preferably 16 ⁇ m or less.
  • the resolution (2) is good, preferably 35 ⁇ m or less, more preferably 30 ⁇ m or less, still more preferably 25 ⁇ m or less, particularly Preferably it is 20 micrometers or less.
  • the values of the minimum mask line width are shown in Table 1. In applications assumed by these examples, it can be evaluated that the adhesion is good when the minimum mask line width is 70 ⁇ m or less, preferably 30 ⁇ m or less, more preferably 25 ⁇ m or less. More preferably, it is 20 ⁇ m or less, particularly preferably 10 ⁇ m or less.
  • this value was used as a resist line width and ranked according to the following criteria: ⁇ (very good): When the resist skirt width is 1.5 ⁇ m or less ⁇ (Good): When the resist skirt width exceeds 1.5 ⁇ m and is 2.5 ⁇ m or less ⁇ (possible): Resist skirt width is 2 When exceeding .5 ⁇ m and not more than 3.5 ⁇ m x (defect): When resist bottom width exceeds 3.5 ⁇ m For Examples 20 to 44 and Comparative Examples 9 to 12, the value of this resist bottom width is It was described in Table 1.
  • the adhesion is good when the value of the resist skirt width is 10 ⁇ m or less, preferably 3 ⁇ m or less, more preferably 2.5 ⁇ m. Or less, more preferably 2 ⁇ m or less, even more preferably 1.5 ⁇ m or less, and particularly preferably 1 ⁇ m or less. See FIG. 1 for the method of measuring the resist hem width.
  • the position of the focus at the time of exposure was adjusted to the resist bottom.
  • the illuminance during exposure was 80 mW / cm 2 .
  • the exposure amount at this time was an exposure amount at which the maximum number of remaining film steps was 6 when exposure was performed using the stove 21-step tablet as a mask and then developed (normal exposure).
  • the reaction rate P of the ethylenic double bond of the cured resist obtained by the above operation was determined by FT-IR (manufactured by Thermo SCIENTIFIC, NICOLET 380). The peak height at a wave number of 810 cm ⁇ 1 was measured and this value was defined as the amount of ethylenic double bonds.
  • the average number (number of functional groups) of ethylenic double bonds in the compound (C) was calculated, and this value was taken as Q.
  • Q was determined in consideration of the content of each component. From the above P and Q, a value of P ⁇ Q / 100 was obtained.
  • Table 1 shows the evaluation results of the examples and comparative examples.
  • Table 2 shows the names of the components represented by abbreviations in Table 1. All the alkali-soluble polymers shown in Table 2 were subjected to blending as a methyl ethyl ketone solution having a solid content concentration shown in the table. Abbreviations in the functional group type column in the compounds having an ethylenic double bond in Table 2 have the following meanings, respectively.
  • Table 3 shows the glass transition temperature (document values) when each monomer used for the synthesis of the alkali-soluble resin is a homopolymer.
  • Photosensitive resin composition of this embodiment and photosensitive resin laminate, resist pattern, and circuit pattern manufactured using the same, printed wiring board, manufacture of flexible printed wiring board, lead frame for mounting IC chip, metal It can be suitably used for manufacturing a mask, a semiconductor package such as BGA or CSP, a tape substrate such as TAB or COF, a semiconductor bump, an ITO electrode, an address electrode, and an electromagnetic wave shield.

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  • General Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Manufacturing & Machinery (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
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  • Health & Medical Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Optics & Photonics (AREA)
  • Materials For Photolithography (AREA)
  • Exposure And Positioning Against Photoresist Photosensitive Materials (AREA)
  • Manufacturing Of Printed Circuit Boards (AREA)
  • Manufacturing Of Printed Wiring (AREA)

Abstract

L'invention concerne une composition de résine photosensible, contenant (A) de 40 à 80 % en masse d'un polymère alcalino-soluble, (B) de 0,1 à 20 % en masse d'un initiateur de photopolymérisation, et (C) de 5 à 50 % en masse d'un composé ayant une double liaison éthylénique, la composition de résine photosensible étant caractérisée en ce que : une couche de résine photosensible dotée d'une épaisseur de 25 µm et constituée de la composition de résine photosensible est formée sur une surface de substrat, la couche de résine photosensible est exposée et développée dans des conditions dans lesquelles la position du point focal pendant l'exposition est décalée par rapport à la surface de substrat de 200 µm vers l'intérieur du substrat dans le sens de l'épaisseur du substrat, et un motif de résist ainsi obtenu a une largeur de pied de résist dans la plage de 0,01 à 3,5 µm ; et la composition de résine photosensible est utilisée dans l'exposition d'insolation par laser.
PCT/JP2015/064644 2014-05-21 2015-05-21 Composition de résine photosensible et procédé de formation de tracé de circuit WO2015178462A1 (fr)

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JP2016521151A JPWO2015178462A1 (ja) 2014-05-21 2015-05-21 感光性樹脂組成物及び回路パターンの形成方法
KR1020197022465A KR20190092622A (ko) 2014-05-21 2015-05-21 감광성 수지 조성물 및 회로 패턴의 형성 방법
CN202010587896.3A CN111694218B (zh) 2014-05-21 2015-05-21 感光性树脂组合物以及电路图案的形成方法
CN201580025748.XA CN106462068B (zh) 2014-05-21 2015-05-21 感光性树脂组合物以及电路图案的形成方法
KR1020217025400A KR20210102494A (ko) 2014-05-21 2015-05-21 감광성 수지 조성물 및 회로 패턴의 형성 방법
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JP2020190735A (ja) * 2020-07-14 2020-11-26 旭化成株式会社 感光性樹脂組成物、感光性樹脂積層体、レジストパターン形成方法及び導体パターン製造方法
WO2021005766A1 (fr) * 2019-07-10 2021-01-14 昭和電工マテリアルズ株式会社 Composition de résine photosensible, film de résine photosensible, procédé de production d'un produit durci, stratifié et composant électronique
KR20220038405A (ko) 2019-11-11 2022-03-28 아사히 가세이 가부시키가이샤 감광성 수지 조성물 및 감광성 수지 적층체
JP2023509860A (ja) * 2019-12-31 2023-03-10 コーロン インダストリーズ インク 感光性樹脂組成物およびそれを用いたドライフィルムフォトレジスト、感光性エレメント、回路基板、およびディスプレイ装置

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CN109690404B (zh) * 2016-12-07 2023-04-04 旭化成株式会社 感光性树脂组合物和感光性树脂层叠体
TWI700183B (zh) * 2017-12-20 2020-08-01 日商旭化成股份有限公司 感光性樹脂積層體
CN108663867A (zh) * 2018-04-11 2018-10-16 华南师范大学 一种染料掺杂的激光防护膜
KR102509152B1 (ko) * 2018-08-09 2023-03-10 아사히 가세이 가부시키가이샤 감광성 수지 조성물 및 레지스트 패턴의 형성 방법
KR102242551B1 (ko) * 2019-12-31 2021-04-20 코오롱인더스트리 주식회사 감광성 수지 조성물 및 이를 이용한 드라이 필름 포토레지스트, 감광성 엘리먼트, 회로기판, 및 디스플레이 장치
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