Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
• • 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
  • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
  • G03F7/11—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having cover layers or intermediate layers, e.g. subbing 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
  • G03F7/26—Processing photosensitive materials; Apparatus therefor
  • G03F7/40—Treatment after imagewise removal, e.g. baking
• • 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
  • G03F7/42—Stripping or agents 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
  • H05K1/00—Printed circuits
  • H05K1/02—Details
  • H05K1/03—Use of materials for the substrate
• • 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
  • H05K3/46—Manufacturing multilayer circuits

Definitions

• the present invention relates to a laminate, and in particular to a laminate that is suitable for use in forming an insulating layer. Furthermore, the present invention also relates to a cured product of the resin composition of the laminate, a printed wiring board including the cured product, and a method for producing the same.
• thermosetting resin composition mainly composed of epoxy resin is generally used as the insulating layer, and vias are formed in the cured product of the thermosetting resin composition using a carbon dioxide laser to provide electrical conductivity between the layers.
• a dry film type resin composition is generally used to form the insulating layer.
• Such dry film type resin compositions have the advantage that a flat layer of the resin composition can be formed by thermocompression bonding to the surface of the printed wiring board using a laminator, making it easy to make highly multi-layered printed wiring boards.
• Patent Document 1 proposes a technology for forming vias using a photosensitive build-up film.
• Patent Document 1 JP 2012-97246 A Summary of the Invention Problems to be Solved by the Invention
• an object of the present invention is to provide a laminate capable of efficiently forming an insulating layer having both excellent via-formability and high dielectric properties.
• Another object of the present invention is to provide a cured product obtained by curing the layer of the resin composition of the above laminate, a printed wiring board including the cured product, and a method for producing the same. Means for solving the problem
• the inventors have conducted extensive research and have found that the above-mentioned problems can be solved by providing a layer of a photosensitive resin composition that is soluble or swellable in an alkaline aqueous solution on one side of the first film in a laminate having a first film and two layers of resin compositions, providing a layer of a non-photosensitive resin composition that is soluble or swellable in an organic solvent on the side of the layer of the photosensitive resin composition opposite to the side in contact with the first film, and adjusting the ratio of the dissolution rate A [ ⁇ m/s] in an organic solvent of the cured layer obtained by photocuring the layer of the photosensitive resin composition to the dissolution rate B [ ⁇ m/s] in an organic solvent of the layer of the non-photosensitive resin composition to be within a specific range.
• the present invention is based on this finding. That is, the gist of the present invention is as follows.
• a first film a layer of a photosensitive resin composition having solubility or swelling in an alkaline aqueous solution provided on one surface of the first film; a layer of a non-photosensitive resin composition having solubility or swelling in an organic solvent, the layer of the photosensitive resin composition being provided on a surface opposite to a surface in contact with the first film,
• a method for manufacturing a printed wiring board having an insulating layer comprising the steps of: (a) laminating a substrate and the laminate according to claim 1 so that one surface of the substrate is in contact with a surface of the layer of the non-photosensitive resin composition of the laminate; (b) a step of irradiating the layer of the photosensitive resin composition of the laminate with light in a pattern to cure the layer; (c) contacting the pattern-shaped cured layer of the photosensitive resin composition with an alkaline aqueous solution and developing the layer to form a pattern-shaped cured product of the photosensitive resin composition; (d) contacting a layer of a non-photosensitive resin composition of the laminate with an organic solvent via the cured product of the patterned photosensitive resin composition and developing the layer, thereby forming a pattern in the layer of the non-photosensitive resin composition that corresponds to the pattern of the cured product of the patterned photosensitive resin composition; and (e) heating and curing the layer of the non-photosensitive resin composition in which the pattern
• the present invention can provide a laminate capable of efficiently forming an insulating layer that combines excellent via-forming properties with high dielectric properties, a cured product obtained by curing a layer of the resin composition of the laminate, a printed wiring board including the cured product, and a method for manufacturing the same.
• the present invention can provide both excellent via-forming properties and high dielectric properties in an insulating layer, which are considered difficult to achieve in pattern formation of an insulating layer by photolithography.
• the laminate of the present invention comprises a first film, a layer of a photosensitive resin composition having solubility or swelling in an alkaline aqueous solution provided on one side of the first film, and a layer of a non-photosensitive resin composition having solubility or swelling in an organic solvent provided on the side opposite to the side of the photosensitive resin composition layer in contact with the first film, and is characterized in that the ratio of the dissolution rate A [ ⁇ m/s] of the cured layer obtained by photocuring the layer of the photosensitive resin composition in an organic solvent (hereinafter, also simply referred to as the "cured layer of the photosensitive resin composition") to the dissolution rate B [ ⁇ m/s] of the layer of the non-photosensitive resin composition in an organic solvent is adjusted to be within a specific range.
• the laminate of the present invention is a laminate in which the first film, the layer of the photosensitive resin composition, and the layer of the non-photosensitive resin composition are laminated in this order.
• the laminate of the present invention is preferably used as a dry film, more preferably used as a dry film for forming an insulating layer, particularly preferably used as a dry film for forming an interlayer insulating layer of a multilayer printed wiring board.
• the laminate of the present invention may have other layers in addition to the first film and each resin composition layer.
• an intermediate layer or the like may be provided between the first film and the photosensitive resin composition layer and between the photosensitive resin composition layer and the non-photosensitive resin composition layer, or a second film may be provided on the surface of the non-photosensitive resin composition layer opposite to the surface in contact with the photosensitive resin composition layer.
• the photosensitive resin composition constituting the layer of the photosensitive resin composition can be used without any particular limitation as long as it has photocurability and is soluble or swellable in an alkaline aqueous solution.
• a resin composition for example, a resin composition containing a photocurable resin having a functional group such as a carboxyl group or a hydroxyl group (including a phenolic hydroxyl group) as a main component can be used.
• Such photocurable resins may be used alone or in combination of two or more.
• a composition containing a carboxyl group-containing resin can be used.
• the carboxyl group-containing resin various conventionally known resins having a carboxyl group in the molecule can be used.
• a carboxyl group-containing resin in the photosensitive resin composition it is possible to impart alkaline developability to the layer of the photosensitive resin composition.
• a photosensitive carboxyl group-containing resin having an ethylenically unsaturated double bond in the molecule is preferable in terms of photocurability and development resistance.
• the ethylenically unsaturated double bond is preferably derived from acrylic acid or methacrylic acid or a derivative thereof.
• carboxyl group-containing resins When using only a carboxyl group-containing resin that does not have an ethylenically unsaturated double bond, it is necessary to use a compound having a plurality of ethylenically unsaturated groups in the molecule, i.e., a photopolymerizable monomer, which will be described later, in combination in order to make the composition photocurable.
• a compound having a plurality of ethylenically unsaturated groups in the molecule i.e., a photopolymerizable monomer, which will be described later, in combination in order to make the composition photocurable.
• Specific examples of carboxyl group-containing resins include the following compounds (which may be either oligomers or polymers).
• a carboxyl group-containing resin obtained by copolymerizing an unsaturated carboxylic acid such as (meth)acrylic acid with an unsaturated group-containing compound such as styrene, ⁇ -methylstyrene, lower alkyl (meth)acrylate, or isobutylene.
• Carboxyl group-containing urethane resins obtained by polyaddition reaction of diisocyanates such as aliphatic diisocyanates, branched aliphatic diisocyanates, alicyclic diisocyanates, and aromatic diisocyanates with carboxyl group-containing dialcohol compounds such as dimethylolpropionic acid and dimethylolbutanoic acid, and diol compounds such as polycarbonate polyols, polyether polyols, polyester polyols, polyolefin polyols, acrylic polyols, bisphenol A alkylene oxide adduct diols, and compounds having phenolic hydroxyl groups and alcoholic hydroxyl groups.
• diisocyanates such as aliphatic diisocyanates, branched aliphatic diisocyanates, alicyclic diisocyanates, and aromatic diisocyanates with carboxyl group-containing dialcohol compounds such as dimethylolpropionic acid and dimethylolbut
• Carboxylic acid-containing photosensitive urethane resins obtained by polyaddition reaction of diisocyanates with bifunctional epoxy resins such as bisphenol A epoxy resins, hydrogenated bisphenol A epoxy resins, bisphenol F epoxy resins, bisphenol S epoxy resins, bixylenol epoxy resins, and biphenol epoxy resins, and monocarboxylic acid compounds having ethylenically unsaturated double bonds such as (meth)acrylic acid, partially acid anhydride-modified products, carboxyl group-containing dialcohol compounds, and diol compounds.
• bifunctional epoxy resins such as bisphenol A epoxy resins, hydrogenated bisphenol A epoxy resins, bisphenol F epoxy resins, bisphenol S epoxy resins, bixylenol epoxy resins, and biphenol epoxy resins
• monocarboxylic acid compounds having ethylenically unsaturated double bonds such as (meth)acrylic acid, partially acid anhydride-modified products, carboxyl group-containing dialcohol compounds, and dio
• a photosensitive urethane resin containing a carboxyl group which is terminated with (meth)acrylation by adding a compound having one hydroxyl group and one or more (meth)acryloyl groups in the molecule, such as hydroxyalkyl (meth)acrylate, during the synthesis of the resin (2) or (3) described above.
• a carboxyl group-containing photosensitive urethane resin that has been (meth)acrylated at the end by adding a compound having one isocyanate group and one or more (meth)acryloyl groups in the molecule, such as an equimolar reactant of isophorone diisocyanate and pentaerythritol triacrylate, during the synthesis of the resin (2) or (3) described above.
• a carboxyl group-containing photosensitive resin obtained by reacting a difunctional or more polyfunctional (solid) epoxy resin with (meth)acrylic acid and adding a dibasic acid anhydride to the hydroxyl groups present in the side chains.
• a carboxyl group-containing photosensitive resin obtained by reacting a polyfunctional epoxy resin in which the hydroxyl groups of a bifunctional (solid) epoxy resin have been further epoxidized with epichlorohydrin, with (meth)acrylic acid, and then adding a dibasic acid anhydride to the resulting hydroxyl groups.
• a carboxyl group-containing polyester resin obtained by reacting a dicarboxylic acid such as adipic acid, phthalic acid, or hexahydrophthalic acid with a bifunctional oxetane resin, and then adding a dibasic acid anhydride such as phthalic anhydride, tetrahydrophthalic anhydride, or hexahydrophthalic anhydride to the resulting primary hydroxyl groups.
• a carboxyl group-containing photosensitive resin obtained by reacting an epoxy compound having multiple epoxy groups in one molecule with a compound having at least one alcoholic hydroxyl group and one phenolic hydroxyl group in one molecule, such as p-hydroxyphenethyl alcohol, and an unsaturated group-containing monocarboxylic acid, such as (meth)acrylic acid, and then reacting the alcoholic hydroxyl group of the resulting reaction product with a polybasic acid anhydride, such as maleic anhydride, tetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, or adipic acid.
• a polybasic acid anhydride such as maleic anhydride, tetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, or adipic acid.
• a carboxyl group-containing photosensitive resin obtained by reacting a compound having multiple phenolic hydroxyl groups in one molecule with an alkylene oxide such as ethylene oxide or propylene oxide, reacting the reaction product obtained with an unsaturated group-containing monocarboxylic acid, and then reacting the resulting reaction product with a polybasic acid anhydride.
• an alkylene oxide such as ethylene oxide or propylene oxide
• a carboxyl group-containing photosensitive resin obtained by reacting a compound having multiple phenolic hydroxyl groups in one molecule with a cyclic carbonate compound such as ethylene carbonate or propylene carbonate, reacting the reaction product obtained with an unsaturated group-containing monocarboxylic acid, and then reacting the resulting reaction product with a polybasic acid anhydride.
• a cyclic carbonate compound such as ethylene carbonate or propylene carbonate
• a carboxyl group-containing photosensitive resin obtained by adding a compound having one epoxy group and one or more (meth)acryloyl groups in one molecule to any one of the resins (1) to (11) above.
• (meth)acrylate is a term that collectively refers to acrylate, methacrylate, and mixtures thereof, and the same applies to other similar expressions.
• the acid value of the carboxyl group-containing resin is preferably 30 to 150 mgKOH/g, and more preferably 50 to 120 mgKOH/g.
• the acid value of the carboxyl group-containing resin is 30 mgKOH/g or more, the alkaline developability of the photosensitive resin composition is improved.
• the acid value of the carboxyl group-containing resin is 150 mgKOH/g or less, dissolution of the exposed area by the developer and the resulting dissolution and peeling without distinction between the exposed area and the unexposed area can be suppressed, making it easier to draw a good resist pattern.
• the weight-average molecular weight of the carboxyl group-containing resin varies depending on the resin skeleton, but is generally preferably 2,000 to 150,000, and more preferably 5,000 to 100,000.
• the weight-average molecular weight of the carboxyl group-containing resin be 2,000 or more, it is possible to suppress the film loss during development that accompanies the decrease in moisture resistance of the coating film after exposure of the photosensitive resin composition, and as a result, it is possible to suppress the decrease in via formability.
• the weight-average molecular weight of the carboxyl group-containing resin be 150,000 or less, it is possible to improve the developability and storage stability of the photosensitive resin composition.
• the weight-average molecular weight of the carboxyl group-containing resin can be measured by gel permeation chromatography (GPC).
• a composition containing a hydroxyl group-containing resin can be used in place of the above-mentioned carboxyl group-containing resin or in combination with the carboxyl group-containing resin.
• a phenolic hydroxyl group-containing resin is preferably used.
• the term "hydroxyl group-containing resin" refers to a resin that contains hydroxyl groups but does not contain carboxyl groups. Specific examples of hydroxyl group-containing resins include the following compounds (which may be either oligomers or polymers):
• a functional hydroxyl group-containing resin obtained by copolymerizing a compound having a hydroxyl group and a (meth)acrylic group (e.g., hydroxy lower alkyl (meth)acrylate) with an unsaturated group-containing compound such as lower alkyl (meth)acrylate or isobutylene.
• a compound having a hydroxyl group and a (meth)acrylic group e.g., hydroxy lower alkyl (meth)acrylate
• an unsaturated group-containing compound such as lower alkyl (meth)acrylate or isobutylene.
• Phenolic hydroxyl group-containing resins with various skeletons synthesized using compounds having one or more skeletons such as a biphenyl skeleton, a phenylene skeleton, and a phenolic hydroxyl group, or compounds having a phenolic hydroxyl group, such as phenol, orthocresol, paracresol, metacresol, 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 3,4-xylenol, 3,5-xylenol, catechol, resorcinol, hydroquinone, methylhydroquinone, 2,6-dimethylhydroquinone, trimethylhydroquinone, pyrogallol, and phloroglucinol.
• skeletons such as a biphenyl skeleton, a phenylene skeleton, and a phenolic hydroxyl group
• phenolic resins such as phenol novolac resin, alkylphenol volac resin, bisphenol A novolac resin, dicyclopentadiene type phenolic resin, Xylok type phenolic resin, terpene modified phenolic resin, polyvinylphenols, bisphenol F, bisphenol S type phenolic resin, poly-p-hydroxystyrene, condensation products of naphthol and aldehydes, and condensation products of dihydroxynaphthalene and aldehydes.
• phenol novolac resin such as phenol novolac resin, alkylphenol volac resin, bisphenol A novolac resin, dicyclopentadiene type phenolic resin, Xylok type phenolic resin, terpene modified phenolic resin, polyvinylphenols, bisphenol F, bisphenol S type phenolic resin, poly-p-hydroxystyrene, condensation products of naphthol and aldehydes, and condensation products of dihydroxynaphthalene and al
• the weight average molecular weight of the hydroxyl-containing resin varies depending on the resin skeleton, but can be approximately the same as that of the carboxyl-containing resin described above.
• the weight average molecular weight of the hydroxyl-containing resin can be measured by gel permeation chromatography (GPC) in the same way as the carboxyl-containing resin.
• the content of each of the above resins in the photosensitive resin composition is not particularly limited as long as the effects of the present invention are achieved, and can be, for example, 10 to 50 mass % in terms of solid content relative to the total mass of the photosensitive resin composition. Note that when multiple types of resins are used in combination, such as a combination of a carboxyl group-containing resin and a hydroxyl group-containing resin, the above content is based on the total mass of the multiple types of resins.
• the photosensitive resin composition may contain a photopolymerizable monomer as required.
• the photopolymerizable monomer is a monomer having an ethylenically unsaturated double bond.
• Examples of such photopolymerizable monomers include commonly known polyester (meth)acrylates, polyether (meth)acrylates, urethane (meth)acrylates, carbonate (meth)acrylates, and epoxy (meth)acrylates.
• alkyl acrylate examples include alkyl acrylates such as 2-ethylhexyl acrylate and cyclohexyl acrylate; hydroxyalkyl acrylates such as 2-hydroxyethyl acrylate and 2-hydroxypropyl acrylate; mono- or diacrylates of alkylene oxide derivatives such as ethylene glycol, propylene glycol, diethylene glycol, and dipropylene glycol; acrylamides such as N,N-dimethylacrylamide, N-methylolacrylamide, and N,N-dimethylaminopropylacrylamide; aminoalkyl acrylates such as N,N-dimethylaminoethyl acrylate and N,N-dimethylaminopropyl acrylate; hexanediol, trimethylolpropane, pentaerythritol, ditrimethylolpropane, dipentaerythritol, and trishydroxyethyl isocyanur
• Polyhydric alcohols such as polyhydric alcohols or their alkylene oxide adducts or ⁇ -caprolactone adducts; phenols such as phenoxy acrylate and bisphenol A diacrylate or their alkylene oxide adducts; acrylates of glycidyl ethers such as glycerin diglycidyl ether, trimethylolpropane triglycidyl ether, and triglycidyl isocyanurate; and at least one of acrylates and melamine acrylates obtained by directly acridating polyols such as polyether polyols, polycarbonate diols, hydroxyl group-terminated polybutadienes, and polyester polyols or by urethane acridating polyols via diisocyanates, as well as methacrylates corresponding to the acrylates, can be appropriately selected and used.
• Such photopolymerizable monomers can also be used as reactive dilu
• Photopolymerizable monomers are particularly effective when using non-photosensitive carboxyl group-containing resins that do not have ethylenically unsaturated double bonds, as they must be used in combination to make the composition photocurable.
• the photosensitive resin composition may contain a photopolymerization initiator as necessary. Any known photopolymerization initiator may be used. The photopolymerization initiator may be used alone or in combination of two or more.
• 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, and bis-(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide.
• bisacylphosphine oxides such as bis-(2,6-dimethoxybenzoyl)-2,5-dimethylphenylphosphine oxide and bis-(2,4,6-trimethylbenzoyl)-phenylphosphine oxide; 2,6-dimethoxybenzoyldiphenylphosphine oxide, 2,6-dichlorobenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoylphenylphosphine acid methyl ester, 2-methylbenzoyldiphenylphosphine oxide, pivaloylphenyl Isopropyl phosphinate, monoacylphosphine oxides such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide; ethyl phenyl(2,4,6-trimethylbenzoyl)phosphinate, 1-hydroxy-cyclohexyl phenyl ketone, 1-[4-(2-hydroxyethoxy)-phen
• a photoinitiator assistant or sensitizer may be used in combination with the above-mentioned photopolymerization initiator.
• the photoinitiator assistant or sensitizer include benzoin compounds, anthraquinone compounds, thioxanthone compounds, ketal compounds, benzophenone compounds, tertiary amine compounds, xanthone compounds, etc.
• thioxanthone compounds such as 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2-isopropylthioxanthone, and 4-isopropylthioxanthone.
• thioxanthone compound can improve deep curing properties.
• these compounds may be used as photopolymerization initiators, it is preferable to use them in combination with a photopolymerization initiator.
• the photoinitiator assistant or sensitizer may be used alone or in combination of two or more types.
• photopolymerization initiators absorb specific wavelengths, and therefore in some cases may have low sensitivity and function as ultraviolet absorbers.
• they are not used solely for the purpose of improving the sensitivity of the photosensitive resin composition. By absorbing light of specific wavelengths as necessary, they can increase the photoreactivity of the surface, change the line shape and openings of the resist to vertical, tapered, or reverse tapered, and improve the precision of the line width and opening diameter.
• the photosensitive resin composition may be blended with a filler as necessary to increase the physical strength and dissolution rate of the coating film.
• a filler 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 pigment fillers to obtain a white appearance and flame retardancy.
• the filler may be surface-treated or may not be surface-treated. Furthermore, the filler may be used alone or in combination of two or more types.
• organic solvent may be blended into the curable resin composition of the present invention for the purpose of adjusting the viscosity during preparation thereof or when applying it to a substrate or film.
• organic solvent include ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; glycol ethers such as 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, and tripropylene glycol monomethyl ether; esters such as ethyl acetate, butyl acetate, butyl lactate, cellosolve acetate, butyl cellosolve acetate, carbit
• the volatilization and drying of the organic solvent can be carried out using a hot air circulation drying oven, an IR oven, a hot plate, a convection oven, etc. (a method in which hot air in the dryer is brought into countercurrent contact with the substrate using a heat source that uses steam for air heating, or a method in which hot air is blown onto the substrate from a nozzle).
• the photosensitive resin composition may further contain, as necessary, colorants, photoinitiator assistants, cyanate compounds, elastomers, mercapto compounds, urethanization catalysts, thixotropic agents, adhesion promoters, block copolymers, chain transfer agents, polymerization inhibitors, copper inhibitors, antioxidants, rust inhibitors, thickeners such as organic bentonite and montmorillonite, at least one of silicone-based, fluorine-based, and polymer-based defoamers and leveling agents, silane coupling agents such as imidazole-based, thiazole-based, and triazole-based, flame retardants such as phosphorus compounds such as phosphinates, phosphate ester derivatives, and phosphazene compounds, and thermosetting components.
• colorants such as photoinitiator assistants, cyanate compounds, elastomers, mercapto compounds, urethanization catalysts, thixotropic agents, adhesion promoters,
• the other additive components known substances in the field of electronic materials can be used.
• the other additive components may be used alone or in combination of two or more.
• the content of the other additive components in the photosensitive resin composition is not particularly limited as long as the effects of the present invention are achieved, and can be appropriately adjusted according to the types of the other additive components, the desired properties to be imparted to the photosensitive resin composition, and the like.
• the layer of photosensitive resin composition may be prepared and molded by appropriately selecting each of the above-mentioned components, or a commercially available product may be used.
• An example of a commercially available product that can be used as the layer of photosensitive resin composition is photosensitive build-up film PV-F008 manufactured by Resonac Co., Ltd.
• Non-photosensitive resin composition constituting the layer of the non-photosensitive resin composition can be any resin composition that is substantially not photocurable, substantially not soluble or swellable in an alkaline aqueous solution, and soluble or swellable in an organic solvent.
• a resin composition containing a thermosetting resin as a main component that is substantially not functional groups such as a carboxyl group or a phenolic hydroxyl group i.e., a thermosetting resin composition
• a thermosetting resin composition can be used as such a resin composition.
• thermosetting resin can be used as the thermosetting resin constituting the thermosetting resin composition.
• known thermosetting resins such as amino resins such as melamine resin, benzoguanamine resin, melamine derivatives, and benzoguanamine derivatives, isocyanate compounds, blocked isocyanate compounds, cyclocarbonate compounds, epoxy compounds, oxetane compounds, oxazoline compounds, episulfide resins, bismaleimide, and carbodiimide resins can be used.
• Each of these thermosetting resins may be monofunctional or polyfunctional.
• an epoxy compound (epoxy resin) is preferably used.
• the thermosetting resin may be used alone or in combination of two or more types.
• thermosetting resin having a cyclic ether group or a cyclic thioether group (hereinafter also referred to as a "cyclic (thio)ether group") in the molecule is preferably used.
• epoxy compounds having an epoxy group in the molecule oxetane compounds having an oxetanyl group in the molecule, oxazoline compounds having an oxazoline group in the molecule, episulfide resins having a thioether group in the molecule, etc. are preferably used.
• the thermosetting resin contains one or more selected from the group consisting of epoxy compounds, polyfunctional oxetane compounds, and oxazoline compounds.
• the thermosetting resin contains one or more selected from the group consisting of epoxy compounds, polyfunctional oxetane compounds, and oxazoline compounds.
• Epoxy compounds include epoxidized vegetable oils; bisphenol A type epoxy resins; hydroquinone type epoxy resins; bisphenol type epoxy resins; thioether type epoxy resins; brominated epoxy resins; novolac type epoxy resins; phenol novolac type epoxy resins; biphenol novolac type epoxy resins; bisphenol F type epoxy resins; hydrogenated bisphenol A type epoxy resins; glycidylamine type epoxy resins; hydantoin type epoxy resins; alicyclic epoxy resins; trihydroxyphenylmethane type epoxy resins; bixylenol type or biphenol type epoxy resins.
• bisphenol S type epoxy resin bisphenol A novolac type epoxy resin; tetraphenylolethane type epoxy resin; heterocyclic epoxy resin; diglycidyl phthalate resin; tetraglycidyl xylenoylethane resin; naphthalene group-containing epoxy resin; epoxy resin having a dicyclopentadiene skeleton; glycidyl methacrylate copolymer epoxy resin; cyclohexylmaleimide and glycidyl methacrylate copolymer epoxy resin; epoxy-modified polybutadiene rubber derivative; CTBN-modified epoxy resin, etc., but are not limited to these.
• These epoxy resins may be used alone or in combination of two or more.
• a polyfunctional oxetane compound having two or more oxetanyl groups in one molecule is preferably used.
• the polyfunctional oxetane compound include polyfunctional oxetanes such as 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 oligomers or
• Oxazoline compounds include, for example, possible compounds having two or more oxazoline groups in one molecule.
• oxazoline compounds include oxazoline group-containing polymers such as polymers of oxazoline group-containing monomers and copolymers of oxazoline group-containing monomers with other monomers.
• oxazoline group-containing monomers examples include 2-vinyl-2-oxazoline, 2-vinyl-4-methyl-2-oxazoline, 2-vinyl-5-methyl-2-oxazoline, 2-isopropenyl-2-oxazoline, 2-isopropenyl-4-methyl-2-oxazoline, 2-isopropenyl-5-ethyl-2-oxazoline, 2-isopropenyl-2-oxazoline, and 2-isopropenyl-4,4-dimethyl-2-oxazoline.
• the episulfide resin may be, for example, a compound in which the oxygen atom constituting the epoxy group in any epoxy compound is replaced with a sulfur atom.
• the epoxy compound may be the same as those mentioned above.
• the method for replacing the oxygen atom constituting the epoxy group in the epoxy compound with a sulfur atom may be a conventional method.
• 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.
• the polyisocyanate compound include aromatic polyisocyanates such as 4,4'-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, naphthalene-1,5-diisocyanate, o-xylylene diisocyanate, m-xylylene diisocyanate, and 2,4-tolylene dimer; aliphatic polyisocyanates such as tetramethylene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, 4,4-methylenebis(cyclohexyl isocyanate), and isophorone diisocyanate; alicyclic polyisocyanates such as bicycloheptane triisocyanate; and adducts, biuret bodies, and isocyanurates of the above-menti
• an addition reaction product between an isocyanate compound and an isocyanate blocking agent can be used.
• isocyanate compounds that can react with an isocyanate blocking agent include the polyisocyanate compounds described above.
• isocyanate blocking agents include phenol-based blocking agents, lactam-based blocking agents, active methylene-based blocking agents, alcohol-based blocking agents, oxime-based blocking agents, mercaptan-based blocking agents, acid amide-based blocking agents, imide-based blocking agents, amine-based blocking agents, imidazole-based blocking agents, and imine-based blocking agents.
• thermosetting resin in the non-photosensitive resin composition is not particularly limited as long as the effects of the present invention are achieved, and can be, for example, 3 to 50 mass % in terms of solid content relative to the total mass of the non-photosensitive resin composition.
• the non-photosensitive resin composition may contain a heat curing catalyst as required.
• the heat curing catalyst include imidazole derivatives such as imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-(2-cyanoethyl)-2-ethyl-4-methylimidazole, and 2-phenyl-4,5-dihydroxymethylimidazole; amine compounds such as dicyandiamide, benzyldimethylamine, 4-(dimethylamino)-N,N-dimethylbenzylamine, 4-methoxy-N,N-dimethylbenzylamine, and 4-methyl-N,N-dimethylbenzylamine; hydrazine compounds such as adipic acid dihydrazide and sebacic acid dihydra
• Examples of commercially available catalysts include 2MZ-A, 2MZ-OK, 2PHZ, 2PHZ-PW, 2P4BHZ, and 2P4MHZ (all of which are trade names for imidazole-based compounds) manufactured by Shikoku Chemical Industry Co., Ltd., and U-CAT 3513N (a trade name for a dimethylamine-based compound), DBU, DBN, and U-CAT SA 102 (all of which are bicyclic amidine compounds and their salts) manufactured by San-Apro Co., Ltd.
• the catalyst is not limited to these, and any catalyst that promotes the reaction of at least one of an epoxy resin or oxetane compound with a carboxyl group and at least one of an epoxy group and an oxetanyl group with a carboxyl group may be used alone or in combination of two or more types.
• S-triazine derivatives such as guanamine, acetoguanamine, benzoguanamine, melamine, 2,4-diamino-6-methacryloyloxyethyl-S-triazine, 2-vinyl-2,4-diamino-S-triazine, 2-vinyl-4,6-diamino-S-triazine ⁇ isocyanuric acid adduct, and 2,4-diamino-6-methacryloyloxyethyl-S-triazine ⁇ isocyanuric acid adduct, and it is preferable to use these compounds that also function as adhesion imparting agents in combination with the heat curing catalyst.
• the heat curing catalyst may be used alone or in combination of two or more.
• the non-photosensitive resin composition may contain one or more of the fillers, organic solvents, and other additives described above for the photosensitive resin composition.
• the layer of non-photosensitive resin composition may be synthesized and molded by appropriately selecting each of the above-mentioned components, or a commercially available product may be used.
• Examples of commercially available products that can be used as the layer of non-photosensitive resin composition include Zaristo 125 manufactured by Taiyo Ink Mfg. Co., Ltd., and Ajinomoto Build-up Film (registered trademark) (ABF) GX-92, GX-T31, GZ-41, and GL-102 manufactured by Ajinomoto Fine-Techno Co., Ltd.
• the laminate of the present invention is adjusted so that the dissolution rates of the above-mentioned photosensitive resin composition layer and non-photosensitive resin composition layer satisfy a specific relationship when they are dissolved separately in the same organic solvent under the same conditions.
• the laminate of the present invention has a two-layer structure of a layer of a photosensitive resin composition having solubility or swelling in an alkaline aqueous solution and a layer of a non-photosensitive resin composition having solubility or swelling in an organic solvent, and the dissolution rate of the photosensitive resin composition layer in an organic solvent and the dissolution rate of the non-photosensitive resin composition layer in an organic solvent are adjusted to satisfy a specific relationship, thereby suppressing the generation of residues during development, and further achieving both excellent via formability and high dielectric properties, which are considered to be difficult to achieve in the pattern formation of a cured product by photolithography.
• a substrate and the laminate of the present invention are laminated so that one side of the substrate and the surface of the layer of the non-photosensitive resin composition of the laminate of the present invention are in contact with each other, the layer of the photosensitive resin composition of the laminate of the present invention is cured in a desired pattern by photolithography, and the layer of the non-photosensitive resin composition of the laminate of the present invention is brought into contact with an organic solvent through the cured product of the photosensitive resin composition of the desired pattern (i.e., as a "mold"), and developed and cured, thereby obtaining a cured product of the non-photosensitive resin composition (insulating layer) in a desired pattern.
• the non-photosensitive resin constituting the non-photosensitive resin composition has a low content of highly polar functional groups such as carboxyl groups and phenolic hydroxyl groups, and therefore the insulating layer formed by the laminate of the present invention can have the high dielectric properties required for an insulating layer.
• “high” or “excellent” in terms of dielectric properties refers to at least one of a state in which the dielectric constant is low and a state in which the dielectric tangent is low.
• a cured product of the photosensitive resin composition having a desired pattern is obtained by photolithography, and the cured product is used as a mold to obtain a cured product of the non-photosensitive resin composition having the desired pattern. Therefore, an insulating layer having a desired pattern can be formed more efficiently with excellent via formation properties than conventional pattern formation using a carbon dioxide laser or UV-YAG laser.
• the dissolution rates of the layer of the photosensitive resin composition and the layer of the cured product of the non-photosensitive resin composition in the laminate of the present invention are measured according to the procedure described in the Examples. ⁇ First film>
• the first film can be any known film without any particular restrictions.
• polyester films such as polyethylene terephthalate (PET) and polyethylene naphthalate, polyimide films, polyamideimide films, polypropylene films, polystyrene films, and other films made of thermoplastic resins can be suitably used.
• PET polyethylene terephthalate
• polyimide films polyamideimide films
• polypropylene films polypropylene films
• polystyrene films polystyrene films
• other films made of thermoplastic resins can be suitably used.
• polyester films are preferably used, and PET films are more preferably used.
• PET films are more preferably used.
• a laminate of these films can also be used as the first film.
• thermoplastic resin film as described above is a film that has been oriented uniaxially or biaxially.
• the thickness of the first film is not particularly limited, but can be, for example, 1 to 150 ⁇ m, or 10 to 60 ⁇ m.
• the method of providing the above-mentioned photosensitive resin composition layer and non-photosensitive resin composition layer on the first film can be a well-known method for manufacturing laminates such as dry films.
• the photosensitive resin composition is diluted with the above-mentioned organic solvent to adjust the viscosity to an appropriate level, and is applied to a uniform thickness on the first film by a coating method such as a comma coater, blade coater, lip coater, rod coater, squeeze coater, reverse coater, transfer roll coater, gravure coater, or spray coater, and is usually dried at a temperature of 50 to 130°C for 1 to 30 minutes to obtain a film.
• a coating method such as a comma coater, blade coater, lip coater, rod coater, squeeze coater, reverse coater, transfer roll coater, gravure coater, or spray coater
• the non-photosensitive resin composition is diluted with the above-mentioned organic solvent to adjust the viscosity to an appropriate level, and is applied to a uniform thickness on the dried film of the photosensitive resin composition by the above-mentioned coating method, and is usually dried at a temperature of 70 to 110°C for 5 to 20 minutes to obtain a film.
• the coating thickness for either the photosensitive resin composition or the non-photosensitive resin composition is generally adjusted appropriately so that the coating thickness after drying is in the range of 1 to 150 ⁇ m, preferably 10 to 60 ⁇ m.
• the second film refers to a film that is peeled off from the layer of the non-photosensitive resin composition before lamination when the layer of the non-photosensitive resin composition of the laminate is laminated by heating or the like so as to be in contact with a base material such as a substrate and integrally molded.
• a polyethylene film, a polytetrafluoroethylene film, a polypropylene film, a surface-treated paper, etc. can be used as the peelable second film, and it is sufficient that the adhesive strength between the layer of the non-photosensitive resin composition and the second film is smaller than the adhesive strength between the layer of the non-photosensitive resin composition and the layer of the photosensitive resin composition when the second film is peeled off.
• the thickness of the second film is not particularly limited, but can be, for example, 10 ⁇ m to 150 ⁇ m.
• the cured product of the present invention is obtained by curing the layer of the non-photosensitive resin composition constituting the laminate of the present invention described above.
• the cured product of the present invention can be suitably used as an insulating layer that combines excellent via formability and excellent (i.e., high) dielectric properties as an insulating layer, and can be particularly suitably used as, for example, a solder resist layer or a build-up material.
• the cured product of the present invention is obtained by laminating a substrate and a laminate of the present invention so that one side of the substrate and the surface of the layer of the non-photosensitive resin composition of the laminate of the present invention are in contact with each other, curing the layer of the photosensitive resin composition of the laminate of the present invention into a desired pattern by photolithography, and developing and curing the layer of the non-photosensitive resin composition through the cured product of the desired pattern of the photosensitive resin composition (i.e., as a "mold") by contacting the layer of the non-photosensitive resin composition with an organic solvent, thereby obtaining a cured product (insulating layer) of the non-photosensitive resin composition in a desired pattern.
• the remaining cured product of the photosensitive resin composition in a pattern may be removed.
• the method for removing the remaining cured product of the photosensitive resin composition is not particularly limited as long as it does not damage the substrate and other components, or the cured product of the present invention (i.e., the cured product of the non-photosensitive resin composition), and examples of the method include a method for removing the cured product of the photosensitive resin composition using hot water.
• the printed wiring board of the present invention has a cured product (insulating layer) of the non-photosensitive resin composition formed by the laminate of the present invention, and can be used as a member of a semiconductor device.
• the printed wiring board of the present invention is produced by a production method (production method of the present invention) including the following steps (a) to (e): (a) a step of laminating a substrate and the laminate of the present invention so that one surface of the substrate is in contact with a surface of the layer of the non-photosensitive resin composition of the laminate of the present invention; (b) a step of irradiating the layer of the photosensitive resin composition of the laminate of the present invention with light in a pattern to cure the layer; (c) a step of contacting the layer of the photosensitive resin composition cured in a pattern shape with an alkaline aqueous solution and developing the layer to form a pattern shape cured product of the photosensitive resin composition; (d) a step of contacting the layer of non-photosensitive resin composition with
• step (a) the substrate and the laminate of the present invention are laminated so that one side of the substrate is in contact with the surface of the layer of the non-photosensitive resin composition of the laminate of the present invention.
• the laminate of the present invention is preferably laminated onto the substrate under pressure and heat using a vacuum laminator or the like.
• a vacuum laminator By using such a vacuum laminator, when a substrate on which a circuit is formed is used, even if the surface of the circuit substrate is uneven, the dry film adheres to the circuit substrate, preventing the inclusion of air bubbles and improving the filling of recesses in the substrate surface.
• the pressure conditions are preferably about 0.1 to 2.0 MPa, and the heating conditions are preferably 40 to 120°C.
• Substrates include printed wiring boards and flexible printed wiring boards with circuits already formed using copper, etc., as well as materials such as paper phenol, paper epoxy, glass cloth epoxy, glass polyimide, glass cloth/non-woven cloth epoxy, glass cloth/paper epoxy, synthetic fiber epoxy, copper-clad laminates for high-frequency circuits using fluororesin, polyethylene, polyphenylene ether, polyphenylene oxide, cyanate, etc., including copper-clad laminates of all grades (FR-4, etc.), as well as metal substrates, polyimide films, polyethylene terephthalate films, polyethylene naphthalate (PEN) films, glass substrates, ceramic substrates, wafer plates, etc.
• materials such as paper phenol, paper epoxy, glass cloth epoxy, glass polyimide, glass cloth/non-woven cloth epoxy, glass cloth/paper epoxy, synthetic fiber epoxy, copper-clad laminates for high-frequency circuits using fluororesin, polyethylene, polyphenylene ether, polyphenylene oxide, cyanate, etc., including copper
• step (b) after laminating the laminate of the present invention on the substrate in step (a) described above, the layer of the photosensitive resin composition is selectively exposed to active energy rays through a photomask having a desired pattern to harden it.
• the timing of peeling off the first film from the laminate of the present invention is not particularly limited as long as the effects of the present invention are achieved, and it may be before or after the exposure described above.
• the exposure machine used for exposure to the active energy rays may be any machine equipped with a high pressure mercury lamp, an ultra-high pressure mercury lamp, a metal halide lamp, a mercury short arc lamp, or the like, and capable of irradiating ultraviolet rays in the range of 350 to 450 nm, and further, a direct imaging machine (for example, a laser direct imaging machine that draws an image directly with a laser based on CAD data from a computer) may also be used.
• the lamp light source or laser light source of the direct imaging machine may have a maximum wavelength in the range of 350 to 450 nm.
• the exposure dose for forming an image varies depending on the film thickness, etc., but is generally within the range of 10 to 1000 mJ/ cm2 , preferably 20 to 800 mJ/ cm2 .
• step (c) after the layer of photosensitive resin composition has been cured into the desired pattern in step (b) described above, the layer of photosensitive resin composition cured into the desired pattern is brought into contact with an alkaline aqueous solution for development, thereby forming a cured product of the photosensitive resin composition in the desired pattern.
• the alkaline aqueous solution used for development in step (c) is not particularly limited as long as it does not damage the substrate, other members, or the layer of the non-photosensitive resin composition, and examples of such solutions include dilute alkaline aqueous solutions such as a 0.3 to 3% by mass aqueous solution of sodium carbonate.
• the cured product of the photosensitive resin composition in the desired pattern may be further irradiated with active energy rays to give the cured product of the photosensitive resin composition in the desired pattern a final finish curing (main curing).
• step (d) the desired pattern is formed in the layer of the non-photosensitive resin composition using the cured product of the photosensitive resin composition in the desired pattern formed in the above-mentioned step (c) as a mold. That is, the layer of the non-photosensitive resin composition is brought into contact with an organic solvent via the cured product of the photosensitive resin composition in the desired pattern, and developed, thereby forming a pattern in the layer of the non-photosensitive resin composition that corresponds to the desired pattern formed in the cured product of the photosensitive resin composition.
• the organic solvent used as the developer in step (d) is not particularly limited, and examples thereof include acetone, methyl ethyl ketone, ethyl acetate, butyl acetate, alkoxyethanol having an alkoxy group having 1 to 4 carbon atoms, ethyl alcohol, isopropyl alcohol, butyl alcohol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, and dipropylene glycol methyl ether.
• the organic solvent may be used alone or in combination of two or more.
• organic solvents used alone include ethyl acetate, dipropylene glycol, dipropylene glycol methyl ether, 1,1,1-trichloroethane, N-methylpyrrolidone, N,N-dimethylformamide, cyclohexanone, methyl ethyl ketone, methyl isobutyl ketone, ⁇ -butyrolactone, and propylene glycol monomethyl ether acetate (propylene glycol 1-monomethyl ether 2-acetate (PGMEA)).
• Dipropylene glycol methyl ether is preferably used as the organic solvent.
• concentration of the organic solvent there are no particular limitations on the concentration of the organic solvent as long as it does not damage the substrate or other components, but it is preferably 2 to 90% by mass relative to the total mass of the developer.
• the temperature of the developer can be set appropriately depending on the type and concentration of the organic solvent contained in the developer and the desired developability.
• the method of contacting the layer of the non-photosensitive resin composition with the developer (organic solvent), i.e., the developing method is not particularly limited as long as it is a method used for developing a cured product of the resin composition, and examples include the dipping method, the bathing method, the spraying method, the high-pressure spraying method, brushing, and slapping.
• One type of developing method may be used alone, or two or more types may be used in combination. From the viewpoint of further improving the resolution of the resulting cured product (insulating layer), the high-pressure spraying method is preferably used.
• step (e) the layer of non-photosensitive resin composition in the desired pattern formed in step (d) above is heated and cured to form an insulating layer.
• the conditions for heating the layer of non-photosensitive resin composition in the desired pattern are not particularly limited as long as the temperature is the same as that used for curing thermosetting resins, and are, for example, 150 to 190°C for 30 to 120 minutes.
• the manufacturing method of the present invention may further include a step (f) of removing the remaining pattern-shaped cured product of the photosensitive resin composition.
• the method of removing the remaining cured product of the photosensitive resin composition can be the same as that described for the cured product described above.
• a hydrophilic copolymer butadiene 60%, methyl acrylate 9%, ethylene methacrylate phosphate 20%, styrene 10% and divinylbenzene 1%
• NPSSO-PB B1000 liquid polybutadiene manufactured by Nippon Soda Co., Ltd.
• This resin composition was applied onto a support film (polyethylene terephthalate (PET) film TN-200 manufactured by Toyobo Co., Ltd., thickness 38 ⁇ m, size 30 cm ⁇ 30 cm) using a bar coater so that the thickness of the resin composition layer after drying would be 30 ⁇ m. Next, it was dried at 70 to 90 ° C. (average 80 ° C.) for 20 minutes using a hot air circulation drying oven to form a layer of photosensitive resin composition 1 on the support film, and a laminate (film) having a layer of photosensitive resin composition 1 was obtained, and used for producing an evaluation board described later.
• PET polyethylene terephthalate
• Non-photosensitive resin composition 1 used in this example was prepared according to the procedure described below. 25 parts of biphenyl/phenol novolac type epoxy resin NC-3000 manufactured by Nippon Kayaku Co., Ltd., 3 parts of tetramethylbiphenyl type epoxy resin jER (registered trademark) YX-4000 manufactured by Mitsubishi Chemical Corporation, 2 parts of bisphenol F type epoxy resin jER (registered trademark) 807 manufactured by Mitsubishi Chemical Corporation, 1.5 parts of bisphenol A type epoxy resin jER (registered trademark) 828 manufactured by Mitsubishi Chemical Corporation, 1.2 parts of naphthalene type epoxy resin EPICLON (registered trademark) HP-4032 manufactured by DIC Corporation, 3 parts of fluorene/tetramethylbiphenyl skeleton-containing phenoxy resin FX293 manufactured by Nippon Steel Chemical Co., Ltd., 1.2 parts of HCA-HQ (10-(2,5-dihydroxyphenyl)-9,10-d
• thermosetting resin composition non-photosensitive resin composition 1
• This resin composition was applied onto a support film (polyethylene terephthalate (PET) film TN-200 manufactured by Toyobo Co., Ltd., thickness 38 ⁇ m, size 30 cm ⁇ 30 cm) using a bar coater so that the thickness of the resin composition layer after drying was 30 ⁇ m.
• PET polyethylene terephthalate
• it was dried at 70 to 90 ° C. (average 80 ° C.) for 10 minutes using a hot air circulation drying oven to form a layer of non-photosensitive resin composition 1 on the support film, and a laminate (film) having a layer of non-photosensitive resin composition 1 was obtained, which was used to prepare an evaluation board described later.
• Non-photosensitive resin composition 2 used in this example was prepared according to the procedure described below. 5 parts of bisphenol AF type epoxy resin jER (registered trademark) YX7760 manufactured by Mitsubishi Chemical Corporation, 4 parts of tetramethylbiphenyl type epoxy resin jER (registered trademark) YX-4000 manufactured by Mitsubishi Chemical Corporation, 8 parts of naphthol aralkyl type epoxy resin ESN-475 manufactured by Nippon Steel Chemical Co., Ltd., 5 parts of cresol novolac resin LA-3018 manufactured by DIC Corporation, 5 parts of active ester type curing agent EPICLON (registered trademark) HPC-8000 having a dicyclopentadienyl diphenol structure manufactured by DIC Corporation, 2 parts of imidazole type epoxy resin curing agent Curesol (registered trademark) 1B2PZ manufactured by Shikoku Chemical Industry Co., Ltd., 20 parts of cyclohexanone, and 70 parts of silica SO
• thermosetting resin composition non-photosensitive resin composition 2
• This resin composition was applied onto a support film (Toyobo Co., Ltd. polyethylene terephthalate (PET) film TN-200, thickness 38 ⁇ m, size 30 cm ⁇ 30 cm) using a bar coater so that the thickness of the resin composition layer after drying would be 30 ⁇ m.
• PET polyethylene terephthalate
• it was dried at 70 to 90 ° C. (average 80 ° C.) for 10 minutes using a hot air circulation drying oven to form a layer of non-photosensitive resin composition 2 on the support film, and a laminate (film) having a layer of non-photosensitive resin composition 2 was obtained, and used for producing an evaluation board described later.
• Each evaluation substrate of the examples and comparative examples was prepared by laminating a layer of the photosensitive resin composition and a layer of the non-photosensitive resin composition shown in Table 1 on a substrate in the following order, the layer of the non-photosensitive resin composition and the layer of the photosensitive resin composition, according to the following procedure. Details of each layer in Table 1 are as follows.
• (X-1) Photosensitive resin composition a photosensitive resin composition (a resin composition containing a hydroxyl group-containing resin) obtained by the above-mentioned Preparation Example of a Photosensitive Resin Composition (X-2)
• PSR-800 AUS410 A dry film solder resist for developing type PKG substrates manufactured by Taiyo Ink Mfg. Co., Ltd.
• Non-photosensitive resin composition 1 a non-photosensitive resin composition obtained by the above-mentioned Preparation Example of Non-photosensitive resin composition 1
• Non-photosensitive resin composition 2 a non-photosensitive resin composition obtained by the above-mentioned Preparation Example of Non-photosensitive resin composition 2
• the above (X-1) and (X-2) are all photocurable and soluble in an alkaline solution.
• the above (Y-1) to (Y-3) are all not photocurable but thermocurable and soluble in an organic solvent.
• Layers (films) of each of the above-mentioned non-photosensitive resin compositions (Y-1) to (Y-3) were laminated on a substrate using a vacuum laminator CVP-300 manufactured by Nikko Materials Co., Ltd., and allowed to stand at room temperature for at least 1 hour after lamination.
• the substrate used was an HL832NS substrate manufactured by Mitsubishi Gas Chemical Co., Ltd. (with the copper foil removed by etching).
• a layer (film) of the above-mentioned (X-1) photosensitive resin composition or (X-2) PSR-800 AUS410 was laminated on each layer (film) of the non-photosensitive resin composition using a vacuum laminator CVP-300 manufactured by Nikko Materials Co., Ltd., to obtain a substrate (laminated substrate) on which each resin composition was laminated.
• the lamination conditions for each resin composition layer were a temperature of 80°C, a pressure of 0.2 MPa, and a pressurization time of 20 seconds after evacuation for 20 seconds.
• each laminate substrate was exposed to ultraviolet light of 150 mJ/cm 2 using a pattern forming device so that a round hole having a diameter of 6 mm was formed using a round hole pattern.
• each laminate substrate was left at room temperature for 60 minutes. Then, it was developed using an alkaline solution (1 mass% sodium carbonate aqueous solution) to form a cured product of the photosensitive resin composition. Then, the entire surface of the patterned cured product of the photosensitive resin composition on each laminate substrate was immersed in each developer at 30 ° C. shown in Table 1 for 30 seconds to be developed.
• the developer was wiped off, the remaining cured product of the photosensitive resin composition was removed with hot water, and further heated at 170 ° C. for 60 minutes to form a layer (insulating layer) of the cured product of the non-photosensitive resin composition having an opening of 6 mm in diameter on each laminate substrate, and each evaluation substrate of the example and comparative example was obtained.
• the dissolution rate A [ ⁇ m/s] of the cured layer obtained by photocuring the layer of the photosensitive resin composition constituting each of the evaluation substrates of Examples 1 to 8 and Comparative Example 1 and the dissolution rate B [ ⁇ m/s] of the layer of the non-photosensitive resin composition were measured according to the following procedure. First, under the same conditions as in the preparation of the evaluation board, a layer of the photosensitive resin composition and a layer of the non-photosensitive resin composition were laminated on different copper-clad laminates. The layer of the photosensitive resin composition was exposed to ultraviolet light of 150 mJ/ cm2 .
• each copper-clad laminate on which the layer of the photosensitive resin composition and the layer of the non-photosensitive resin composition were laminated was immersed for 30 seconds in each developer at 30 ° C. shown in Table 1.
• the dielectric properties of the non-photosensitive resin composition layers were measured using an ENA network analyzer (Agilent Technologies) and a slip post dielectric resonator (SPDR) to measure the dielectric loss tangent at 10 GHz.
• the dielectric loss tangent of each non-photosensitive resin composition layer was confirmed to be 0.015 for Zaristo 125G, 0.013 for non-photosensitive resin composition 1, and 0.0044 for non-photosensitive resin composition 2.

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• 2023
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