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
• • 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
• • 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
  • G03F7/004—Photosensitive materials
  • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
• • 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
• • 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
  • G03F7/26—Processing photosensitive materials; Apparatus therefor
  • G03F7/30—Imagewise removal using liquid means
• • 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

Definitions

• the present invention relates to a photosensitive resin composition and the like.
• a photosensitive resin laminate comprising a photosensitive resin layer laminated on a support film, and further a protective film laminated on the photosensitive resin layer as necessary, A so-called dry film photoresist (hereinafter sometimes referred to as DF) is used.
• DF dry film photoresist
• the photosensitive resin layer is generally of an alkali development type using a weak alkaline aqueous solution as a developer.
• the following steps are performed.
• DF has a protective film
• the protective film is first peeled off.
• DF is laminated on a permanent circuit fabrication substrate such as a copper clad laminate or a flexible substrate using a laminator or the like, and exposure is performed through a wiring pattern mask film or the like.
• the support film is peeled off, and a photosensitive resin layer of an uncured portion (for example, an unexposed portion in a negative type) is dissolved or dispersed and removed by a developer, and a cured resist pattern (hereinafter simply referred to as a resist pattern) is formed on the substrate. (Sometimes called a resist pattern).
• the process of forming a circuit after forming a resist pattern is roughly divided into two methods.
• the first method is a method in which a substrate surface not covered with a resist pattern (for example, a copper surface of a copper clad laminate) is removed by etching, and then the resist pattern portion is removed with an alkaline aqueous solution stronger than a developer (etching method). It is.
• the substrate surface is plated with copper, solder, nickel, tin, etc., and then the resist pattern portion is removed in the same manner as in the first method.
• This is a method (plating method) for etching a copper surface of a copper-clad laminate.
• Patent Document 1 describes a photosensitive resin composition whose resolution is enhanced by a specific thermoplastic resin, a monomer, and a photopolymerizable initiator. .
• the position of the focal point greatly affects the resolution and the line width reproducibility. For example, if the focus position at the time of exposure deviates from the substrate surface due to warpage and distortion of the substrate, setting failure of the exposure apparatus, etc., resolution and resist line width reproducibility are greatly deteriorated. As a result, a short circuit problem may occur when a circuit is formed by an etching method, and problems such as chipping, disconnection, or poor plating may occur when a circuit is formed by a plating method.
• the present invention provides a photosensitive resin laminate that exhibits high resolution and good line width reproducibility, and a support film and a photosensitive film for forming the same, even when the focus during exposure is deviated. It is an object to provide a conductive resin composition, and to provide a resist pattern forming method and a conductor pattern forming method using the photosensitive resin laminate.
• a photosensitive resin laminate comprising a support film and a photosensitive resin composition layer containing a photosensitive resin composition formed on the support film, wherein at any 10 locations of the support film, a side of 5 mm
• a photosensitive resin laminate in which the number of fine particles of 1.5 ⁇ m or more and less than 4.5 ⁇ m contained in each small piece when the square pieces are cut out is an average of 0 to 200 in the 10 places.
• the photosensitive resin composition is based on the total solid content of the photosensitive resin composition, and the following components: (A) Alkali-soluble polymer: 10% by mass to 90% by mass; (B) Compound having ethylenically unsaturated double bond: 5% by mass to 70% by mass; and (C) Photopolymerization initiator: 0.01% by mass to 20% by mass; The photosensitive resin laminate according to any one of [1] to [6]. [8] The photosensitive resin laminate according to [7], wherein the monomer component of the (A) alkali-soluble polymer has an aromatic hydrocarbon group.
• a laminating step of laminating the photosensitive resin laminate according to any one of [1] to [16] on a substrate A resist pattern forming method, comprising: an exposure step of exposing a photosensitive resin layer of the photosensitive resin laminate; and a development step of developing and removing an unexposed portion of the photosensitive resin layer.
• a resist pattern forming method comprising: an exposure step of exposing a photosensitive resin layer of the photosensitive resin laminate; and a development step of developing and removing an unexposed portion of the photosensitive resin layer.
• the resist pattern forming method according to [17] wherein the exposure step is performed by an exposure method by direct drawing of a drawing pattern or an exposure method of projecting a photomask image through a lens.
• a photosensitive resin laminate that exhibits high resolution and good line width reproducibility even when the focus is shifted during exposure, and a support film and a photosensitive resin composition for forming the same. It is possible to provide a method for forming a resist pattern and a method for forming a conductor pattern using the photosensitive resin laminate. As a result, even when the focus position at the time of exposure deviates from the substrate surface due to warpage and distortion of the substrate, setting failure of the exposure apparatus, etc., it is possible to reduce the short circuit problem when forming a circuit by the etching method. In addition, when a circuit is formed by a plating method, problems such as chipping, disconnection, and plating failure can be reduced. Also, a desired circuit width can be obtained.
• the photosensitive resin laminate of the present invention is a photosensitive resin laminate comprising a support film and a photosensitive resin composition layer containing the photosensitive resin composition formed on the support film, and the support film
• the number of fine particles of 1.5 ⁇ m or more and less than 4.5 ⁇ m contained in each small piece when a square piece having a side of 5 mm is cut out at any one of 10 places is an average of 0 to 200 in 10 places. It is a photosensitive resin laminate.
• the fine particles having a diameter of 1.5 ⁇ m or more and less than 4.5 ⁇ m include a primary particle having a diameter of 1.5 ⁇ m or more and less than 4.5 ⁇ m and a primary particle aggregate having a diameter of the aggregate of the primary particles of 1.5 ⁇ m or more and less than 4.5 ⁇ m. included. If the primary particles are not perfect spheres, the longest width of the primary particles is taken as the diameter of the primary particles. When the primary particle aggregate is not a perfect sphere, the longest width of the primary particle aggregate is taken as the diameter of the primary particle aggregate.
• the photosensitive resin laminate may have a protective layer on the surface of the photosensitive resin layer opposite to the support layer side.
• the present inventors have performed exposure with the focal position aligned with the surface of the base material, and positions shifted from the base material surface to the inside of the base material (deviation of the focal position, such as the amount of waviness on the surface).
• the photosensitive resin laminate is designed by paying attention to the difference in line width and resolution when the exposure is performed with the focus position adjusted to the reference value set as a very large deviation amount with respect to the quantity. Has been found to be effective in solving the above problems.
• the focal position at the time of exposure when the number of fine particles of 1.5 ⁇ m or more and less than 4.5 ⁇ m contained in a square piece of 5 mm on a side of the support film is 0 to 200 on average in any 10 places It is possible to suppress an increase in line width and a deterioration in resolution when deviating.
• the size of the fine particles that affect these performances is 1.5 ⁇ m or more and less than 4.5 ⁇ m, and the normal exposure does not affect these performances. If the focus of the exposed portion is deviated due to the distortion of the substrate, insufficient adsorption of the substrate to the stage, and unevenness of the substrate surface, the influence of light scattering by the fine particles increases.
• the line width increases and resolution (particularly, omission) deteriorates.
• resolution is deteriorated even during normal exposure.
• fine particles of less than 1.5 ⁇ m no increase in line width or deterioration in resolution is observed even when the focus during exposure shifts.
• the number of fine particles of 1.5 ⁇ m or more and less than 4.5 ⁇ m contained in a small piece of the support film is an average of 10 points from the viewpoint of suppressing the increase in line width and resolution when the focal position is shifted during exposure. It is preferably 180 or less, preferably 150 or less, preferably 120 or less, preferably 100 or less, more preferably 80 or less, more preferably 50 or less, still more preferably 30 or less, 20 More preferably, no more than 15, particularly preferably not more than 15, more preferably not more than 10, and most preferably not more than 6.
• fine-particles of 1.5 micrometers or more and less than 4.5 micrometers is 1 or more at the point which the adhesiveness of a support film and the photosensitive resin layer is excellent.
• the support film contains one or more fine particles of 1.5 ⁇ m or more and less than 4.5 ⁇ m in an average of any 10 locations, the support film can be slippery and the support film can be peeled off. Become. When the support film is partially peeled after lamination to the substrate, oxygen enters between the support film and the photosensitive resin composition layer, and even if the photosensitive resin composition is exposed due to the oxygen, Hardening failure may occur.
• the number of fine particles of 1.5 ⁇ m or more and less than 4.5 ⁇ m in the support film may be 2 or more, 3 or more, 5 or more, 8 or more, Or 10 or more.
• the photosensitive resin laminate is the right of the present invention. Suppose that it is within the range. That is, even if the prescribed number of particles is not satisfied when measured at a certain 10 places, the photosensitive resin laminate is within the scope of the present invention when the prescribed number of particles is satisfied when measured at another 10 places. Be within.
• the fine particles of 1.5 ⁇ m or more and less than 4.5 ⁇ m included in the support film are, for example, inorganic fine particles or organic fine particles, such as lubricants, additive aggregates, foreign matters mixed in raw materials, foreign matters mixed in the manufacturing process, etc.
• the fine particles include inorganic particles such as calcium carbonate, calcium phosphate, silica (silicon dioxide), kaolin, talc, titanium dioxide, alumina (aluminum oxide), barium sulfate, calcium fluoride, lithium fluoride, zeolite, and molybdenum sulfide.
• organic particles such as crosslinked polymer particles and calcium oxalate. These may be used alone or in combination of two or more.
• the fine particles are blended into the film according to a conventional method. In order to produce the support film of the present invention, for example, a method of filtering the resin with a filter having an eye of 4.5 ⁇ m or less can be used.
• the support film is preferably a transparent support film that transmits light emitted from the exposure light source.
• support films include polyethylene terephthalate film, polyvinyl alcohol film, polyvinyl chloride film, vinyl chloride copolymer film, polyvinylidene chloride film, vinylidene chloride copolymer film, polymethyl methacrylate copolymer film, Examples thereof include a polystyrene film, a polyacrylonitrile film, a styrene copolymer film, a polyamide film, and a cellulose derivative film. These films can be stretched if necessary.
• the support film is preferably one having a haze of 5% or less, more preferably 2% or less, still more preferably 1.5% or less, particularly preferably 1.0% or less, from the viewpoint of suppressing light scattering during exposure.
• the surface roughness Ra of the surface in contact with the photosensitive layer is preferably 30 nm or less, more preferably 20 nm or less, and particularly preferably 10 nm or less. The thinner the film is, the more advantageous it is for improving the image forming property and the economical efficiency, but a film having a thickness of 10 to 30 ⁇ m is preferably used in order to maintain the strength of the photosensitive resin laminate.
• the support film may have a single layer structure or a multilayer structure in which resin layers formed from a plurality of compositions are laminated.
• a multilayer structure there may be an antistatic layer.
• a resin layer containing fine particles is formed on one side A, and fine particles are formed on the other side B in the same manner as (1) surface A.
• (2) contains a smaller amount of fine particles than the surface A
• (3) contains fine particles finer than the surface A
• (4) does not contain fine particles.
• the protective layer used in the photosensitive resin laminate is that the adhesion with the photosensitive resin layer is sufficiently smaller than that of the holding layer and can be easily peeled off.
• a polyethylene film or a polypropylene film can be preferably used as the protective layer.
• a film having excellent releasability disclosed in JP-A-59-202457 can be used.
• the thickness of the protective layer is preferably 10 ⁇ m to 100 ⁇ m, more preferably 10 ⁇ m to 50 ⁇ m.
• a gel called fish eye on the surface of the polyethylene film.
• the fish eyes may be transferred to the photosensitive resin layer.
• the fish eye is transferred to the photosensitive resin layer, air may be entrained during lamination to form voids, leading to a defect in the resist pattern.
• stretched polypropylene is preferred as the material for the protective layer.
• Alpha E-200A manufactured by Oji Paper Co., Ltd. can be mentioned.
• the thickness of the photosensitive resin layer in the photosensitive resin laminate varies depending on the application, but is preferably 1 ⁇ m to 300 ⁇ m, more preferably 3 ⁇ m to 100 ⁇ m, particularly preferably 5 ⁇ m to 60 ⁇ m, and most preferably 10 ⁇ m to 30 ⁇ m.
• the photosensitive resin composition used for the photosensitive resin layer is mixed with a solvent that dissolves the photosensitive resin composition to form a uniform solution, first applied onto the support layer using a bar coater or roll coater, and then dried to form the solvent. By removing, a photosensitive resin layer made of a photosensitive resin composition can be laminated on the support layer. Then, if necessary, a photosensitive resin laminate can be produced by laminating a protective layer on the photosensitive resin layer.
• the photosensitive resin composition preferably includes (A) an alkali-soluble polymer, (B) a compound having an ethylenically unsaturated double bond, and (C) a photopolymerization initiator.
• the photosensitive resin composition comprises (A) an alkali-soluble polymer: 10% by mass to 90% by mass; (B) a compound having an ethylenically unsaturated double bond, based on the total solid content of the photosensitive resin composition. : 5 mass% to 70 mass%; and (C) Photopolymerization initiator: 0.01 mass% to 20 mass% is preferably included.
• each component will be described in order.
• the (A) alkali-soluble polymer includes a polymer that is easily soluble in an alkaline substance. More specifically, the amount of carboxyl groups contained in (A) the alkali-soluble polymer is from 100 to 600, preferably from 250 to 450, as an acid equivalent.
• the acid equivalent means the mass (unit: gram) of a polymer having 1 equivalent of a carboxyl group in the molecule.
• the carboxyl group in the alkali-soluble polymer is necessary for giving the photosensitive resin layer developability and releasability with respect to an aqueous alkali solution.
• the acid equivalent is a value measured by a potentiometric titration method using a potentiometric titrator and titrating with a 0.1 mol / L NaOH aqueous solution.
• the weight average molecular weight of the alkali-soluble polymer is preferably 5,000 to 500,000.
• a weight average molecular weight of 500,000 or less is preferable from the viewpoint of improving resolution and developability.
• the weight average molecular weight is more preferably 100,000 or less, still more preferably 60,000 or less, and particularly preferably 50,000 or less.
• setting the weight average molecular weight to 5,000 or more is a viewpoint for controlling the properties of the development aggregate and the properties of the unexposed film such as the edge fuse property and the cut chip property when the photosensitive resin laminate is used.
• the weight average molecular weight is more preferably 10,000 or more, and further preferably 20,000 or more.
• the edge fuse property refers to the degree of ease of protrusion of the photosensitive resin layer (that is, the layer made of the photosensitive resin composition) from the end surface of the roll when the photosensitive resin laminate is wound into a roll.
• Cut chip property refers to the degree of ease of chip flying when an unexposed film is cut with a cutter. If this chip adheres to the upper surface of the photosensitive resin laminate, it is transferred to a mask in a later exposure process or the like, causing defective products.
• the degree of dispersion of the alkali-soluble polymer is preferably 1.0 to 6.0, more preferably 1.0 to 5.0, and more preferably 1.0 to 4.0. More preferably, it is 1.0 to 3.0.
• the photosensitive resin composition has an aromatic hydrocarbon group as an alkali-soluble polymer (A) from the viewpoint of suppressing the increase in line width and the resolution when the focal position at the time of exposure shifts.
• the monomer component is included.
• examples of such an aromatic hydrocarbon group include a substituted or unsubstituted phenyl group and a substituted or unsubstituted aralkyl group.
• the content ratio of the monomer component having an aromatic hydrocarbon group in the (A) alkali-soluble polymer is preferably 20% by mass or more based on the total mass of all monomer components, and is 40% by mass.
• the content rate of the monomer component which has an aromatic hydrocarbon group in the case of containing multiple types of (A) alkali-soluble polymer was calculated
• Examples of the monomer having an aromatic hydrocarbon group include a monomer having an aralkyl group, styrene, and a polymerizable styrene derivative (for example, methylstyrene, vinyltoluene, tert-butoxystyrene, acetoxystyrene, 4-vinyl). Benzoic acid, styrene dimer, styrene trimer, etc.). Among them, a monomer having an aralkyl group or styrene is preferable.
• Examples of the aralkyl group include a substituted or unsubstituted phenylalkyl group (excluding benzyl group), a substituted or unsubstituted benzyl group, and the like, and a substituted or unsubstituted benzyl group is preferable.
• Examples of the comonomer having a phenylalkyl group include phenylethyl (meth) acrylate.
• Examples of the comonomer having a benzyl group include (meth) acrylates having a benzyl group, such as benzyl (meth) acrylate, chlorobenzyl (meth) acrylate, etc .; vinyl monomers having a benzyl group, such as vinylbenzyl chloride, vinylbenzyl alcohol, etc. Is mentioned. Of these, benzyl (meth) acrylate is preferred.
• the (A) alkali-soluble polymer containing a monomer component having an aromatic hydrocarbon group includes at least one of a monomer having an aromatic hydrocarbon group and a first monomer described below and / or It is preferably obtained by polymerizing at least one second monomer described below.
• the (A) alkali-soluble polymer not containing a monomer component having an aromatic hydrocarbon group is preferably obtained by polymerizing at least one of the first monomers described below. More preferably, it is obtained by copolymerizing at least one monomer and at least one second monomer described below.
• the first monomer is a monomer having a carboxyl group in the molecule.
• Examples of the first monomer include (meth) acrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, 4-vinylbenzoic acid, maleic anhydride, maleic acid half ester, and the like.
• (meth) acrylic acid is preferable.
• (meth) acrylic acid means acrylic acid or methacrylic acid
• (meth) acryloyl group means acryloyl group or methacryloyl group
• the copolymerization ratio of the first monomer 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, more preferably 15% by mass or more, and further preferably 20% by mass or more. . Setting the copolymerization ratio to 50% by mass or less is preferable from the viewpoint of the high resolution and sword shape of the resist pattern, and further from the viewpoint of chemical resistance of the resist pattern. In these viewpoints, 35% by mass. The following is more preferable, 30% by mass or less is further preferable, and 27% by mass or less is particularly preferable.
• the second monomer is a monomer that is non-acidic and has at least one polymerizable unsaturated group in the molecule.
• Examples of the second monomer include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, and isobutyl (meth) acrylate.
• the monomer which has an aralkyl group, and / or styrene as a monomer from a viewpoint of suppressing the line
• a copolymer containing methacrylic acid, benzyl methacrylate, and styrene a copolymer containing methacrylic acid, methyl methacrylate, benzyl methacrylate, and styrene are preferable.
• the alkali-soluble polymer can be used alone or in combination of two or more.
• two types of alkali-soluble polymers containing a monomer component having an aromatic hydrocarbon group are used in combination, or a monomer component having an aromatic hydrocarbon group
• a mixture of an alkali-soluble polymer containing alkenyl and an alkali-soluble polymer not containing a monomer component having an aromatic hydrocarbon group is preferable to use a mixture of an alkali-soluble polymer containing alkenyl and an alkali-soluble polymer not containing a monomer component having an aromatic hydrocarbon group.
• the proportion of the alkali-soluble polymer containing the monomer component having an aromatic hydrocarbon group is preferably 50% by mass or more based on the total amount of the (A) alkali-soluble polymer. More preferably, it is 80 mass% or more, and it is more preferable that it is 90 mass% or more.
• the synthesis of the alkali-soluble polymer is carried out by diluting one or more monomers described above with a solvent such as acetone, methyl ethyl ketone, isopropanol, etc., and adding benzoyl peroxide, azoisobutyronitrile, etc. It is preferable to carry out by adding an appropriate amount of a radical polymerization initiator and stirring with heating. In some cases, the synthesis is performed while a part of the mixture is dropped into the reaction solution. After completion of the reaction, a solvent may be further added to adjust to a desired concentration. As synthesis means, bulk polymerization, suspension polymerization, or emulsion polymerization may be used in addition to solution polymerization.
• Weight average Tg total glass transition temperature Tg of the (A) alkali-soluble polymer is preferably at 30 ° C. or higher 135 ° C. or less. Tg total is calculated by the method described in Examples described later. In the photosensitive resin composition, by using the (A) alkali-soluble polymer having a Tg total of 135 ° C. or lower, it is possible to suppress the increase in the line width and the deterioration of the resolution when the focal position at the time of exposure shifts. it can. From this viewpoint, the Tg total of the (A) alkali-soluble polymer is more preferably 120 ° C. or less, further preferably 115 ° C. or less, more preferably 110 ° C. or less, and 105 ° C. or less.
• the Tg total of the (A) alkali-soluble polymer is more preferably 40 ° C. or higher, further preferably 50 ° C. or higher, and particularly preferably 60 ° C. or higher.
• the ratio of the alkali-soluble polymer to the total solid mass of the photosensitive resin composition is preferably in the range of 10% by mass to 90% by mass, more preferably 30% by mass to 70% by mass, More preferably, it is 40% by mass to 60% by mass. Setting the ratio of (A) the alkali-soluble polymer to the photosensitive resin composition to 90% by mass or less is preferable from the viewpoint of controlling the development time. On the other hand, it is preferable from the viewpoint of improving edge fuse resistance that the ratio of (A) the alkali-soluble polymer to the photosensitive resin composition be 10% by mass or more.
• the compound having an ethylenically unsaturated double bond preferably contains a compound having a (meth) acryloyl group in the molecule from the viewpoint of curability and compatibility with (A) an alkali-soluble polymer.
• the number of (meth) acryloyl groups in a compound should just be one or more.
• the (B) compound having one (meth) acryloyl group for example, a compound obtained by adding (meth) acrylic acid to one end of polyalkylene oxide, or (meth) acrylic at one end of polyalkylene oxide
• a compound in which an acid is added and the other end is alkyl etherified or allyl etherified, a phthalic acid compound, and the like can be mentioned, which is preferable from the viewpoint of peelability and cured film flexibility.
• 4-normal nonyl phenoxy pentae which is a (meth) acrylate of a compound obtained by adding polyethylene glycol with 4-normal nonylphenoxyoctaethylene glycol (meth) acrylate (for example, Toagosei Co., Ltd.) which is an acrylate of
• Examples of the compound having two (meth) acryloyl groups in the molecule include, for example, a compound having a (meth) acryloyl group at both ends of an alkylene oxide chain, or an alkylene in which an ethylene oxide chain and a propylene oxide chain are bonded randomly or in blocks. Examples thereof include compounds having (meth) acryloyl groups at both ends of the oxide chain.
• Examples of such a compound include tetraethylene glycol di (meth) acrylate, pentaethylene glycol di (meth) acrylate, hexaethylene glycol di (meth) acrylate, heptaethylene glycol di (meth) acrylate, octaethylene glycol di (Poly (ethylene glycol) (meth) acrylates such as (meth) acrylate, nonaethylene glycol di (meth) acrylate, decaethylene glycol di (meth) acrylate, and compounds having (meth) acryloyl groups at both ends of 12 moles of ethylene oxide chain Polypropylene glycol di (meth) acrylate, polybutylene glycol di (meth) acrylate and the like can be mentioned.
• polyalkylene oxide di (meth) acrylate compounds containing ethylene oxide groups and propylene oxide groups in the compound for example, an average of 3 mol of ethylene oxide is further added to both ends of polypropylene glycol to which an average of 12 mol of propylene oxide is added.
• a compound having (meth) acryloyl groups at both ends by modifying alkylene oxide with bisphenol A has improved resolution and adhesion. From the viewpoint, it is preferable.
• R1 and R2 each independently represent a hydrogen atom or a methyl group
• A is C 2 H 4
• B is C 3 H 6
• n1 and n3 are each independently 1 to 39
• N1 + n3 is an integer of 2 to 40
• n2 and n4 are each independently an integer of 0 to 29, and n2 + n4 is an integer of 0 to 30, and-(AO)-and-
• the arrangement of the (BO) — repeating unit may be random or block. In the case of a block, either — (A—O) — or — (B—O) — may be on the bisphenyl group side. ⁇
• the compound represented by these can be used.
• polyethylene glycol dimethacrylate having an average of 5 moles of ethylene oxide added to both ends of bisphenol A and polyethylene glycol having an average of 2 moles of ethylene oxide added to both ends of bisphenol A, respectively.
• polyethylene glycol dimethacrylate having an average of 1 mole of ethylene oxide added to both ends of dimethacrylate and bisphenol A is preferable.
• hetero atom examples include a halogen atom
• substituent examples include an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, an aryl group having 6 to 18 carbon atoms, and a phenacyl group.
• substituents may form a condensed ring, or a hydrogen atom in these substituents may be substituted with a hetero atom such as a halogen atom.
• the aromatic ring in the general formula (I) has a plurality of substituents, the plurality of substituents may be the same or different.
• the compound having 3 or more (meth) acryloyl groups in the molecule has at least 3 moles of a group capable of adding an alkylene oxide group in the molecule as a central skeleton, and includes an ethyleneoxy group, a propyleneoxy group, It can be obtained by using (meth) acrylate as an alcohol obtained by adding an alkyleneoxy group such as a butyleneoxy group.
• examples of the compound that can be a central skeleton include glycerin, trimethylolpropane, pentaerythritol, dipentaerythritol, and isocyanurate rings.
• These compounds include tri (meth) acrylates such as ethoxylated glycerin tri (meth) acrylate, ethoxylated isocyanuric acid tri (meth) acrylate, pentaerythritol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate (eg Trimethacrylate obtained by adding an average of 21 moles of ethylene oxide to trimethylolpropane and trimethacrylate obtained by adding an average of 30 moles of ethylene oxide to trimethylolpropane are preferable from the viewpoints of flexibility, adhesion, and bleedout suppression), etc .; (Meth) acrylates such as ditrimethylolpropane tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate ; Penta (meth) acrylate, for example, dip
• a compound having 3 or more (meth) acryloyl groups is preferable from the viewpoint of resolution, adhesion, and resist shape, and more preferably a compound having 3 or more methacryl groups.
• the tetra (meth) acrylate pentaerythritol tetra (meth) acrylate is preferable.
• the pentaerythritol tetra (meth) acrylate may be tetra (meth) acrylate in which 1 to 40 moles of alkylene oxide is added to the four terminals of pentaerythritol.
• Hexa (meth) acrylate is hexa (meth) acrylate in which 1 to 40 moles of ethylene oxide is added to 6 terminals of dipentaerythritol, and 1 to 20 moles of ⁇ in total at 6 terminals of dipentaerythritol.
• -Hexa (meth) acrylate with added caprolactone is preferred.
• the (meth) acrylate compounds described above can be used independently or in combination.
• the photosensitive resin composition may also contain other compounds as the compound (B) having an ethylenically unsaturated bond.
• Other compounds include urethane-bonded (meth) acrylates, compounds obtained by reacting polyhydric alcohols with ⁇ , ⁇ -unsaturated carboxylic acids, and glycidyl group-containing compounds with ⁇ , ⁇ -unsaturated carboxylic acids. And a compound obtained by the reaction, 1,6-hexanediol di (meth) acrylate, and the like.
• the ratio of the compound having an ethylenically unsaturated double bond to the total solid content of the photosensitive resin composition is preferably 5% by mass to 70% by mass. Setting this ratio to 5% by mass or more is preferable from the viewpoints of sensitivity, resolution, and adhesion. This ratio is more preferably 20% by mass or more, and further preferably 30% by mass or more. On the other hand, setting this ratio to 70% by mass or less is preferable from the viewpoint of suppressing the delay of peeling of the edge fuse and the cured resist. More preferably, this ratio is 50% by mass or less.
• a photopolymerization initiator is a compound that polymerizes a monomer by light.
• the photosensitive resin composition contains (C) a compound generally known in the art as a photopolymerization initiator.
• the total content of the photopolymerization initiator (C) in the photosensitive resin composition is preferably 0.01 to 20% by mass, more preferably 0.05 to 10% by mass, and still more preferably 0.1% by mass. % To 7% by mass, particularly preferably in the range of 0.1% to 6% by mass.
• the total content of the photopolymerization initiator is preferably 0.01% by mass or more from the viewpoint of obtaining sufficient sensitivity, and sufficiently transmits light to the bottom surface of the resist to provide good high resolution. It is preferable that it is 20 mass% or less from a viewpoint of obtaining.
• Photopolymerization initiators include quinones, aromatic ketones, acetophenones, acylphosphine oxides, benzoin or benzoin ethers, dialkyl ketals, thioxanthones, dialkylaminobenzoic acid esters, oxime esters
• Acridines for example, 9-phenylacridine, bisacridinylheptane, 9- (p-methylphenyl) acridine, 9- (m-methylphenyl) acridine are preferred in terms of sensitivity, resolution, and adhesion).
• hexaarylbiimidazole, pyrazoline compounds, anthracene compounds for example, 9,10-dibutoxyanthracene and 9,10-diethoxyanthracene are preferable in terms of sensitivity, resolution, and adhesion
• coumarin compounds for example, 7-diethylamino-4-methyl Coumarin is preferred in terms of sensitivity, resolution, and adhesion
• N-aryl amino acids or ester compounds thereof eg, N-phenylglycine is preferred in terms of sensitivity, resolution, and adhesion
• halogen compounds eg, Tribromomethylphenylsulfone
• 2,2-dimethoxy-1,2-diphenylethane-1-one, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, 2,4,6-trimethylbenzo Ir-diphenyl-phosphine oxide and triphenylphosphine oxide may be used.
• aromatic ketones examples include benzophenone, Michler's ketone [4,4′-bis (dimethylamino) benzophenone], 4,4′-bis (diethylamino) benzophenone, 4-methoxy-4′-dimethylaminobenzophenone. Can do. These can be used alone or in combination of two or more. Among these, 4,4'-bis (diethylamino) benzophenone is preferable from the viewpoint of adhesion. Furthermore, from the viewpoint of transmittance, the content of aromatic ketones in the photosensitive resin composition is preferably 0.01% by mass to 0.5% by mass, more preferably 0.02% by mass to 0.3%. It is in the range of mass%.
• hexaarylbiimidazole examples include 2- (o-chlorophenyl) -4,5-diphenylbiimidazole, 2,2 ′, 5-tris- (o-chlorophenyl) -4- (3,4-dimethoxyphenyl) -4 ', 5'-diphenylbiimidazole, 2,4-bis- (o-chlorophenyl) -5- (3,4-dimethoxyphenyl) -diphenylbiimidazole, 2,4,5-tris- (o-chlorophenyl) ) -Diphenylbiimidazole, 2- (o-chlorophenyl) -bis-4,5- (3,4-dimethoxyphenyl) -biimidazole, 2,2′-bis- (2-fluorophenyl) -4,4 ′ , 5,5'-tetrakis- (3-methoxyphenyl) -biimid
• the content of the hexaarylbisimidazole compound in the photosensitive resin composition is preferably 0.05% by mass to 7% by mass from the viewpoint of improving the peeling characteristics and / or sensitivity of the photosensitive resin layer. %, More preferably in the range of 0.1% to 6% by weight, still more preferably in the range of 1% to 5% by weight.
• the photosensitive resin composition preferably also contains a pyrazoline compound as a photosensitizer.
• the pyrazoline compound include 1-phenyl-3- (4-tert-butyl-styryl) -5- (4-tert-butyl-phenyl) -pyrazoline, 1- (4- (benzoxazol-2-yl) Phenyl) -3- (4-tert-butyl-styryl) -5- (4-tert-butyl-phenyl) -pyrazoline, 1-phenyl-3- (4-biphenyl) -5- (4-tert-butyl- Phenyl) -pyrazoline, 1-phenyl-3- (4-biphenyl) -5- (4-tert-octyl-phenyl) -pyrazoline, 1-phenyl-3- (4-isopropylstyryl) -5
• the content of the photosensitizer in the photosensitive resin composition is preferably 0.05% by mass to 5% by mass from the viewpoint of improving the peeling property and / or sensitivity of the photosensitive resin layer. More preferably, it is within the range of 0.1% by mass to 3% by mass.
• the photosensitive resin composition further contains (D) phenol derivative.
• the phenol derivative (p) include p-methoxyphenol, hydroquinone, pyrogallol, tert-butylcatechol, 2,6-di-tert-butyl-p-cresol, 2,2′-methylenebis (4-methyl-6- tert-butylphenol), 2,2′-methylenebis (4-ethyl-6-tert-butylphenol), 2,6-di-tert-butyl-4-methylphenol, 2,5-di-tert-amylhydroquinone, , 5-di-tert-butylhydroquinone, 2,2'-methylenebis (4-methyl-6-tert-butylphenol), bis (2-hydroxy-3-tert-butyl-5-ethylphenyl) methane, triethylene glycol -Bis [3- (3-tert-but)
• (D) It is preferable to contain a phenol derivative from the viewpoint of suppressing an increase in line width and a deterioration in resolution when the focal position at the time of exposure shifts, and hindered phenol or biphenol is preferable from the same viewpoint. From the same viewpoint, the (D) phenol derivative preferably has two or more phenol nuclei.
• the ratio of the phenol derivative to the total solid mass of the photosensitive resin composition is preferably 0.001% by mass to 10% by mass.
• This ratio is preferably 0.001% by mass or more, and preferably 0.005% by mass or more from the viewpoint of suppressing an increase in line width and a deterioration in resolution when the focal position during exposure is shifted.
• this ratio is preferably 10% by mass or less, more preferably 5% by mass or less, and more preferably 3% by mass or less, from the viewpoint of little reduction in sensitivity and improvement in resolution. Is more preferably 2% by mass or less, and most preferably 1.5% by mass or less.
• the photosensitive resin composition may contain additives such as dyes, plasticizers, antioxidants, and stabilizers as desired.
• additives listed in JP2013-156369A may be used.
• the photosensitive resin composition may further contain at least one selected from the group consisting of dyes (for example, leuco dyes, fluoran dyes, etc.) and coloring substances, if desired.
• the coloring substance examples include fuchsin, phthalocyanine green, auramine base, paramadienta, crystal violet, methyl orange, Nile blue 2B, Victoria blue, malachite green (for example, Eisen (registered trademark) MALACHITE GREEN manufactured by Hodogaya Chemical Co., Ltd.), Examples thereof include Basic Blue 20 and Diamond Green (for example, Eizen (registered trademark) DIAMOND GREEN GH manufactured by Hodogaya Chemical Co., Ltd.).
• 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.
• the content of 0.001% by mass or more is preferable from the viewpoint of improving the handleability of the photosensitive resin composition.
• the photosensitive resin composition is preferable in terms of visibility because the exposed portion develops color by containing a dye, and when the inspection machine reads the alignment marker for exposure, the exposed portion and the unexposed portion
• Preferred dyes from this viewpoint include leuco dyes and fluoran dyes.
• the leuco dye include tris (4-dimethylaminophenyl) methane [leuco crystal violet], bis (4-dimethylaminophenyl) phenylmethane [leucomalachite green], and the like.
• leuco crystal violet it is preferable to use leuco crystal violet as the leuco dye.
• the content of the leuco dye in the photosensitive resin composition is preferably 0.1% by mass to 10% by mass with respect to the total solid mass of the photosensitive resin composition. Setting this 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 particularly preferably 0.4% by mass or more. On the other hand, the content is preferably 10% by mass or less from the viewpoint of maintaining storage stability. The content is more preferably 5% by mass or less, and particularly preferably 2% by mass or less.
• the 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%. % To 3% by mass is preferable from the viewpoint of maintaining the storage stability of the hue in the photosensitive layer.
• the photosensitive resin composition further contains at least one compound selected from the group consisting of radical polymerization inhibitors, benzotriazoles, and carboxybenzotriazoles, in order to improve thermal stability and storage stability. Also good.
• radical polymerization inhibitors include naphthylamine, cuprous chloride, nitrosophenylhydroxyamine aluminum salt, diphenylnitrosamine and the like. In order not to impair the sensitivity of the photosensitive resin composition, a nitrosophenylhydroxyamine aluminum salt is preferred.
• 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.
• 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, benzotriazoles, and carboxybenzotriazoles is preferably 0.01% by mass to 100% by mass when the total solid content of the photosensitive resin composition is 100% by mass. It is 3% by mass, and more preferably 0.05% by mass to 1% by mass.
• the content of 0.01% by mass or more is preferable from the viewpoint of imparting storage stability to the photosensitive resin composition.
• the content of 3% by mass or less is preferable from the viewpoint of maintaining sensitivity and suppressing dye decolorization.
• the decolorization of the dye can be measured by the transmittance at a wavelength of 630 nm. A high transmittance at a wavelength of 630 nm indicates that the dye is decolorized.
• the transmittance of the laminate of the support film and the photosensitive resin composition layer at a wavelength of 630 nm is preferably 80% or less, preferably 78% or less, preferably 75% or less, and 72% or less. Preferably, it is 70% or less, preferably 68% or less, preferably 65% or less, preferably 62% or less, preferably 60% or less, It is preferably 58% or less, preferably 55% or less, preferably 52% or less, and preferably 50% or less.
• This transmittance is the transmittance of the laminate of the support film and the photosensitive resin composition layer, and does not include the protective layer.
• the photosensitive resin composition may further contain epoxy compounds of bisphenol A.
• bisphenol A epoxy compounds include compounds obtained by modifying bisphenol A with polypropylene glycol and epoxidizing the ends.
• the photosensitive resin composition may further contain a plasticizer.
• plasticizer examples include phthalic acid esters (eg, diethyl flate), o-toluenesulfonic acid amide, p-toluenesulfonic acid amide, tributyl citrate, triethyl citrate, acetyl triethyl citrate, acetyl citrate tri -N-propyl, tri-n-butyl acetyl citrate, polyethylene glycol, polypropylene glycol, polyethylene glycol alkyl ether, polypropylene glycol alkyl ether and the like.
• phthalic acid esters eg, diethyl flate
• o-toluenesulfonic acid amide examples include tributyl citrate, triethyl citrate, acetyl triethyl citrate, acetyl citrate tri -N-propyl, tri-n-butyl acetyl citrate, polyethylene glycol, polyprop
• Adecanol SDX-1569, Adecanol SDX-1570, Adecanol SDX-1571, Adecanol SDX-479 (manufactured by Asahi Denka Co., Ltd.), New Pole BP-23P, New Pole BP-3P, New Pole BP-5P, New Pole Pole BPE-20T, New Pole BPE-60, New Pole BPE-100, New Pole BPE-180 (manufactured by Sanyo Chemical Co., Ltd.), Unior DB-400, Unior DAB-800, Unior DA-350F, Unior DA- Examples thereof include compounds having a bisphenol skeleton such as 400, Uniol DA-700 (manufactured by Nippon Oil & Fats Co., Ltd.), BA-P4U glycol, BA-P8 glycol (manufactured by Nippon Emulsifier Co., Ltd.).
• the content of the plasticizer in the photosensitive resin composition is preferably 1% by mass to 50% by mass, more preferably 1% by mass to 30% by mass with respect to the total solid content mass of the photosensitive resin composition. It is. Setting the content to 1% by mass or more is preferable from the viewpoint of suppressing delay in development time and imparting flexibility to the cured film. On the other hand, setting the content to 50% by mass or less is preferable from the viewpoint of suppressing insufficient curing and cold flow.
• the water content in the photosensitive resin composition is 0.7% or less based on the photosensitive resin composition after applying the photosensitive resin composition preparation liquid to the support film and drying. Is preferred.
• the water content in the photosensitive resin composition is preferably 0.65% or less, preferably 0.6% or less, preferably 0.55% or less, and 0.5% or less. It is preferably 0.45% or less, preferably 0.4% or less, preferably 0.35% or less, preferably 0.3% or less, and It is preferably 25% or less, and preferably 0.2% or less.
• the photosensitive resin composition can be dissolved in a solvent and used in the production of a photosensitive resin laminate in the form of a photosensitive resin composition preparation.
• the solvent include ketones and alcohols.
• the ketones are typified by methyl ethyl ketone (MEK) and acetone.
• the alcohols are typified by methanol, ethanol, and isopropanol.
• the solvent is photosensitive in such an amount that the viscosity at 25 ° C. of the photosensitive resin composition preparation applied on the support layer is 500 mPa ⁇ s to 4,000 mPa ⁇ s. It is preferable to add to the resin composition.
• the method includes a lamination step of laminating a photosensitive resin laminate on a substrate, an exposure step of exposing a photosensitive resin layer of the photosensitive resin laminate, and a development step of developing and removing unexposed portions of the photosensitive resin layer Can be included.
• resist patterns include printed wiring boards, semiconductor elements, printing plates, liquid crystal display panels, flexible substrates, lead frame substrates, COF (chip on film) substrates, semiconductor package substrates, liquid crystal transparent electrodes, and liquid crystal TFTs. Patterns for wiring, PDP (plasma display panel) electrodes, and the like.
• a method for manufacturing a printed wiring board will be described as follows.
• a printed wiring board is manufactured through the following steps.
• (1) Laminating process First, in the laminating process, a photosensitive resin layer is formed on a substrate using a laminator. Specifically, when the photosensitive resin laminate has a protective layer, the protective layer is peeled off, and then the photosensitive resin layer is heat-pressed and laminated on the substrate surface with a laminator. Examples of the material of the substrate include copper, stainless steel (SUS), glass, indium tin oxide (ITO), and the like. In the present embodiment, the photosensitive resin layer may be laminated on only one surface of the substrate surface, or may be laminated on both surfaces as necessary. The heating temperature during lamination is generally 40 ° C to 160 ° C.
• substrate of the resist pattern obtained can be improved by performing the thermocompression bonding at the time of lamination twice or more.
• a two-stage laminator provided with two rolls may be used, or the lamination of the substrate and the photosensitive resin layer may be repeated several times and passed through the roll.
• Exposure step In this step, an exposure method using an active light source by closely attaching a mask film having a desired wiring pattern on a support layer, an exposure method by direct drawing of a drawing pattern which is a desired wiring pattern, or The photosensitive resin layer is exposed by an exposure method in which an image of a photomask is projected through a lens.
• the advantages of the photosensitive resin composition according to the present embodiment are more remarkable in an exposure method by direct drawing of a drawing pattern or an exposure method in which an image of a photomask is projected through a lens, and exposure by direct drawing of a drawing pattern. Particularly noticeable in the method.
• the support layer on the photosensitive resin layer is peeled off, and then the unexposed area is developed and removed using a developer of an alkaline aqueous solution, whereby the resist pattern is formed on the substrate.
• an alkaline aqueous solution an aqueous solution of Na 2 CO 3 or K 2 CO 3 is used.
• the alkaline aqueous solution is appropriately selected according to the characteristics of the photosensitive resin layer, but an aqueous Na 2 CO 3 solution having a concentration of about 0.2% by mass to about 2% by mass and about 20 ° C. to about 40 ° C. is preferable.
• a resist pattern can be obtained through the above steps (1) to (3). After these steps, a heating step of about 100 ° C.
• heating to about 300 ° C. can be further performed in some cases.
• chemical resistance can be further improved.
• a hot-air, infrared, or far-infrared heating furnace can be used. Moreover, you may implement this heating process after an exposure process.
• the substrate surface exposed by development (for example, the copper surface of a copper-clad laminate) is etched or plated to produce a conductor pattern.
• Stripping process Thereafter, the resist pattern is stripped from the substrate with an aqueous solution having alkalinity stronger than the developer.
• the alkaline aqueous solution for peeling is not particularly limited, but an aqueous solution of NaOH or KOH having a concentration of about 2% by mass to about 5% by mass and a temperature of about 40 to about 70 ° C. is preferable.
• a small amount of a water-soluble solvent can also be added to the stripping solution.
• the photosensitive resin laminate of the present embodiment is a conductive pattern such as a printed wiring board, a flexible substrate, a lead frame substrate, a COF substrate, a semiconductor package substrate, a liquid crystal transparent electrode, a liquid crystal TFT wiring, and a PDP electrode. It is the photosensitive resin laminated body suitable for manufacture of this. Note that the various parameters described above are measured according to a method understood by a person skilled in the art to be equivalent to the measurement method in Examples described later or the same unless otherwise specified.
• the present embodiment will be described more specifically with reference to examples and comparative examples.
• the present embodiment is not limited to the following examples unless departing from the gist thereof.
• the physical properties in the examples were measured by the following methods. The measurement of the physical property value of the polymer, the calculation of the glass transition temperature of the polymer, and the method for producing samples for evaluation of Examples and Comparative Examples are described. Moreover, the evaluation method about the obtained sample and its evaluation result are shown.
• the weight average molecular weight or number average molecular weight of the polymer is determined by gel permeation chromatography (GPC) manufactured by JASCO Corporation (pump: Gulliver, PU-1580 type, column: Shodex (registered trademark) manufactured by Showa Denko KK). KF-807, KF-806M, KF-806M, KF-802.5) in series, moving bed solvent: tetrahydrofuran, polystyrene standard sample (use of calibration curve with Shodex STANDARD SM-105 manufactured by Showa Denko KK) It calculated
• an acid equivalent means the mass (gram) of the polymer which has a 1 equivalent carboxyl group in a molecule
• Hiranuma automatic titrator (COM-555) was used, and the acid equivalent was measured by potentiometric titration using a 0.1 mol / L aqueous sodium hydroxide solution.
• the weight average value Tg total of the glass transition temperature Tg of the alkali-soluble polymer is represented by the following formula: ⁇ Wherein W i is the solid weight of each alkali-soluble polymer, T g i is the glass transition temperature determined by the Fox formula of each alkali-soluble polymer, and W total is each alkali-soluble polymer.
• the total solid weight of the polymer, and n is the number of types of alkali-soluble polymer contained in the photosensitive resin composition ⁇ Is the value obtained according to
• Tgi glass transition temperature
• the glass transition temperature of a homopolymer composed of a comonomer that forms the corresponding alkali-soluble polymer is determined by Brandrup, J. et al. Immergut, E .; H.
• the value shown in the edit “Polymer handbook, Third edition, John Wiley & Sons, 1989, p. 209 Chapter VI“ Glass transition temperatures of polymers ” is used.
• Table 3 shows the glass transition temperature of the homopolymer composed of each comonomer used in the calculation in the examples.
• the evaluation sample was prepared as follows. ⁇ Preparation of photosensitive resin laminate>
• the photosensitive resin composition preparation liquid is obtained by sufficiently stirring and mixing the components shown in Table 1 to be described later (however, the numbers of the respective components indicate the blending amount (part by mass) as the solid content) and the solvent. It was.
• the names of the components represented by abbreviations in Table 1 are shown in Table 2 below.
• As a support film a polyethylene terephthalate film having a thickness of 16 ⁇ m shown in Table 1 was prepared. The total number of fine particles of 1.5 ⁇ m or more and less than 4.5 ⁇ m contained in each polyethylene terephthalate film was determined by the following method.
• the number of fine particles of 1.5 ⁇ m or more and less than 4.5 ⁇ m present in a square piece having a side of 5 mm of a polyethylene terephthalate film was measured over the entire thickness direction using an optical microscope.
• the longest width of the fine particles is taken as the diameter of the fine particles. This measurement was performed at any 10 locations within the surface of the polyethylene terephthalate film, and the average value was calculated.
• the prepared solution was uniformly applied to the surface of the polyethylene terephthalate film and dried in a dryer at 95 ° C. for 2.5 minutes to form a photosensitive resin composition layer.
• the dry thickness of the photosensitive resin composition layer was 25 ⁇ m.
• a 19 ⁇ m-thick polyethylene film (manufactured by Tamapoly Co., Ltd., GF-818) was bonded as a protective layer on the surface of the photosensitive resin composition layer on which the polyethylene terephthalate film was not laminated. Got the body.
• ⁇ Board surface preparation> In Examples 1 to 13 and Comparative Example 1, a 0.4 mm-thick copper-clad laminate in which 35 ⁇ m rolled copper foil was laminated was used as an evaluation board for image quality, and a soft etching agent (CPE-900, manufactured by Hishie Chemical Co., Ltd.). Then, the substrate surface was cleaned with 10 mass% H 2 SO 4 .
• ⁇ Laminate> While peeling off the polyethylene film (protective layer) of the photosensitive resin laminate, the photosensitive resin laminate was applied to a copper clad laminate preheated to 60 ° C. using a hot roll laminator (Asahi Kasei Co., Ltd., AL-700). Lamination was performed at a roll temperature of 105 ° C. The air pressure was 0.35 MPa, and the laminating speed was 1.5 m / min.
• ⁇ Exposure> With a direct drawing exposure machine (Hitachi Via Mechanics Co., Ltd., DE-1DH, light source: GaN blue-violet diode, main wavelength 405 ⁇ 5 nm), a stove 41 step tablet or a mask pattern for predetermined direct imaging (DI) exposure was exposed under the conditions of an illuminance of 85 mW / cm 2. The exposure was performed with an exposure amount at which the maximum number of remaining film steps when the exposure and development were performed using the stove 41 step tablet as a mask was 14 steps.
• DI direct imaging
• ⁇ Evaluation of line width thickening A> The position of the focal point at the time of exposure was shifted from the polyethylene terephthalate film surface to the inner side of the 400 ⁇ m substrate in the thickness direction of the evaluation substrate. Except this, it was the same as the measurement of the line width (normal) described above. A value obtained by subtracting the above-described line width (normal) from the line width at this time was defined as the value of line width thickening A.
• ⁇ Evaluation of line width thickening B> The position of the focal point at the time of exposure was shifted from the surface of the polyethylene terephthalate film to the inside of the 800 ⁇ m substrate in the thickness direction of the evaluation substrate. Except this, it was the same as the measurement of the line width (normal) described above. A value obtained by subtracting the above-described line width (normal) from the line width at this time is defined as a value of line width thickening B.
• the cured resist pattern there was no residual resist on the unexposed portion of the substrate surface, and the substrate surface was exposed, and there was no protrusion of the resist component from the cured resist, and the minimum diameter of the hole formed normally was evaluated.
• As the resolution value 30 ⁇ m or less was obtained in 2 ⁇ m increments, 30 ⁇ m or more and 50 ⁇ m or less was obtained in 5 ⁇ m increments, and 50 ⁇ m or more was exposed using a drawing pattern obtained in 10 ⁇ m increments. Note that the pattern in which the unexposed portion is a circular hole is a much stricter evaluation than the normal resolution evaluation because the unexposed portion is difficult to be developed because the periphery of the unexposed portion is surrounded by the exposed portion.
• ⁇ Evaluation of resolution B> The focal position at the time of exposure was shifted from the surface of the polyethylene terephthalate film to the inside of the 200 ⁇ m substrate in the thickness direction of the evaluation substrate. Except this, it was the same as the measurement of the resolution A described above, and the resolution B was evaluated.
• ⁇ Evaluation of resolution C> The position of the focal point at the time of exposure was shifted from the polyethylene terephthalate film surface to the inner side of the 400 ⁇ m substrate in the thickness direction of the evaluation substrate. Except this, it was the same as the measurement of the resolution A described above, and the resolution C was evaluated.
• the number of fine particles of 1.5 ⁇ m or more and less than 4.5 ⁇ m contained in the small piece of the support film is 0 to 200 on an average of 10 positions.
• the difference, that is, resolution B-resolution A, resolution C-resolution A is suppressed to be smaller than that of Comparative Example 1 in which the number of fine particles is larger than 200, and line width thickening A and line width thickening B are also kept small.
• Example 3 The same photosensitive resin composition as in Example 3 was used, using a 16 ⁇ m thick polyethylene terephthalate film (manufactured by Toray Industries, Inc., 16QS68) having the same number of fine particles of 1.5 ⁇ m or more and less than 4.5 ⁇ m as in Example 3.
• 16QS68 polyethylene terephthalate film
• Example 1 partial peeling of the polyethylene terephthalate film was not observed after lamination to the substrate.
• Example 7 the polyethylene terephthalate film was partially peeled after lamination to the substrate. Observed. If the support film is peeled off from the photosensitive resin composition layer before exposure, oxygen enters between the support film and the photosensitive resin composition layer, and curing of the photosensitive resin composition is possible even if exposure is caused by the oxygen. Defects may occur.
• the support film and the photosensitive resin composition of the present embodiment in comparison with Examples and Comparative Examples, even when the focus during exposure is deviated, there is little increase in line width and little deterioration in resolution. You can see that it is possible.
• the polyethylene terephthalate film or the photosensitive resin composition when forming a pattern by an etching method or a plating method, the mask line width reproducibility is good even when irregularities and undulations exist on the substrate surface, and the short A high-definition circuit free from problems such as defects, chipping, disconnection, and plating defects can be formed.
• the photosensitive resin laminate of the present invention can suppress the increase in line width and the resolution when the focal position shifts at the time of exposure, exposure due to warpage and distortion of the substrate, setting failure of the exposure apparatus, etc. Even when the position of the focal point deviates from the substrate surface, short circuit problems are prevented when a circuit is formed by an etching method, and problems such as chipping, disconnection, and plating defects are formed when a circuit is formed by a plating method. And a desired circuit width can be obtained. Therefore, the photosensitive resin laminate includes a printed wiring board, a flexible substrate, a lead frame substrate, a COF (chip on film) substrate, a semiconductor package substrate, a liquid crystal transparent electrode, a liquid crystal TFT wiring, a PDP (plasma display). It can be suitably used for the production of conductor patterns such as electrodes for panels).

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• Physics & Mathematics (AREA)
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• Spectroscopy & Molecular Physics (AREA)
• Architecture (AREA)
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• Chemical Kinetics & Catalysis (AREA)
• Chemical & Material Sciences (AREA)
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• Materials For Photolithography (AREA)
• Manufacturing Of Printed Circuit Boards (AREA)
• Manufacturing Of Printed Wiring (AREA)
• Exposure And Positioning Against Photoresist Photosensitive Materials (AREA)
• Laminated Bodies (AREA)

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• 2017
  • 2017-12-05 JP JP2018555021A patent/JP6985291B2/ja active Active
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  • 2017-12-05 CN CN201780055093.XA patent/CN109690404B/zh active Active
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• 2021
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