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WO2023054637A1 - Procédé de fabrication de stratifié - Google Patents

Procédé de fabrication de stratifié Download PDF

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Publication number
WO2023054637A1
WO2023054637A1 PCT/JP2022/036573 JP2022036573W WO2023054637A1 WO 2023054637 A1 WO2023054637 A1 WO 2023054637A1 JP 2022036573 W JP2022036573 W JP 2022036573W WO 2023054637 A1 WO2023054637 A1 WO 2023054637A1
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WO
WIPO (PCT)
Prior art keywords
resin composition
photosensitive resin
region
substrate
composition layer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2022/036573
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English (en)
Japanese (ja)
Inventor
大地 岡本
優之 志村
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Taiyo Holdings Co Ltd
Original Assignee
Taiyo Ink Mfg Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Taiyo Ink Mfg Co Ltd filed Critical Taiyo Ink Mfg Co Ltd
Priority to JP2023551876A priority Critical patent/JPWO2023054637A1/ja
Publication of WO2023054637A1 publication Critical patent/WO2023054637A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • G03F7/20—Exposure; Apparatus therefor
    • 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

Definitions

  • the present invention relates to a method for producing a laminate, and more particularly to a method for producing a laminate comprising a substrate and a cured film covering the surface of the substrate, wherein the cured film has regions with different thicknesses.
  • the amount of exposure light may be adjusted according to the thickness of the solder resist layer in order to cure the solder resist layer well. For good curing of the solder-resist layer, if the thickness of the solder-resist layer is large, the solder-resist layer is exposed and cured with a larger amount of light, while if the thickness of the solder-resist layer is small, a smaller It is necessary to expose and harden the solder resist layer with the amount of light.
  • solder resist such as a photosensitive resin composition
  • a solder resist layer a solder resist layer
  • exposing and curing the solder resist layer to form a solder resist. It is obtained by forming a cured film.
  • conductors such as copper are placed on the surface of printed wiring boards and package substrates.
  • the thickness of the formed solder resist layer may be different. That is, in some cases, the thickness of the solder resist layer formed in the area where the conductor is not arranged is larger than that in the area where the conductor is arranged.
  • Patent Document 1 the formation of a pattern with good resolution and line width roughness includes exposing the same photoresist film multiple times and includes a heating step of the photoresist film between exposures. A method is proposed. Further, in Patent Document 2, a solder resist ink layer containing an epoxy resin and an acrylic resin with a partial residual carboxylic acid is cured with different amounts of light irradiation or drying heat, thereby having regions with different refractive indices and different transparency.
  • a method of manufacturing a circuit board which includes forming a cured product. Further, in Patent Document 3, when forming a pattern of a resin composition film on a wiring board, a first portion and a second portion of the resin composition coating film applied on the wiring board are irradiated with different amounts of light. A method for manufacturing a coated wiring board has been proposed that includes an exposure step that exposes and does not expose a third portion. Further, in Patent Document 4, using a photocurable thermosetting resin composition containing a specific coloring agent and a specific dye, solder resist formation and marking formation are performed in one exposure step and one development step. A printed wiring board manufacturing method has been proposed in which
  • Patent Documents 1 to 4 provide a method for curing each of the plurality of regions with different thicknesses in the solder resist layer satisfactorily without causing undercuts or halation. Therefore, in the production of a laminate comprising a base material and a cured film covering the surface of the base material, each of the plurality of regions with different thicknesses in the solder resist layer formed on the surface of the base material is undercut or A technical problem is to provide a good curing method without causing halation.
  • the present invention provides a plurality of regions having different thicknesses in a photosensitive resin composition layer formed on the surface of the base material.
  • the object of the present invention is to provide a method for satisfactorily curing each of the above without causing undercuts or halation.
  • the gist of the present invention is as follows.
  • a method for producing a laminate comprising a base material and a cured film covering at least part of the surface of the base material, forming a photosensitive resin composition layer so as to cover at least part of the surface of the substrate; and exposing and curing the photosensitive resin composition layer to form the cured film.
  • the photosensitive resin composition layer formed to cover at least a portion of the surface of the substrate includes at least two regions R1 having a thickness of 1 to 30 ⁇ m and a region R2 having a thickness of 10 to 70 ⁇ m.
  • a method for producing a laminate comprising a base material and a cured film covering the surface of the base material, wherein the photosensitive resin composition layer formed on the surface of the base material has different thicknesses. It is possible to provide a laminate in which each of the plurality of regions has a cured film that is well cured and formed without causing undercutting or halation.
  • the production method of the present invention is a method for producing a laminate comprising a base material and a cured film covering at least part of the surface of the base material, comprising: (i) covering at least part of the surface of the base material with and (ii) exposing and curing the photosensitive resin composition layer to form the cured coating.
  • the photosensitive resin composition layer formed so as to cover at least a part of the surface of the substrate includes a region R1 having a thickness of 1 to 30 ⁇ m and a thickness of 10 to 10 ⁇ m.
  • the thickness of the photosensitive resin composition layer in the region R1 is T1
  • the thickness of the photosensitive resin composition layer in the region R2 is T2
  • the relationship of T1 ⁇ T2 is satisfied, and the integrated amount of light for exposing the region R1 is E1
  • the integrated amount of light for exposing the region R2 is E2
  • the relationship of E1 ⁇ E2 meet.
  • the laminate produced by the production method of the present invention may be a laminate comprising a base material and a cured film covering at least part of the surface of the base material.
  • the substrate is not particularly limited, and may be a substrate having a conductor (for example, a printed wiring board, a printed circuit board, a semiconductor substrate such as a package substrate) or a substrate having no conductor.
  • a conductor for example, a printed wiring board, a printed circuit board, a semiconductor substrate such as a package substrate
  • a substrate having no conductor In the substrate provided with a conductor, when a photosensitive resin composition layer is formed by applying a photosensitive resin composition described later, a plurality of regions having different thicknesses are likely to occur in the photosensitive resin composition layer.
  • a substrate having a conductor is used as a suitable laminate, and a printed wiring board is used as a particularly suitable laminate.
  • the base material and the photosensitive resin composition used for producing the laminate are described in detail below.
  • Base material As the base material constituting the laminate, the surface thereof is coated with a photosensitive resin composition described later to form a photosensitive resin composition layer, and the photosensitive resin composition layer is exposed and cured to obtain a photosensitive resin composition layer. Any material can be used without particular limitation as long as it has mechanical strength capable of forming a cured film of the resin composition.
  • Materials constituting the base material include, for example, polyimide resin, polyamideimide resin, polyamide resin, polyethylene terephthalate resin, polybutylene terephthalate resin, polyethylene naphthalate resin, polycarbonate resin, acrylonitrile-butadiene-styrene (ABS) resin, polystyrene, Cycloolefin polymer, liquid crystal polymer, polyether ether ketone, polyphenylene sulfide resin, polyphenylsulfone, polyphenylene ether, acrylic resin such as poly(meth)methyl acrylate, polyvinylidene fluoride resin, polyvinyl chloride resin, polyvinylidene chloride resin, Polyvinyl alcohol resin, polyethylene resin, polypropylene resin, urethane resin, silicon, silicon carbide, gallium nitride, sapphire, ceramics, glass, glass epoxy resin, glass polyimide, paper phenol, diamond-like carbon, alumina, polyester fiber, polyamide
  • the substrate is preferably insulating and may be porous. Moreover, the substrate may consist of a single layer, or may consist of a plurality of layers. When the substrate is composed of multiple layers, the multiple layers may be composed of the same material or may be composed of different materials.
  • the conductor is not particularly limited as long as it is commonly used in semiconductor substrates.
  • the conductor is not particularly limited as long as it is commonly used in semiconductor substrates.
  • copper, aluminum, gold, silver, etc. can be used, and copper is preferably used. be done.
  • the cured film constituting the laminate is formed by exposing and curing a photosensitive resin composition layer formed by applying a photosensitive resin composition so as to cover the surface of the substrate.
  • the photosensitive resin composition layer is formed to cover at least part of the substrate surface.
  • the photosensitive resin composition that constitutes the photosensitive resin composition layer is not particularly limited as long as it is a resin composition that cures when exposed to light, and its composition can be set as appropriate.
  • the photosensitive resin composition includes, for example, a carboxyl group-containing resin, a photopolymerizable resin, a thermosetting resin, a photopolymerization initiator, and the like.
  • the photosensitive resin composition may further contain a sensitizer, a coloring agent, a filler, a thermosetting catalyst, an organic solvent, and the like, if necessary.
  • the photosensitive resin composition various conventionally known resins having a carboxyl group in the molecule can be used as the carboxyl group-containing resin.
  • a carboxyl group-containing resin in the photosensitive resin composition, alkali developability can be imparted to the photosensitive resin composition.
  • a carboxyl group-containing photosensitive resin having an ethylenically unsaturated double bond in the molecule is preferable from the viewpoint of photocurability and development resistance.
  • the ethylenically unsaturated double bonds are preferably derived from acrylic acid or methacrylic acid or derivatives thereof.
  • carboxyl group-containing resins When only a carboxyl group-containing resin having no ethylenically unsaturated double bonds is used, in order to make the composition photocurable, a compound having a plurality of ethylenically unsaturated groups in the molecule, i.e., photo It is necessary to use a polymerizable resin together.
  • carboxyl group-containing resins include the following compounds (both oligomers and polymers).
  • Carboxyl group-containing resins may be used alone or in combination of two or more.
  • Carboxyl group-containing resins obtained by copolymerizing unsaturated carboxylic acids such as (meth)acrylic acid and unsaturated group-containing compounds such as styrene, ⁇ -methylstyrene, lower alkyl (meth)acrylates, and isobutylene.
  • Diisocyanates such as aliphatic diisocyanates, branched aliphatic diisocyanates, alicyclic diisocyanates and aromatic diisocyanates; Polyols, polyester polyols, polyolefin polyols, acrylic polyols, bisphenol A alkylene oxide adduct diols, carboxyl group-containing urethane resins obtained by polyaddition reaction of diol compounds such as compounds having phenolic hydroxyl groups and alcoholic hydroxyl groups.
  • a diisocyanate such as a bisphenol A type epoxy resin, a hydrogenated bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a bisphenol S type epoxy resin, a bixylenol type epoxy resin, or a biphenol type epoxy resin ( Carboxyl group-containing photosensitivity obtained by polyaddition reaction of partial acid anhydride-modified reaction product with monocarboxylic acid compound having ethylenically unsaturated double bond such as meth)acrylic acid, carboxyl group-containing dialcohol compound and diol compound Urethane resin.
  • a bifunctional epoxy resin such as a bisphenol A type epoxy resin, a hydrogenated bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a bisphenol S type epoxy resin, a bixylenol type epoxy resin, or a biphenol type epoxy resin ( Carboxyl group-containing photosensitivity obtained by polyaddition reaction of partial acid anhydride-modified reaction product with monocarboxylic acid compound having
  • one isocyanate group and one or more (meth)acryloyl groups are added in the molecule, such as an equimolar reaction product of isophorone diisocyanate and pentaerythritol triacrylate.
  • a carboxyl group-containing photosensitive resin obtained by reacting (meth)acrylic acid with a polyfunctional (solid) epoxy resin having two or more functionalities and adding a dibasic acid anhydride to the hydroxyl groups present in the side chains.
  • Group-containing photosensitive resin A carboxyl obtained by reacting (meth)acrylic acid with a polyfunctional epoxy resin obtained by further epoxidizing the hydroxyl group of a bifunctional (solid) epoxy resin with epichlorohydrin, and adding a dibasic acid anhydride to the resulting hydroxyl group.
  • a bifunctional oxetane resin is reacted with a dicarboxylic acid such as adipic acid, phthalic acid, and hexahydrophthalic acid, and the resulting primary hydroxyl group is treated with a dibasic such as phthalic anhydride, tetrahydrophthalic anhydride, and hexahydrophthalic anhydride.
  • a dicarboxylic acid such as adipic acid, phthalic acid, and hexahydrophthalic acid
  • a dibasic such as phthalic anhydride, tetrahydrophthalic anhydride, and hexahydrophthalic anhydride.
  • Carboxyl group-containing polyester resin to which acid anhydride is added.
  • an epoxy compound having a plurality of epoxy groups in one molecule a compound having at least one alcoholic hydroxyl group and one phenolic hydroxyl group in one molecule, such as p-hydroxyphenethyl alcohol;
  • a carboxyl group-containing photosensitive resin obtained by reacting a polybasic acid anhydride such as an acid.
  • (11) Obtained by reacting a reaction product obtained by reacting a compound having a plurality of phenolic hydroxyl groups in one molecule with a cyclic carbonate compound such as ethylene carbonate or propylene carbonate with a monocarboxylic acid containing an unsaturated group.
  • a carboxyl group-containing photosensitive resin obtained by reacting a reaction product with a polybasic acid anhydride.
  • a carboxyl group-containing photosensitive resin obtained by further adding a compound having one epoxy group and one or more (meth)acryloyl groups in one molecule to the resins of (1) to (11).
  • (meth)acrylate is a generic term for acrylate, methacrylate and mixtures thereof, and the same applies to other similar expressions.
  • the carboxyl group-containing resins (10) and (11) are preferably used.
  • carboxyl group-containing resin is not limited to the carboxyl group-containing resins described above, and resins synthesized according to the procedures described in the examples described later can also be used.
  • the acid value of the carboxyl group-containing resin is preferably 40-150 mgKOH/g.
  • the acid value of the carboxyl group-containing resin is preferably 40-150 mgKOH/g.
  • the weight average molecular weight of the carboxyl group-containing resin varies depending on the resin skeleton, it is generally preferable to be 2,000 to 150,000. By setting the weight average molecular weight to 2,000 or more, tack-free performance and resolution can be improved. Further, by setting the weight average molecular weight to 150,000 or less, the developability and storage stability can be improved. More preferably from 5,000 to 100,000. Weight average molecular weight can be measured by gel permeation chromatography (GPC).
  • the blending amount of the carboxyl group-containing resin is preferably 20 to 60% by mass in terms of solid content in the photosensitive resin composition. By making it 20% by mass or more, the strength of the coating film can be improved. Moreover, by making it 60% by mass or less, the viscosity becomes appropriate and the processability improves. More preferably, it is 30 to 50% by mass.
  • photopolymerizable resins can be polymers, oligomers, monomers, and the like.
  • the photopolymerizable resin may be used singly or in combination of two or more.
  • photopolymerizable oligomers As the compound having an ethylenically unsaturated double bond, known and commonly used photopolymerizable oligomers, photopolymerizable monomers, and the like can be used. Among them, it is preferable to use a photopolymerizable monomer because it can impart more crosslinkability and curability to the cured film.
  • photopolymerizable resins include commonly known polyester (meth)acrylates, polyether (meth)acrylates, urethane (meth)acrylates, carbonate (meth)acrylates, epoxy (meth)acrylates, and the like.
  • alkyl acrylates such as 2-ethylhexyl acrylate and cyclohexyl acrylate
  • hydroxyalkyl acrylates such as 2-hydroxyethyl acrylate and 2-hydroxypropyl acrylate
  • alkylene glycols such as ethylene glycol, propylene glycol, diethylene glycol and dipropylene glycol.
  • acrylamides such as N,N-dimethylacrylamide, N-methylolacrylamide and N,N-dimethylaminopropylacrylamide; N,N-dimethylaminoethyl acrylate, N,N-dimethylaminopropyl Aminoalkyl acrylates such as acrylates; Polyhydric alcohols such as hexanediol, trimethylolpropane, pentaerythritol, ditrimethylolpropane, dipentaerythritol and trishydroxyethyl isocyanurate, or their alkylene oxide adducts or ⁇ -caprolactone adducts, etc.
  • polyvalent acrylates phenols such as phenoxy acrylate and bisphenol A diacrylate or polyvalent acrylates such as alkylene oxide adducts thereof; glycidyls such as glycerin diglycidyl ether, trimethylolpropane triglycidyl ether, and triglycidyl isocyanurate Ether acrylates; not limited to the above, acrylates and melamine acrylates obtained by directly acrylated polyols such as polyether polyols, polycarbonate diols, hydroxyl-terminated polybutadiene, and polyester polyols, or urethane acrylated via diisocyanate, and the above acrylates can be appropriately selected from at least one of the methacrylates corresponding to and used.
  • photopolymerizable resins can also be used as reactive diluents.
  • examples of commercially available photopolymerizable resins include KAYARAD DPHA (dipentaerythritol hexaacrylate) manufactured by Nippon Kayaku Co., Ltd., and the like.
  • the blending amount of the photopolymerizable resin is preferably 1 to 50 parts by mass with respect to 100 parts by mass of the carboxyl group-containing resin.
  • the blending amount is 1 part by mass or more, the photocurability is good, and pattern formation is facilitated in alkali development after irradiation with active energy rays.
  • the content is 50 parts by mass or less, halation is less likely to occur and good resolution can be obtained.
  • the photopolymerizable resin especially when using a carboxyl group-containing non-photosensitive resin that does not have an ethylenically unsaturated double bond, must be used in combination with a photopolymerizable resin in order to make the composition photocurable. Therefore, it is valid.
  • thermosetting resins In the photosensitive resin composition, conventionally known thermosetting resins can be used as the thermosetting resin. By adding a thermosetting resin to the photosensitive resin composition, it can be expected that the heat resistance of the photosensitive resin composition is improved.
  • thermosetting resins include melamine resins, benzoguanamine resins, melamine derivatives, amino resins such as benzoguanamine derivatives, isocyanate compounds, blocked isocyanate compounds, cyclocarbonate compounds, epoxy compounds, oxetane compounds, episulfide resins, bismaleimide, and carbodiimide resins.
  • thermosetting resin such as Thermosetting resins having a plurality of cyclic ether groups or cyclic thioether groups (hereinafter abbreviated as cyclic (thio)ether groups) in the molecule are particularly preferably used.
  • Thermosetting resins may be used singly or in combination of two or more.
  • thermosetting resin having a plurality of cyclic (thio) ether groups in the molecule is a compound having a plurality of 3-, 4- or 5-membered cyclic (thio) ether groups in the molecule.
  • Compounds having epoxy groups i.e. polyfunctional epoxy compounds, compounds having multiple oxetanyl groups in the molecule, i.e. polyfunctional oxetane compounds, compounds having multiple thioether groups in the molecule, i.e., episulfide resins, and the like.
  • polyfunctional epoxy compounds epoxidized vegetable oil; bisphenol A type epoxy resin; hydroquinone type epoxy resin; bisphenol type epoxy resin; thioether type epoxy resin; brominated epoxy resin; type epoxy resin; hydrogenated bisphenol A type epoxy resin; glycidylamine type epoxy resin; hydantoin type epoxy resin; alicyclic epoxy resin; Bisphenol S type epoxy resin; bisphenol A novolac type epoxy resin; tetraphenylolethane type epoxy resin; heterocyclic epoxy resin; diglycidyl phthalate resin; Glycidyl methacrylate copolymer epoxy resin; cyclohexyl maleimide and glycidyl methacrylate copolymer epoxy resin; epoxy-modified polybutadiene rubber derivative; CTBN-modified epoxy resin, etc., but not limited to these .
  • Examples of commercially available polyfunctional epoxy compounds include jER828 manufactured by Mitsubishi Chemical Corporation.
  • polyfunctional oxetane compounds include bis[(3-methyl-3-oxetanylmethoxy)methyl]ether, bis[(3-ethyl-3-oxetanylmethoxy)methyl]ether, 1,4-bis[(3- methyl-3-oxetanylmethoxy)methyl]benzene, 1,4-bis[(3-ethyl-3-oxetanylmethoxy)methyl]benzene, (3-methyl-3-oxetanyl)methyl acrylate, (3-ethyl-3- Oxetanyl)methyl acrylate, (3-methyl-3-oxetanyl)methyl methacrylate, (3-ethyl-3-oxetanyl)methyl methacrylate, and polyfunctional oxetanes such as their oligomers or copolymers, as well as oxetane alcohols and novolak resins , poly(p-hydroxystyrene), cardo-type bisphenols,
  • Examples of compounds having multiple cyclic thioether groups in the molecule include bisphenol A-type episulfide resins. Also, an episulfide resin obtained by replacing the oxygen atom of the epoxy group of the novolac type epoxy resin with a sulfur atom by using a similar synthesis method can be used.
  • Amino resins such as melamine derivatives and benzoguanamine derivatives include methylol melamine compounds, methylol benzoguanamine compounds, methylol glycoluril compounds and methylol urea compounds.
  • a polyisocyanate compound can be blended as the isocyanate compound.
  • Polyisocyanate compounds include 4,4′-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, naphthalene-1,5-diisocyanate, o-xylylene diisocyanate, m-xylylene diisocyanate and Aromatic polyisocyanates such as 2,4-tolylene dimer; Aliphatic polyisocyanates such as tetramethylene diisocyanate, hexamethylene diisocyanate, methylene diisocyanate, trimethylhexamethylene diisocyanate, 4,4-methylenebis(cyclohexyl isocyanate) and isophorone diisocyanate; bicyclo alicyclic polyisocyanates such as heptane triisocyanate; and adducts, biurets and isocyanurates
  • An addition reaction product of an isocyanate compound and an isocyanate blocking agent can be used as the blocked isocyanate compound.
  • the isocyanate compound that can react with the isocyanate blocking agent include the aforementioned polyisocyanate compounds.
  • isocyanate blocking agents include phenolic blocking agents; lactam blocking agents; active methylene blocking agents; alcohol blocking agents; oxime blocking agents; mercaptan blocking agents; Amine-based blocking agents; imidazole-based blocking agents; imine-based blocking agents, and the like.
  • the amount of the thermosetting resin to be incorporated in the photosensitive resin composition is such that the number of functional groups of the thermosetting resin that reacts with respect to 1 mol of the carboxyl group contained in the carboxyl group-containing resin is preferably 0.3 to 3.0 mol. More preferably 0.5 to 2.5 mol.
  • a conventionally known photopolymerization initiator can be used as the photopolymerization initiator in the photosensitive resin composition.
  • a photopolymerization initiator By adding a photopolymerization initiator to the photosensitive resin composition, the carboxyl group-containing resin and the photopolymerizable resin can be reacted by exposure.
  • a photoinitiator may be used individually by 1 type, and may be used in combination of 2 or more type.
  • photopolymerization initiators include bis-(2,6-dichlorobenzoyl)phenylphosphine oxide, bis-(2,6-dichlorobenzoyl)-2,5-dimethylphenylphosphine oxide, bis-(2, 6-dichlorobenzoyl)-4-propylphenylphosphine oxide, bis-(2,6-dichlorobenzoyl)-1-naphthylphosphine oxide, bis-(2,6-dimethoxybenzoyl)phenylphosphine oxide, bis-( 2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide, bis-(2,6-dimethoxybenzoyl)-2,5-dimethylphenylphosphine oxide, bis-(2,4,6- Bisacylphosphine oxides such as trimethylbenzoyl)-phenylphosphine oxide; 2,6-dimethoxybenzoyl
  • photopolymerization initiators it is preferable to use a photopolymerization initiator classified as a so-called oxime ester photopolymerization initiator.
  • commercially available photopolymerization initiators include, for example, oxime ester photopolymerization initiator Irgacure OXE02 manufactured by BASF Japan Ltd.
  • the amount of the photopolymerization initiator (excluding the oxime ester-based photopolymerization initiator) in the photosensitive resin composition is preferably 1 to 20 parts by mass with respect to 100 parts by mass of the carboxyl group-containing resin.
  • the content is 1 part by mass or more, the photocurability of the resin composition is improved, the film is difficult to peel off, and the film properties such as chemical resistance are improved.
  • the content is 20 parts by mass or less, the effect of reducing outgassing is obtained, the light absorption on the surface of the solder resist coating film is improved, and the deep-part curability is less likely to deteriorate. More preferably, it is 3 to 10 parts by mass.
  • the amount of the oxime ester photopolymerization initiator in the photosensitive resin composition is preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of the carboxyl group-containing resin.
  • the resin composition has good photocurability and good film properties such as heat resistance and chemical resistance.
  • the amount is 20 parts by mass or less, the light absorption of the solder resist film is improved, and the deep-part curability is less likely to deteriorate. More preferably, it is 0.5 to 10 parts by mass.
  • a photoinitiation aid or a sensitizer may be used in combination with the photopolymerization initiator described above.
  • Photoinitiation aids or sensitizers include benzoin compounds, anthraquinone compounds, thioxanthone compounds, ketal compounds, benzophenone compounds, tertiary amine compounds, xanthone compounds, and the like.
  • Thioxanthone compounds such as 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2-isopropylthioxanthone, and 4-isopropylthioxanthone are particularly preferred.
  • Inclusion of a thioxanthone compound can improve deep-part curability.
  • These compounds can be used as a photopolymerization initiator in some cases, but are preferably used in combination with the photopolymerization initiator.
  • Each of the photoinitiator aid and the sensitizer may be used alone or
  • photopolymerization initiators since these photopolymerization initiators, photoinitiator aids, and sensitizers absorb specific wavelengths, the sensitivity may be lowered in some cases, and they may function as ultraviolet absorbers. However, these are not used only for the purpose of improving the sensitivity of the composition. It absorbs light of a specific wavelength as needed to increase the photoreactivity of the surface, change the line shape and opening of the resist to vertical, tapered, and reverse tapered shapes, and improve the accuracy of the line width and opening diameter. can be improved.
  • the photosensitive resin composition may contain components such as colorants, fillers, thermosetting catalysts, and organic solvents. These components may be used individually by 1 type, and may be used in combination of 2 or more type.
  • coloring agent for example, known coloring agents such as red, blue, green, and yellow can be used, and any of pigments, dyes, and pigments can be used. However, it is preferable not to contain a halogen from the viewpoint of environmental load reduction and influence on the human body.
  • red colorants examples include monoazo, disazo, azo lake, benzimidazolone, perylene, diketopyrrolopyrrole, condensed azo, anthraquinone, and quinacridone colorants. Color Index (C.I.; issued by The Society of Dyers and Colorists) numbered.
  • Examples of monoazo red colorants include Pigment Red 1, 2, 3, 4, 5, 6, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 112, 114, 146, 147, 151, 170, 184, 187, 188, 193, 210, 245, 253, 258, 266, 267, 268, 269 and the like.
  • Examples of disazo-based red colorants include Pigment Red 37, 38, 41, and the like.
  • a monoazo lake-based red colorant for example, Pigment Red 48:1, 48:2, 48:3, 48:4, 49:1, 49:2, 50:1, 52:1, 52:2, 53:1, 53:2, 57:1, 58:4, 63:1, 63:2, 64:1, 68 and the like.
  • Examples of benzimidazolone-based red coloring agents include Pigment Red 171, 175, 176, 185, and 208.
  • Examples of perylene-based red colorants include Solvent Red 135, 179, Pigment Red 123, 149, 166, 178, 179, 190, 194, 224 and the like.
  • Examples of diketopyrrolopyrrole-based red colorants include Pigment Red 254, 255, 264, 270, 272 and the like.
  • Examples of condensed azo red colorants include Pigment Red 220, 144, 166, 214, 220, 221, 242 and the like.
  • anthraquinone-based red colorants include Pigment Red 168, 177, 216 and Solvent Red 52, 149, 150, 207.
  • quinacridone-based red colorants include Pigment Red 122, 202, 206, 207, and 209.
  • Blue colorants include, for example, phthalocyanine-based, anthraquinone-based, etc.
  • Pigment-based compounds are classified into pigments, for example, Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 60, and examples of dyes include Solvent Blue 35, 63, 67, 68, 70, 83, 87, 94, 97, 122, 136, etc. be done.
  • metal-substituted or unsubstituted phthalocyanine compounds can also be used.
  • yellow colorants examples include monoazo-based, disazo-based, condensed azo-based, benzimidazolone-based, isoindolinone-based, and anthraquinone-based coloring agents.
  • examples of anthraquinone-based yellow colorants include Solvent Yellow 163, Pigment Yellow 24, 108, 193, 147, 199, 202 and the like.
  • Examples of isoindolinone-based yellow colorants include Pigment Yellow 110, 109, 139, 179, 185 and the like.
  • condensed azo yellow colorants examples include Pigment Yellow 93, 94, 95, 128, 155, 166, 180 and the like.
  • Examples of benzimidazolone yellow colorants include Pigment Yellow 120, 151, 154, 156, 175, 181 and the like.
  • As the monoazo yellow colorant for example, Pigment Yellow 1, 2, 3, 4, 5, 6, 9, 10, 12, 61, 62, 62: 1, 65, 73, 74, 75, 97, 100, 104, 105, 111, 116, 167, 168, 169, 182, 183 and the like.
  • Disazo-based yellow colorants include, for example, Pigment Yellow 12, 13, 14, 16, 17, 55, 63, 81, 83, 87, 126, 127, 152, 170, 172, 174, 176, 188, 198 and the like.
  • coloring agents such as purple, orange, brown, black, and white may be added.
  • Pigment Black 1, 6, 7, 8, 9, 10, 11, 12, 13, 18, 20, 25, 26, 28, 29, 30, 31, 32, Pigment Violet 19, 23, 29 , 32, 36, 38, 42, Solvent Violet 13, 36, C.I. I. Pigment Orange 1, 5, 13, 14, 16, 17, 24, 34, 36, 38, 40, 43, 46, 49, 51, 61, 63, 64, 71, 73, Pigment Brown 23, 25, carbon black, Titanium oxide etc. are mentioned.
  • colorants may be used singly or in combination of two or more.
  • the amount of the colorant to be added in the photosensitive resin composition is not particularly limited, it may be 0.1 to 1.0 parts by mass based on 100 parts by mass of the carboxyl group-containing resin in terms of solid content. can.
  • filler By adding a filler to the photosensitive resin composition, it is possible to improve the physical strength of the cured film of the photosensitive resin composition layer.
  • conventionally known inorganic or organic fillers can be used, and barium sulfate, spherical silica, hydrotalcite and talc are particularly preferably used.
  • titanium oxide, metal oxides, and metal hydroxides such as aluminum hydroxide can be used as extender fillers in order to obtain a white appearance and flame retardancy.
  • barium sulfate is preferably used, and surface-treated barium sulfate is particularly preferably used.
  • Commercially available fillers include surface-treated barium sulfate B-30 manufactured by Sakai Chemical Industry Co., Ltd., for example.
  • fillers may be used singly or in combination of two or more.
  • the amount of filler compounded is preferably 80% by mass or less of the total amount of the photosensitive resin composition.
  • the amount of the filler compounded exceeds 80% by mass of the total amount of the composition, the viscosity of the insulating composition increases, the application and moldability deteriorate, and the cured product becomes brittle. More preferably 20 to 60% by mass.
  • thermosetting catalysts include imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1- Imidazole derivatives such as (2-cyanoethyl)-2-ethyl-4-methylimidazole; dicyandiamide, benzyldimethylamine, 4-(dimethylamino)-N,N-dimethylbenzylamine, 4-methoxy-N,N-dimethylbenzyl amines, amine compounds such as 4-methyl-N,N-dimethylbenzylamine; hydrazine compounds such as adipic acid dihydrazide and sebacic acid dihydrazide; and phosphorus compounds such
  • commercially available products include, for example, 2MZ-A, 2MZ-OK, 2PHZ, 2P4BHZ, and 2P4MHZ manufactured by Shikoku Kasei Co., Ltd. (all are trade names of imidazole compounds), and U-CAT manufactured by San-Apro Co., Ltd. 3513N (trade name of dimethylamine compound), DBU, DBN, U-CAT SA 102 (all bicyclic amidine compounds and salts thereof), and the like.
  • it is not limited to these, and it may be a thermosetting catalyst for an epoxy resin or an oxetane compound, or any one that promotes the reaction between at least one of an epoxy group and an oxetanyl group and a carboxyl group.
  • a mixture of seeds or more may be used.
  • a compound that also functions is used in conjunction with a thermosetting catalyst.
  • thermosetting catalysts may be used singly or in combination of two or more.
  • thermosetting catalyst can be used singly or in combination of two or more.
  • the amount of the thermosetting catalyst compounded is preferably 1 to 20 parts by mass, more preferably 2 to 15 parts by mass, per 100 parts by mass of the carboxyl group-containing resin. When it is 1 part by mass or more, the heat resistance is excellent. If it is 20 parts by mass or less, it leads to an improvement in storage stability.
  • An organic solvent can be added to the photosensitive resin composition for the purpose of preparing the photosensitive resin composition and adjusting the viscosity when applying the photosensitive resin composition to a substrate or film.
  • organic solvents examples include ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene and tetramethylbenzene; cellosolve, methyl cellosolve, butyl cellosolve, carbitol, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether; , dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, diethylene glycol monomethyl ether acetate, tripropylene glycol monomethyl ether; ethyl acetate, butyl acetate, butyl lactate, cellosolve acetate, butyl cellosolve acetate, carbitol acetate, butyl carbi Esters such as tall acetate, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate, and propylene carbonate; aliphatic
  • Volatilization drying of organic solvents is carried out by using a hot air circulating drying furnace, IR furnace, hot plate, convection oven, etc. (equipped with a heat source that heats the air using steam), and a method in which the hot air in the dryer is brought into contact with the counter current and supported by a nozzle. method of spraying on the body) can be used.
  • the blending amount of the organic solvent in the photosensitive resin composition can be appropriately changed according to the viscosity of the intended photosensitive resin composition, etc., according to the materials constituting the photosensitive resin composition.
  • a substrate and a photosensitive resin composition are prepared.
  • a photosensitive resin composition is applied so as to cover at least part of the surface of the prepared base material to form a layer of the photosensitive resin composition (photosensitive resin composition layer) on the surface of the base material.
  • the base material the same material as explained in the section on the above base material can be used.
  • the photosensitive resin composition is applied to the surface of the substrate by a method such as dip coating, flow coating, roll coating, bar coating, spray coating, screen printing, or curtain coating. Among these, application by screen printing is preferably used.
  • the photosensitive resin composition layer may be formed from a dry film of a photosensitive resin composition.
  • the photosensitive resin composition is applied onto the first film and dried to form a resin layer.
  • An example of using a photosensitive resin composition formed into a dry film is shown below.
  • a dry film is a laminate having a structure in which a first film, a resin layer, and an optionally peelable second film are laminated in this order.
  • the resin layer is a layer formed by applying and drying a photosensitive resin composition on the first film or the second film. After forming the resin layer on the first film, the second film is laminated thereon, or the resin layer is formed on the second film and the resulting laminate is laminated on the first film. A dry film is thus obtained.
  • any known film can be used without particular limitation.
  • a thermoplastic film such as a polyester film such as polyethylene terephthalate or polyethylene naphthalate having a thickness of 2 to 150 ⁇ m is used.
  • the resin layer is formed by uniformly applying a photosensitive resin composition to the first film or the second film with a blade coater, lip coater, comma coater, film coater, etc. to a thickness of, for example, 10 to 150 ⁇ m, and drying. It is formed.
  • the second film for example, a polyethylene film, a polypropylene film, or the like can be used, but it is preferable to use a film that has a smaller adhesive force to the resin layer than the first film.
  • the photosensitive resin composition layer to be formed has at least two regions R1 and R2 with different thicknesses, and the thickness of the photosensitive resin composition layer in the region R1 is T1,
  • T1 is 1 to 30 ⁇ m
  • T2 is 10 to 70 ⁇ m
  • T1 ⁇ T2 is applied to the surface of the substrate so as to satisfy
  • region R1 is the thickness of the photosensitive resin composition layer formed on the surface of the conductor
  • region 2 is the thickness of the photosensitive resin composition layer formed on the surface of the substrate. is the thickness of the material layer.
  • Step of curing the photosensitive resin composition to form a cured film Next, the photosensitive resin composition layer formed on the surface of the substrate is exposed and cured to form a cured film of the photosensitive resin composition.
  • E1 is the integrated amount of light for exposing the region R1 of the photosensitive resin composition layer
  • E2 is the integrated amount of light for exposing the region R2.
  • the following formula: E1 ⁇ E2 The photosensitive resin composition layer is exposed so as to satisfy When E1 and E2 satisfy the relationship of the above formula, each of the regions R1 and R2 of the photosensitive resin composition layer formed on the surface of the substrate can be cured satisfactorily without causing undercut or halation. can be done.
  • E1 and E2 may be an integrated amount of light in any wavelength range, but preferably an integrated amount of light with one or more wavelengths selected from the wavelength range of 330 to 430 nm, more preferably 365 nm. and the integrated amount of light with a wavelength of 405 nm.
  • the "integrated amount of light” means the integrated amount of light of that wavelength when E1 and E2 are each exposed with light of a single wavelength, and E1 and E2 are different. In the case of exposure with light including a plurality of wavelength regions, it means a value calculated by the sum of the integrated amount of light of those wavelengths (total integrated amount of light).
  • the "integrated amount of light” is the sum of the integrated amounts of light with wavelengths of 365 nm and 405 nm (total integrated amount of light). shall mean a calculated value.
  • E1 and E2 are not particularly limited as long as they satisfy the relationship of the above formula, but in relation to the thicknesses T1 and T2 of the photosensitive resin composition layer in the regions R1 and R2, they are preferably as follows. can.
  • E1 When the thickness T1 of the photosensitive resin composition layer in the region R1 is less than 10 ⁇ m, E1 has an integrated amount of light with a wavelength of 365 nm and an integrated amount of light with a wavelength of 405 nm that are independently 0 to 200 mJ/cm. 2 , and the sum of the integrated amount of light with a wavelength of 365 nm and the integrated amount of light with a wavelength of 405 nm is preferably 10 to 200 mJ/cm 2 .
  • E1 When the thickness T1 of the photosensitive resin composition layer in the region R1 is 10 ⁇ m or more, E1 has an integrated amount of light with a wavelength of 365 nm and an integrated amount of light with a wavelength of 405 nm, each independently from 0 to 300 mJ/cm. 2 , and the sum of the integrated amount of light with a wavelength of 365 nm and the integrated amount of light with a wavelength of 405 nm is preferably 10 to 300 mJ/cm 2 .
  • E2 When the thickness T2 of the photosensitive resin composition layer in the region R2 is less than 25 ⁇ m, E2 has an integrated amount of light with a wavelength of 365 nm and an integrated amount of light with a wavelength of 405 nm, each independently from 0 to 400 mJ/cm. 2 , and the sum of the integrated amount of light with a wavelength of 365 nm and the integrated amount of light with a wavelength of 405 nm is preferably 100 to 400 mJ/cm 2 .
  • E2 has an integrated amount of light with a wavelength of 365 nm and an integrated amount of light with a wavelength of 405 nm, each independently from 0 to 800 mJ/cm. 2 , and the sum of the integrated amount of light with a wavelength of 365 nm and the integrated amount of light with a wavelength of 405 nm is preferably 100 to 800 mJ/cm 2 .
  • the order of exposing the regions R1 and R2 can be appropriately set according to the thickness T1 and T2 of each region, the integrated amounts of light E1 and E2 for exposing each region, the amount of light exposing each region, and the like. can be done.
  • Regions R1 and R2 may be exposed with the same amount of light or may be exposed with different amounts of light.
  • regions R1 and R2 may be exposed simultaneously or separately. Also, the regions R1 and R2 may be exposed once, or may be exposed stepwise over two or more times.
  • one example of an exposure method is to expose only region R2 and then expose regions R1 and R2 simultaneously.
  • regions R1 and R2 are exposed to different amounts of light
  • one example of an exposure method is to expose region 1 and then region R2, or expose region R2 and then expose region R2. do.
  • the regions R1 and R2 are exposed simultaneously.
  • the exposure of the regions R1 and R2 described above can preferably be performed by an apparatus capable of controlling the irradiation location and irradiation amount of light.
  • apparatuses include, for example, a direct imaging exposure apparatus, a direct writing exposure apparatus, a maskless aligner, and the like.
  • a carboxyl group-containing resin constituting a photosensitive resin composition was prepared according to the following procedure.
  • An autoclave equipped with a thermometer, a nitrogen introduction device and an alkylene oxide introduction device, and a stirring device was charged with 119.4 g of a novolak cresol resin (Shownol CRG951, manufactured by Showa Denko K.K., OH equivalent: 119.4) and 1 potassium hydroxide. 0.19 g and 119.4 g of toluene were added, nitrogen was introduced into the autoclave while stirring, the temperature was raised, and a mixture was obtained.
  • a novolak cresol resin Showa Denko K.K., OH equivalent: 119.4
  • reaction solution was cooled to room temperature, neutralized by adding 35.35 g of a 15% sodium hydroxide aqueous solution, and then washed with water. Then, the toluene was replaced with 118.1 g of diethylene glycol monoethyl ether aceteate by an evaporator and distilled off to obtain a novolac type acrylate resin solution. Then, 332.5 g of the obtained novolak-type acrylate resin solution and 1.22 g of triphenylphosphine were charged into a reactor equipped with a stirrer, a thermometer and an air blowing tube, and air was added at a rate of 10 ml/min.
  • [Preparation of photosensitive resin composition] 150 parts of the carboxyl group-containing resin solution prepared by the method described above, 1.0 parts of a photopolymerization initiator (manufactured by BASF Japan Ltd., Irgacure OXE02), a thermosetting resin (manufactured by Mitsubishi Chemical Corporation, jER828). 30 parts, photopolymerizable resin (manufactured by Nippon Kayaku Co., Ltd., KAYARAD DPHA (dipentaerythritol hexaacrylate)), colorant C.I. I. Pigment Blue 15:3 0.8 part, C.I. I.
  • Photosensitive dry film A 300 g of methyl ethyl ketone was added to 200 g of the photosensitive resin composition prepared by the above method for dilution, and the diluted product was stirred for 15 minutes with a stirrer to obtain a coating solution of the photosensitive resin composition.
  • the resulting coating liquid is applied to the surface of a polyethylene terephthalate film (manufactured by Unitika Ltd., Embret PTH-25) with a thickness of 38 ⁇ m and dried at 80° C. for 15 minutes to form a photosensitive resin composition with a thickness of 30 ⁇ m. formed a layer.
  • a 18 ⁇ m-thick polypropylene film manufactured by Futamura Chemical Co., Ltd., OPP-FOA
  • Photosensitive dry film B 300 g of methyl ethyl ketone was added to 200 g of the photosensitive resin composition prepared by the above method for dilution, and the diluted product was stirred for 15 minutes with a stirrer to obtain a coating solution of the photosensitive resin composition.
  • the resulting coating solution was applied to the surface of a polyethylene terephthalate film (manufactured by Unitika Ltd., Embret PTH-25) with a thickness of 38 ⁇ m and dried at 80° C. for 15 minutes to form a photosensitive resin composition with a thickness of 7 ⁇ m. formed a layer.
  • a 18 ⁇ m-thick polypropylene film manufactured by Futamura Chemical Co., Ltd., OPP-FOA
  • Photosensitive dry film C 300 g of methyl ethyl ketone was added to 200 g of the photosensitive resin composition prepared by the above method for dilution, and the diluted product was stirred for 15 minutes with a stirrer to obtain a coating solution of the photosensitive resin composition.
  • the resulting coating solution was applied to the surface of a polyethylene terephthalate film (manufactured by Unitika Ltd., Embret PTH-25) with a thickness of 38 ⁇ m and dried at 80° C. for 15 minutes to form a photosensitive resin composition with a thickness of 15 ⁇ m. formed a layer.
  • a 18 ⁇ m-thick polypropylene film manufactured by Futamura Chemical Co., Ltd., OPP-FOA
  • Photosensitive dry film D 300 g of methyl ethyl ketone was added to 200 g of the photosensitive resin composition prepared by the above method for dilution, and the diluted product was stirred for 15 minutes with a stirrer to obtain a coating solution of the photosensitive resin composition.
  • the resulting coating liquid is applied to the surface of a polyethylene terephthalate film (manufactured by Unitika Ltd., Embret PTH-25) with a thickness of 38 ⁇ m and dried at 80° C. for 15 minutes to form a photosensitive resin composition with a thickness of 45 ⁇ m. formed a layer.
  • a 18 ⁇ m-thick polypropylene film manufactured by Futamura Chemical Co., Ltd., OPP-FOA
  • Printed wiring boards for evaluation (boards for evaluation A-1, B, C, and D) for evaluation were prepared according to the following procedure using each of the photosensitive dry films A to D prepared by the above-described method.
  • evaluation board A-1 Examples 1 to 5
  • the surface of a substrate (remaining copper rate: 50%, substrate size: 500 mm ⁇ 600 mm ⁇ 0.4 mmt) on which a circuit with a copper circuit height of 20 ⁇ m was formed was chemically polished.
  • the polyethylene film was peeled off from the photosensitive dry film A produced by the method described above.
  • a photosensitive resin composition layer of a photosensitive dry film is attached to the chemically polished surface of the substrate, and then a vacuum laminator (manufactured by Nikko Materials Co., Ltd., CVP-300) is used to form the first
  • a vacuum laminator manufactured by Nikko Materials Co., Ltd., CVP-300
  • the substrate and the photosensitive resin composition layer are closely adhered by heat lamination with a diaphragm under the conditions of pressure degree: 0.8 Mpa, 70 ° C., 1 minute, vacuum degree: 133.3 Pa, and the second pressure bonding step.
  • a flattening press process was performed on the SUS plate.
  • a substrate having a closely adhered photosensitive resin composition layer obtained through these steps was used as an evaluation substrate A-1 in Examples 1 to 5.
  • the region with the copper circuit corresponds to the region R1 in the present specification, and the thickness (T1) of the photosensitive resin composition layer in the same region was 20 ⁇ m.
  • the region without the copper circuit that is, the region where the base material is exposed (base region) corresponds to the region R2 in the present specification, and the thickness of the photosensitive resin composition layer in the same region (T2) was 40 ⁇ m.
  • a photosensitive resin composition layer of a photosensitive dry film is attached to the chemically polished surface of the substrate, and then a vacuum laminator (manufactured by Nikko Materials Co., Ltd., CVP-300) is used to form the first
  • a vacuum laminator manufactured by Nikko Materials Co., Ltd., CVP-300
  • the substrate and the photosensitive resin composition layer are closely adhered by heat lamination with a diaphragm under the conditions of pressure degree: 0.8 Mpa, 70 ° C., 1 minute, vacuum degree: 133.3 Pa, and the second pressure bonding step.
  • a flattening press process was performed on the SUS plate.
  • a substrate having a closely adhered photosensitive resin composition layer obtained through these steps was used as an evaluation substrate B in Examples 6 to 10.
  • the area having the copper circuit corresponds to the area R1 in this specification, and the thickness (T1) of the photosensitive resin composition layer in this area was 3 ⁇ m.
  • the region where there is no copper circuit that is, the region where the base material is exposed (base region) corresponds to the region R2 in the present specification, and the thickness of the photosensitive resin composition layer in the same region (T2 ) was 11 ⁇ m.
  • a photosensitive resin composition layer of a photosensitive dry film is attached to the chemically polished surface of the substrate, and then a vacuum laminator (manufactured by Nikko Materials Co., Ltd., CVP-300) is used to form the first
  • a vacuum laminator manufactured by Nikko Materials Co., Ltd., CVP-300
  • the substrate and the photosensitive resin composition layer are closely adhered by heat lamination with a diaphragm under the conditions of pressure degree: 0.8 Mpa, 70 ° C., 1 minute, vacuum degree: 133.3 Pa, and the second pressure bonding step.
  • a flattening press process was performed on the SUS plate.
  • a substrate having a closely adhered photosensitive resin composition layer obtained through these steps was used as an evaluation substrate C in Examples 11 to 15.
  • the area where the copper circuit is present corresponds to the area R1 in this specification, and the thickness (T1) of the photosensitive resin composition layer in this area was 5 ⁇ m.
  • the region where there is no copper circuit that is, the region where the base material is exposed (base region) corresponds to the region R2 in the present specification, and the thickness of the photosensitive resin composition layer in the same region (T2 ) was 25 ⁇ m.
  • a photosensitive resin composition layer of a photosensitive dry film is attached to the chemically polished surface of the substrate, and then a vacuum laminator (manufactured by Nikko Materials Co., Ltd., CVP-300) is used to form the first
  • a vacuum laminator manufactured by Nikko Materials Co., Ltd., CVP-300
  • the substrate and the photosensitive resin composition layer are closely adhered by heat lamination with a diaphragm under the conditions of pressure degree: 0.8 Mpa, 70 ° C., 1 minute, vacuum degree: 133.3 Pa, and the second pressure bonding step.
  • a flattening press process was performed on the SUS plate.
  • a substrate having a closely adhered photosensitive resin composition layer obtained through these steps was used as an evaluation substrate D in Examples 16 to 20.
  • the region having the copper circuit corresponds to region R1 in this specification, and the thickness (T1) of the photosensitive resin composition layer in this region was 20 ⁇ m.
  • the region where there is no copper circuit that is, the region where the base material is exposed (base region) corresponds to the region R2 in the present specification, and the thickness of the photosensitive resin composition layer in the same region (T2 ) was 70 ⁇ m.
  • Each evaluation substrate prepared by the above-described method is subjected to a predetermined pattern using a direct imaging exposure device (manufactured by Oak Manufacturing Co., Ltd., model number Mms-60) with the integrated amount of each light (E1 and E2) shown in Table 1. Then, after peeling off the polyethylene terephthalate film from each evaluation substrate, development was performed for 60 seconds using a spray-type developing machine containing a 1 wt % NaCO 3 aqueous solution (liquid temperature: 30° C.).
  • a photosensitive resin composition layer of a photosensitive dry film is attached to the chemically polished surface of the substrate, and then a vacuum laminator (manufactured by Nikko Materials Co., Ltd., CVP-300) is used to form the first
  • a vacuum laminator manufactured by Nikko Materials Co., Ltd., CVP-300
  • the substrate and the photosensitive resin composition layer are closely adhered by heat lamination with a diaphragm under the conditions of pressure degree: 0.8 Mpa, 70 ° C., 1 minute, vacuum degree: 133.3 Pa, and the second pressure bonding step.
  • a flattening press step was performed on the SUS plate to obtain a laminate substrate having a photosensitive resin composition layer in close contact.
  • a region having a copper circuit corresponds to the region R1 in this specification, and the thickness (T1) of the photosensitive resin composition layer in this region was 20 ⁇ m.
  • the area where there is no copper circuit that is, the area where the base material is exposed (base material area) corresponds to the area R2 in the present specification, and the thickness (T2) of the photosensitive resin composition layer in the same area was 40 ⁇ m.
  • the laminate substrate was pattern-exposed at a wavelength of 365 nm with an integrated amount of 200 mJ/cm 2 in the region R2.
  • R1 and region R2 were pattern-exposed at a wavelength of 365 nm with an integrated amount of 200 mJ/cm 2.
  • a 1 wt% NaCO 3 aqueous solution liquid temperature 30°C was applied. Development was carried out for 60 seconds using a spray type developing machine inserted in. The substrate having a cured film obtained through these steps was used in Example 21 as an evaluation substrate A-2.
  • a photosensitive resin composition layer of a photosensitive dry film is attached to the chemically polished surface of the substrate, and then a vacuum laminator (manufactured by Nikko Materials Co., Ltd., CVP-300) is used to form the first
  • a vacuum laminator manufactured by Nikko Materials Co., Ltd., CVP-300
  • the substrate and the photosensitive resin composition layer are closely adhered by heat lamination with a diaphragm under the conditions of pressure degree: 0.8 Mpa, 70 ° C., 1 minute, vacuum degree: 133.3 Pa, and the second pressure bonding step.
  • a flattening press step was performed on the SUS plate to obtain a laminate substrate having a photosensitive resin composition layer in close contact.
  • a region having a copper circuit corresponds to the region R1 in this specification, and the thickness (T1) of the photosensitive resin composition layer in this region was 20 ⁇ m.
  • the area where there is no copper circuit that is, the area where the base material is exposed (base material area) corresponds to the area R2 in the present specification, and the thickness (T2) of the photosensitive resin composition layer in the same area was 40 ⁇ m.
  • This laminate substrate was pattern-exposed at a wavelength of 365 nm with an integrated amount of 200 mJ/cm 2 in the area R1 using a direct imaging exposure apparatus (manufactured by ORC Manufacturing Co., Ltd., model number Mms-60).
  • Example 22 A pattern was exposed to R2 at a wavelength of 365 nm with an integrated amount of 400 mJ/cm 2. Next, after peeling off the polyethylene terephthalate film from the laminate substrate, a 1 wt% NaCO 3 aqueous solution (liquid temperature 30°C) was sprayed. The substrate having a cured coating obtained through these steps was used in Example 22 as an evaluation substrate A-3.
  • a photosensitive resin composition layer of a photosensitive dry film is attached to the chemically polished surface of the substrate, and then a vacuum laminator (manufactured by Nikko Materials Co., Ltd., CVP-300) is used to form the first
  • a vacuum laminator manufactured by Nikko Materials Co., Ltd., CVP-300
  • the substrate and the photosensitive resin composition layer are closely adhered by heat lamination with a diaphragm under the conditions of pressure degree: 0.8 Mpa, 70 ° C., 1 minute, vacuum degree: 133.3 Pa, and the second pressure bonding step.
  • a flattening press step was performed on the SUS plate to obtain a laminate substrate having a photosensitive resin composition layer in close contact.
  • a region having a copper circuit corresponds to the region R1 in this specification, and the thickness (T1) of the photosensitive resin composition layer in this region was 20 ⁇ m.
  • the area where there is no copper circuit that is, the area where the base material is exposed (base material area) corresponds to the area R2 in the present specification, and the thickness (T2) of the photosensitive resin composition layer in the same area was 40 ⁇ m.
  • This laminate substrate was pattern-exposed at a wavelength of 365 nm with an integrated amount of 400 mJ/cm 2 in the area R2 using a direct imaging exposure apparatus (manufactured by ORC Manufacturing Co., Ltd., model number Mms-60).
  • Example 23 An evaluation substrate A-4.
  • the photosensitive resin composition layer to be formed has at least two regions R1 and R2 with different thicknesses, and the photosensitive resin composition layer in the region R1.
  • T1 is 1 to 30 ⁇ m
  • T2 is 10 to 70 ⁇ m
  • T1 ⁇ T2 is satisfied.
  • E1 is the integrated amount of light for exposing the region R1
  • E2 is the integrated amount of light for exposing the region R2

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Abstract

Le problème décrit par la présente invention est de fournir un procédé permettant, dans la fabrication d'un stratifié qui comprend un substrat et un revêtement durci recouvrant au moins une partie de la surface du substrat, de durcir de manière satisfaisante chaque région d'une pluralité de régions présentant des épaisseurs différentes dans une couche de composition de résine photosensible formée sur la surface du substrat sans provoquer de contre-dépouille ou de halo. Dans la solution selon l'invention, lors de la fabrication d'un stratifié comprenant un substrat et un revêtement durci recouvrant au moins une partie de la surface du substrat, lorsque la couche de composition de résine sensible formée sur la surface du substrat comporte une pluralité de régions ayant différentes épaisseurs, la quantité de lumière intégrée pour exposer chaque région de la pluralité de régions est conçue de façon à présenter une relation spécifique.
PCT/JP2022/036573 2021-09-30 2022-09-29 Procédé de fabrication de stratifié Ceased WO2023054637A1 (fr)

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Citations (4)

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JP2005142254A (ja) * 2003-11-05 2005-06-02 Toppan Printing Co Ltd 配線基板及びその製造方法
JP2007164059A (ja) * 2005-12-16 2007-06-28 Cmk Corp ソルダーレジスト用露光システム及びプリント配線板の製造方法
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