WO2016158362A1 - Film sec, produit durci, stratifié et procédé de formation de motif de réserve - Google Patents

Film sec, produit durci, stratifié et procédé de formation de motif de réserve Download PDF

Info

Publication number
WO2016158362A1
WO2016158362A1 PCT/JP2016/058045 JP2016058045W WO2016158362A1 WO 2016158362 A1 WO2016158362 A1 WO 2016158362A1 JP 2016058045 W JP2016058045 W JP 2016058045W WO 2016158362 A1 WO2016158362 A1 WO 2016158362A1
Authority
WO
WIPO (PCT)
Prior art keywords
photosensitive layer
component
dry film
group
resin
Prior art date
Application number
PCT/JP2016/058045
Other languages
English (en)
Japanese (ja)
Inventor
健一 岩下
泰治 村上
中村　彰宏
藤本　大輔
正樹 森田
明子 伊藤
Original Assignee
日立化成株式会社
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
Priority claimed from JP2015066538A external-priority patent/JP2018087832A/ja
Priority claimed from JP2015087885A external-priority patent/JP2018087835A/ja
Application filed by 日立化成株式会社 filed Critical 日立化成株式会社
Publication of WO2016158362A1 publication Critical patent/WO2016158362A1/fr

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
    • C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/14—Polyamide-imides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • 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
    • 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 disclosure relates to a dry film, a cured product thereof, a laminate, and a method for forming a resist pattern.
  • semiconductor components such as LSIs and chips have become more highly integrated, and the form of semiconductor components has rapidly increased in number and size. Has changed. Further, packaging forms such as a package-on-package in which a semiconductor device is stacked on a semiconductor device are actively performed, and it is expected that the mounting density of the semiconductor device will be further increased in the future.
  • vias openings
  • the number of flip chip pins mounted on a printed wiring board increases, it is necessary to provide as many vias as the number of pins.
  • conventional printed wiring boards have a low mounting density, and the semiconductor to be mounted Since the number of pins of the device is designed from several thousand pins to around 10,000 pins, it is not necessary to provide vias having a small diameter and a narrow pitch.
  • each via must be formed one by one, and it takes time to provide a large number of vias.
  • the adhesive force between the insulating layer and the plated copper is not sufficient, and the conductor pattern may peel off.
  • An object of the present disclosure is to solve the above-described problems and to form a dry film that can form a resist pattern that has excellent adhesion to plated copper and that has excellent resolution, and a cured product, laminate, and the dry film. It is to provide a method of forming a resist pattern using
  • the dry film of the present disclosure includes a photosensitive layer and a non-photosensitive layer, and the non-photosensitive layer includes a thermosetting resin.
  • the non-photosensitive layer is used as an insulating layer when, for example, a multilayer wiring board is manufactured, and a conductor pattern (wiring layer) can be formed by plating the surface thereof.
  • the non-photosensitive layer improves the adhesion between the insulating layer formed from the non-photosensitive layer and the conductor pattern formed by plating on the insulating layer, and the electric circuit of the formed circuit Reliability can be improved.
  • the non-photosensitive layer can also be called an adhesion auxiliary layer. Since the non-photosensitive layer of the present disclosure has low solubility in a chemical solution such as a developer, it has been found that the surface roughness after the roughening treatment is small.
  • the present inventors have shown that the non-photosensitive layer in the dry film of the present disclosure has better adhesion to the plated copper than the single insulating layer obtained by mixing the non-photosensitive layer and the photosensitive layer of the present disclosure. It was found that it can be secured.
  • the dry film of the present disclosure not only the via can be formed without using a laser, but also a finer via pattern can be formed as compared with the case where a laser is used. That is, it has been found that by using the above-described dry film, a fine via can be formed by combining the non-photosensitive layer and the photosensitive layer. Furthermore, by forming an insulating layer using the dry film of the present disclosure, the generation of via residues can be suppressed, and the insulation reliability between layers can be improved.
  • the non-photosensitive layer preferably contains (A) component: epoxy resin, (B-1) component: epoxy resin curing agent, and (C) component: resin having amide group or imide group.
  • the non-photosensitive layer further contains (E) component: an ester group-containing compound.
  • the non-photosensitive layer preferably contains (A) component: epoxy resin, (B-2) component: epoxy resin curing accelerator, and (E) component: ester group-containing compound.
  • the non-photosensitive layer has a small surface roughness after the ultraviolet irradiation treatment and can ensure good adhesion to the plated copper.
  • the non-photosensitive layer further contains (D) component: an inorganic filler.
  • the thickness of the photosensitive layer is preferably 1 to 50 ⁇ m.
  • the thickness of the non-photosensitive layer is preferably 10 ⁇ m or less.
  • the photosensitive layer has (F) component: a resin having a phenolic hydroxyl group, and (G) component: at least one selected from the group consisting of an aromatic ring, a heterocyclic ring and an alicyclic ring, and a methylol group or an alkoxyalkyl group.
  • the dry film according to claim 8 comprising 20 to 70 parts by mass of the component (H) with respect to 100 parts by mass of the component (F).
  • the photosensitive layer further contains a component (D ′): an inorganic filler.
  • the component (D ′) is preferably an inorganic filler having an average primary particle size of 100 nm or less.
  • the component (D ′) is preferably silica.
  • the above dry film can be used for forming an interlayer insulating layer.
  • the present disclosure also provides a cured product obtained using the dry film.
  • the method for forming a resist pattern of the present disclosure includes a step of forming a photosensitive layer and a non-photosensitive layer on a substrate in this order using the dry film, a step of exposing the photosensitive layer to a predetermined pattern, And developing the exposed photosensitive layer and subjecting it to a heat treatment.
  • the resist pattern forming method further includes a heat treatment step before the exposed photosensitive layer is developed.
  • the present disclosure is a dry film including a photosensitive layer and a non-photosensitive layer, wherein a photosensitive layer and a non-photosensitive layer are formed in this order on a substrate, the photosensitive layer is exposed, and the dry film is formed.
  • a dry film is provided in which an unexposed portion of a photosensitive layer is eluted and a non-photosensitive layer on the unexposed portion is broken, and a via can be formed at a location where the non-photosensitive layer is broken by heat treatment after development.
  • vias can be formed without using a laser, and a large number of vias can be easily formed at a time.
  • the present disclosure provides a laminate in which a base material, a photosensitive layer, and a non-photosensitive layer containing a thermosetting resin are laminated in this order.
  • the resist pattern forming method of the present disclosure includes a step of forming a photosensitive layer by applying a photosensitive composition on a substrate, and a non-photosensitive layer by applying a resin composition containing a thermosetting resin on the photosensitive layer. A step of exposing the photosensitive layer to a predetermined pattern, and a step of developing and heat-treating the exposed photosensitive layer.
  • the present disclosure it is possible to provide a dry film capable of forming a resist pattern that is excellent in adhesiveness with plated copper and excellent in resolution. Moreover, according to this indication, the formation method of the resist pattern using the hardened
  • (meth) acrylate means at least one of acrylate and methacrylate corresponding thereto.
  • the term “process” is not limited to an independent process, and is included in the term if the intended action of the process is achieved even when it cannot be clearly distinguished from other processes. It is.
  • the term “layer” includes not only a structure having a shape formed on the entire surface but also a structure having a shape formed on a part when observed as a plan view.
  • a numerical range indicated by using “to” indicates a range including the numerical values described before and after “to” as the minimum value and the maximum value, respectively.
  • the upper limit value or lower limit value of a numerical range of a certain step may be replaced with the upper limit value or lower limit value of the numerical range of another step.
  • the upper limit value or the lower limit value of the numerical range may be replaced with the values shown in the examples.
  • FIG. 1 is a schematic cross-sectional view of a dry film 10 according to this embodiment.
  • the dry film 10 according to this embodiment includes a non-photosensitive layer 3 and a photosensitive layer 5.
  • the non-photosensitive layer 3 is a layer formed using a resin composition described later
  • the photosensitive layer 5 is a layer formed using a photosensitive composition described later.
  • the dry film 10 may be formed on the support 1 so that the non-photosensitive layer 3 and the support 1 are in contact with each other. That is, the dry film 10 according to the present embodiment may include the support 1, the non-photosensitive layer 3, and the photosensitive layer 5 in this order.
  • a protective layer 7 that covers the photosensitive layer 5 may be further provided on the photosensitive layer 5.
  • a polymer film having heat resistance and solvent resistance can be used.
  • the support 1 polymer film
  • examples of the support 1 (polymer film) include polyolefins such as polypropylene and polyethylene, and polyesters such as polyethylene terephthalate.
  • the thickness of the support 1 (polymer film) is preferably 5 to 25 ⁇ m.
  • One polymer film may be used as the support 1 and the other polymer film as the protective layer 7.
  • the protective layer 7 for example, a polymer film having heat resistance and solvent resistance can be used.
  • the protective layer 7 include polyolefins such as polypropylene and polyethylene, and polyesters such as polyethylene terephthalate.
  • the non-photosensitive layer 3 and the photosensitive layer 5 can be formed by applying a resin composition and a photosensitive composition on a support or a protective layer, respectively.
  • the coating method include a dipping method, a spray method, a bar coating method, a roll coating method, and a spin coating method.
  • the dry film of this embodiment can be obtained by the following method. First, the non-photosensitive layer 3 is formed by coating and drying on a polymer film or copper foil serving as a support using the resin composition. Next, the photosensitive composition is applied on the non-photosensitive layer 3 and dried to form the photosensitive layer 5, whereby the dry film of this embodiment is obtained. In addition, the dry film of this embodiment may be obtained by bonding the non-photosensitive layer 3 formed on the support 1 and the protective layer 7 formed with the photosensitive layer 5 together.
  • the thickness of the non-photosensitive layer 3 may be 10 ⁇ m or less, 0.1 to 10 ⁇ m, 0.1 to 5 ⁇ m, or 0.2 to 1.5 ⁇ m. 0.3 to 1 ⁇ m.
  • the transmittance of the non-photosensitive layer 3 may be 80% or more, 85% or more, or 90% or more. Since the transmittance of the non-photosensitive layer 3 is 80% or more, a decrease in sensitivity of the photosensitive layer 5 can be sufficiently suppressed, so that the resolution is improved.
  • the upper limit is not particularly limited, but may be less than 100%.
  • the transmittance can be measured using a known method.
  • the preferable range of the thickness of the photosensitive layer 5 varies depending on the application, but the thickness of the photosensitive layer 5 is preferably 1 to 50 ⁇ m, more preferably 5 to 40 ⁇ m, and still more preferably 10 to 30 ⁇ m. . By setting the thickness of the photosensitive layer 5 in the above-described range, the resolution tends to be further improved.
  • the resin composition of the present embodiment does not have photosensitivity and is used for forming a non-photosensitive layer.
  • the resin composition of this embodiment contains a thermosetting resin.
  • the thermosetting resin is not particularly limited as long as it is a component composed of a reactive compound that causes a crosslinking reaction by heat.
  • epoxy resin for example, epoxy resin, cyanate ester resin, maleimide resin, allyl nadiimide resin, phenol resin, Urea resin, melamine resin, alkyd resin, acrylic resin, unsaturated polyester resin, diallyl phthalate resin, silicone resin, resorcinol formaldehyde resin, xylene resin, furan resin, polyurethane resin, ketone resin, triallyl cyanurate resin, polyisocyanate resin, Examples include resins containing tris (2-hydroxyethyl) isocyanurate, resins containing triallyl trimellitate, thermosetting resins synthesized from cyclopentadiene, thermosetting resins by trimerization of aromatic dicyanamide, etc. It is.
  • the resin composition may contain a curing agent for a thermosetting resin.
  • the resin composition of this embodiment may contain (A) component: epoxy resin, (B-1) component: epoxy resin curing agent, and (C) component: resin having amide group or imide group.
  • the resin composition used to form the resin layer of the present embodiment includes (A) component: epoxy resin, (B-2) component: epoxy resin curing accelerator, and (E) component: ester group-containing compound. It may contain.
  • these components may be simply referred to as (A) component, (B-1) component, (B-2) component, (C) component, (E) component and the like.
  • the resin layer of this embodiment can be used suitably in the formation method provided with a plating process.
  • epoxy resin although a preferable compound changes with uses, it is preferable that it is a polyfunctional epoxy resin.
  • preferable epoxy resins include cresol novolak type epoxy resins, phenol novolak type epoxy resins, naphthol novolak type epoxy resins, bisphenol F type epoxy resins, bisphenol S type epoxy resins, bisphenol T type epoxy resins, bisphenol Z type epoxy resins.
  • Tetrabromobisphenol A type epoxy resin biphenyl type epoxy resin, biphenyl aralkyl type epoxy resin, tetramethylbiphenyl type epoxy resin, triphenyl type epoxy resin, tetraphenyl type epoxy resin, naphthol aralkyl type epoxy resin, naphthalenediol aralkyl type epoxy Resin, fluorene type epoxy resin, epoxy resin having dicyclopentadiene skeleton, epoxy having skeleton derived from butanediol Resin, epoxy resin having a skeleton derived from pentadiol, epoxy resin having a skeleton derived from hexanediol, epoxy resin having a skeleton derived from heptanediol, epoxy resin having a skeleton derived from octanediol, alicyclic epoxy resin, etc.
  • biphenyl aralkyl epoxy resin or an epoxy resin having a skeleton derived from hexanediol is more preferable.
  • examples of commercially available products include biphenyl aralkyl type epoxy resins (manufactured by Nippon Kayaku Co., Ltd., trade name: NC-3000). These epoxy resins may be used in combination of two or more from the viewpoint of further improving the insulation reliability and heat resistance.
  • the content of the component (A) is preferably 20 to 90 parts by weight, and preferably 30 to 80 parts by weight with respect to 100 parts by weight of the total solid content of the resin composition used for forming the non-photosensitive layer. It is more preferable.
  • solid content refers to the component in compositions other than volatile substances, such as a water
  • ⁇ (B-1) component> As an epoxy resin hardening
  • curing agent although a preferable compound changes with uses, for example, phenol resins, acid anhydrides, amines, hydragits, etc. are mentioned.
  • phenol resin a novolac type phenol resin such as a cresol novolac type phenol resin, a resol type phenol resin, or the like can be used.
  • acid anhydrides phthalic anhydride, benzophenone tetracarboxylic dianhydride, methyl hymic anhydride and the like can be used.
  • As the amines dicyandiamide, diaminodiphenylmethane, guanylurea and the like can be used.
  • the content of component (B-1) is preferably 0.5 to 1.5 equivalents relative to the epoxy group of component (A).
  • the content of the epoxy resin curing agent is 0.5 to 1.5 equivalents relative to the epoxy group of the component (A)
  • Tg glass transition temperature
  • Component (B-2) that can be used in the resin composition of the present embodiment As an epoxy resin curing accelerator, a preferred compound varies depending on the use, but a general curing accelerator used for curing component (A) Can be used.
  • epoxy resin curing accelerator examples include 2-methylimidazole, 2-ethyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 2-heptadecylimidazole, 2-undecylimidazole, 1-cyanoethyl- Imidazole compounds such as 2-phenylimidazolium trimellitate; Organic phosphite compounds such as triphenylphosphine and tributylphosphine; Organic phosphite compounds such as trimethylphosphite and triethylphosphite; Ethyltriphenylphosphonium bromide and tetraphenyl Phosphonium salt compounds such as phosphonium tetraphenylborate; Trialkylamines such as triethylamine and tributylamine; 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6-to Amine compounds such as bis (dimethylaminomethyl)
  • the content of the component (B-2) is preferably 0.02 to 1.5 parts by mass, and 0.8 to 1.3 parts by mass with respect to 100 parts by mass of the component (A). It is more preferable. If the amount is 0.02 parts by mass or more, the component (A) tends to be sufficiently cured and heat resistance can be maintained. On the other hand, if the amount is 1.5 parts by mass or less, the storage stability of the resin composition, B The handleability of the staged resin composition is improved.
  • ⁇ (C) component examples include polyamide, polyamideimide, and polyimide.
  • Examples of diamines that can be used in these production include aromatic diamines and aliphatic diamines.
  • the component (C) can be said to be a heat resistant resin.
  • aromatic diamines include diaminobenzene, diaminotoluene, diaminophenol, diaminodimethylbenzene, diaminomesitylene, diaminonitrobenzene, diaminodiazobenzene, diaminonaphthalene, diaminobiphenyl, diaminodimethoxybiphenyl, diaminodiphenyl ether, diaminodimethyldiphenyl ether, methylene Diamine, methylenebis (dimethylaniline), methylenebis (methoxyaniline), methylenebis (dimethoxyaniline), methylenebis (ethylaniline), methylenebis (diethylaniline), methylenebis (ethoxyaniline), methylenebis (diethoxyaniline), isopropylidenedianiline, Diaminobenzophenone, diaminodimethylbenzophenone, diamy Anthraquinone, diaminobenz
  • aliphatic diamine examples include ethylenediamine, propanediamine, hydroxypropanediamine, butanediamine, heptanediamine, hexanediamine, diaminodiethylamine, diaminopropylamine, cyclopentanediamine, cyclohexanediamine, azapentanediamine, and triazaundecadiamine. Etc. These aromatic diamines and aliphatic diamines may be used alone or in combination of two or more.
  • Examples of the dicarboxylic acid used for the production of a resin having an amide group or an imide group include aromatic dicarboxylic acids, aliphatic dicarboxylic acids, and oligomers having carboxyl groups at both ends.
  • aromatic dicarboxylic acid examples include phthalic acid, isophthalic acid, terephthalic acid, biphenyldicarboxylic acid, methylene dibenzoic acid, thiodibenzoic acid, carbonyl dibenzoic acid, sulfonyl dibenzoic acid, naphthalenedicarboxylic acid, hydroxyisophthalic acid , Hydroxyphthalic acid, hydroxyterephthalic acid, dihydroxyisophthalic acid, dihydroxyterephthalic acid and the like. These aromatic dicarboxylic acids may be used alone or in combination of two or more.
  • oligomers having a carboxyl group at both ends include oligomers having a number average molecular weight of 200 to 10,000, preferably a number average molecular weight of 500 to 5,000.
  • Specific examples include polybutadiene having carboxyl groups at both ends, butadiene-acrylonitrile copolymer, styrene-butadiene copolymer, polyisoprene, ethylene propylene copolymer, polyether, polyester, polycarbonate, polyacrylate, polyacrylate.
  • examples include methacrylate, polyurethane, and silicone rubber.
  • NPC gel permeation chromatography
  • tetrahydrofuran is used as an eluent, and measurement is performed at a temperature of 30 ° C. and a flow rate of 1.0 mL / min.
  • a copolymer of polyamide and polybutadiene (also referred to as “polybutadiene-modified polyamide resin”) can be used from the viewpoint of further improving the adhesion to the plated copper.
  • a polybutadiene-modified polyamide resin include a phenolic hydroxyl group-containing polybutadiene-modified polyamide obtained by polycondensation of a diamine, a dicarboxylic acid having a phenolic hydroxyl group, and a polybutadiene having a carboxyl group at both ends.
  • a phenolic hydroxyl group-containing polybutadiene-modified polyamide is prepared by, for example, catalyzing a diamine, a phenolic hydroxyl group-containing dicarboxylic acid, and a polybutadiene having carboxyl groups at both ends in an organic solvent such as N-methyl-2-pyrrolidone (NMP). Can be obtained by polycondensation of a carboxyl group and an amino group in the presence of a phosphite ester and a pyridine derivative.
  • NMP N-methyl-2-pyrrolidone
  • dicarboxylic acid having a phenolic hydroxyl group and polybutadiene having a carboxyl group at both ends a dicarboxylic acid having no phenolic hydroxyl group may be added. Examples of such a commercially available phenolic hydroxyl group-containing polybutadiene-modified polyamide resin include BPAM-155 manufactured by Nippon Kayaku Co., Ltd.
  • polyamideimide that can be contained as the component (C) for example, polyamideimide synthesized by a so-called isocyanate method by reaction of trimellitic anhydride or a reaction product of trimellitic anhydride and diamine with an aromatic diisocyanate.
  • isocyanate method for synthesizing polyamideimide a method in which an aromatic tricarboxylic acid anhydride and the above diamine compound are reacted in the presence of excess diamine compound and then a diisocyanate is reacted (for example, as described in Japanese Patent No. 2897186). Method) and a method of reacting an aromatic diamine compound and trimellitic anhydride (for example, a method described in JP-A No. 04-182466).
  • Examples of commercially available polyamide imide resins include Bilomax HR11NN and Bilomax HR16NN manufactured by Toyobo Co., Ltd.
  • the polyimide that can be contained as the component (C) may be synthesized by a general synthesis method currently used industrially. For example, tetracarboxylic dianhydride and the above diamine are polymerized in equimolar amounts to obtain a polyamic acid that is a polyimide precursor, and then subjected to a dehydration reaction and a cyclization reaction using heating at 200 ° C. or higher or using a catalyst. By proceeding, polyimide can be obtained. When using a catalyst, an amine compound can be used, and a carboxylic acid anhydride may be used in combination as a dehydrating agent for quickly removing water generated by imidization.
  • (C) component mentioned above may each be used independently, and may be used in combination of 2 or more types.
  • the content of the component (C) is preferably 3 to 30% by mass, preferably 15 to 25% by mass with respect to the total solid content of the component (A), the component (B-1) and the component (C). More preferably.
  • the said resin composition may contain (D) component: an inorganic filler from a viewpoint of stabilizing a roughening shape and improving adhesiveness.
  • (D) component can be used individually by 1 type or in mixture of 2 or more types.
  • inorganic fillers examples include aluminum oxide, aluminum hydroxide, calcium carbonate, calcium hydroxide, barium sulfate, barium carbonate, magnesium oxide, magnesium hydroxide, silica, or inorganic fillers derived from mineral products such as talc and mica. Can be mentioned.
  • examples of the silica include fused spherical silica, fused and ground silica, fumed silica, and sol-gel silica.
  • the type of the inorganic filler is not particularly limited, but the thermal expansion coefficient is preferably 5.0 ⁇ 10 ⁇ 6 / ° C. or less.
  • silica such as fused spherical silica, fumed silica, sol-gel silica, and the like is used. preferable. Among them, fumed silica or sol-gel silica is more preferable.
  • a silane coupling agent may be used.
  • a known particle size distribution meter When measuring the particle diameter of each inorganic filler, a known particle size distribution meter can be used.
  • the amount is preferably 1 to 40 parts by mass with respect to 100 parts by mass of the total solid content of the resin composition. More preferably, it is part by mass.
  • the inorganic filler contained in the non-photosensitive layer preferably has an average primary particle size of 100 nm or less, and particularly 50 nm or less from the viewpoint of further excellent photosensitivity. Is preferred. When the average primary particle size is 100 nm or less, the resolution tends to be further improved.
  • the “primary particle size” is a value obtained by conversion from the specific surface area of particles actually measured by the BET method. In the BET method, an adsorbate (for example, an inert gas such as nitrogen) is physically adsorbed on the surface of solid particles at a low temperature, and the specific surface area can be estimated from the molecular cross-sectional area and adsorbed amount of the adsorbate.
  • Component (D) dispersed in the resin composition from the viewpoint of suppressing light scattering in the exposure wavelength region (for example, 300 to 450 nm) of the resin composition, that is, suppressing a decrease in transmittance in the exposure wavelength region.
  • the average particle diameter is preferably 80 nm or less, more preferably 50 nm or less, and still more preferably 30 nm or less.
  • the minimum of the average particle diameter of (D) component in a resin composition is not specifically limited, For example, it can be 5 nm or more.
  • the inorganic filler is preferably dispersed with a maximum particle size of 1 ⁇ m or less when dispersed in the resin composition, and is dispersed within 0.5 ⁇ m or less. More preferably, it is more preferable to be dispersed to 0.1 ⁇ m or less.
  • the “average particle diameter” of the component (D) is the average particle diameter of the inorganic filler in a state dispersed in the resin composition, and is a value obtained by measurement as follows.
  • the resin composition 1000 After diluting (or dissolving) the resin composition 1000 times with methyl ethyl ketone, using a submicron particle analyzer (trade name: N5, manufactured by Beckman Coulter Co., Ltd.), in accordance with the international standard ISO 13321, The particles dispersed in the solvent at a refractive index of 1.38 are measured, and the particle size at an integrated value of 50% (volume basis) in the particle size distribution is taken as the average particle size. Further, the particle diameter at the integrated value 99.9% (volume basis) in the particle size distribution is defined as the maximum particle diameter.
  • a submicron particle analyzer trade name: N5, manufactured by Beckman Coulter Co., Ltd.
  • the dry film is exposed to the entire surface to prevent elution of the photosensitive layer, and then 1000 times using a solvent as described above. After dilution (or dissolution) in (volume ratio), measurement can be performed using the submicron particle analyzer.
  • the resin composition may contain (E) component: ester group-containing compound.
  • ester group-containing compound one or more ester groups are contained in one molecule, and an epoxy resin can be cured without containing a hydroxyl group.
  • aliphatic or aromatic carboxylic acid and aliphatic or aromatic hydroxy examples include ester compounds obtained from the compounds.
  • an ester compound composed of an aliphatic carboxylic acid, an aliphatic hydroxy compound, or the like can increase the solubility in an organic solvent and the compatibility with an epoxy resin by including an aliphatic chain.
  • an ester compound composed of an aromatic carboxylic acid, an aromatic hydroxy compound, or the like can improve the heat resistance of the resin composition by having an aromatic ring.
  • ester group-containing compound examples include, for example, a mixture of an aromatic carboxylic acid, a monohydric phenol compound, and a polyhydric phenol compound as raw materials, the aromatic carboxylic acid, the monohydric phenol compound, and a polyhydric compound.
  • An aromatic ester obtained by a condensation reaction with a phenolic hydroxyl group of a polyhydric phenol compound is mentioned.
  • aromatic carboxylic acid examples include those in which 2 to 4 hydrogen atoms of an aromatic ring such as benzene, naphthalene, biphenyl, diphenylpropane, diphenylmethane, diphenyl ether, diphenylsulfone, and benzophenone are substituted with a carboxyl group.
  • an aromatic ring such as benzene, naphthalene, biphenyl, diphenylpropane, diphenylmethane, diphenyl ether, diphenylsulfone, and benzophenone are substituted with a carboxyl group.
  • monohydric phenol type compound what substituted one hydrogen atom of the above-mentioned aromatic ring by the hydroxyl group is mentioned.
  • polyhydric phenol compound examples include those in which 2 to 4 hydrogen atoms of the aromatic ring are substituted with a hydroxyl group.
  • Examples of the aromatic carboxylic acid include phthalic acid, isophthalic acid, terephthalic acid, and benzenetricarboxylic acid.
  • Examples of the monohydric phenol compound include phenol, various cresols, ⁇ -naphthol, ⁇ -naphthol and the like.
  • Examples of the polyhydric phenol compounds include hydroquinone, resorcin, catechol, 4,4′-biphenol, 4,4′-dihydroxydiphenyl ether, bisphenol A, bisphenol, bisphenol S, bisphenol Z, brominated bisphenol A, and brominated.
  • Examples thereof include bisphenol F, brominated bisphenol S, methylated bisphenol S, various dihydroxynaphthalenes, various dihydroxybenzophenones, various trihydroxybenzophenones, various tetrahydroxybenzophenones, and phloroglycine.
  • the ester group-containing compound may be a resin having one or more ester groups in one molecule, and is also available as a commercial product. Examples include “EXB-9460”, “EXB-9460S”, “EXB-9470”, “EXB-9480”, “EXB-9420” manufactured by DIC Corporation, and “BPN80” manufactured by Mitsui Chemicals, Inc. . These ultraviolet active ester group-containing compounds may be used alone or in combination of two or more.
  • the content of the ester group-containing compound is preferably 0.75 to 1.25 equivalents with respect to 1 equivalent of the epoxy group of the component (A).
  • it is 0.75 equivalent or more, sufficient tackiness and curability between the support and the non-photosensitive layer can be obtained sufficiently, and when it is 1.25 equivalent or less, sufficient curability, heat resistance and chemical resistance are obtained. It becomes easy to obtain.
  • the above resin composition is obtained by adding other components to the components (A) to (E) as necessary, sufficiently stirring and mixing them, and then standing until there are no bubbles.
  • a known kneading and dispersing method such as a kneader, ball mill, bead mill, three rolls, or nanomizer may be used.
  • the resin composition is mixed or diluted or dispersed in a solvent to form a varnish.
  • the solvent include methyl ethyl ketone, xylene, toluene, acetone, ethylene glycol monoethyl ether, cyclohexanone, ethyl ethoxypropionate, N, N-dimethylformamide, N, N-dimethylacetamide and the like. These solvents may be used singly or in combination of two or more.
  • the ratio of the solvent to the resin composition may be a conventionally used ratio, and the amount used can be adjusted according to the equipment for forming the non-photosensitive layer.
  • the resin composition can be further diluted or dispersed with the above solvent to prepare a varnish.
  • the photosensitive composition used to form the photosensitive layer of the present embodiment can be used in accordance with a desired purpose as long as its properties change (for example, it cures) when irradiated with light. It may be negative or positive.
  • the term “photosensitive” means that the photosensitive layer is exposed, then subjected to heat treatment after exposure, if necessary, and then developed (removed) using a developer for removing the photosensitive composition. ) Means that a resin pattern can be formed.
  • the photosensitive composition may contain (F) component: a resin having a phenolic hydroxyl group, (G ′) component: a crosslinking agent, and (I) component: a photosensitive acid generator.
  • Component (G ′) A crosslinking agent is a compound that forms a bond with a resin or a bond between crosslinkers by the action of heat, acid, or the like.
  • (G ′) component may contain a compound having (G) component: at least one selected from the group consisting of an aromatic ring, a heterocyclic ring and an alicyclic ring, and having a methylol group or an alkoxyalkyl group,
  • (G) Component and (H) Both components may be included.
  • the photosensitive composition of this embodiment is (D ') component: an inorganic filler, (J) component: Amine, (K) component: Organic peroxide, (L) component: Silane cup as needed.
  • a ring agent, (M) component: leveling agent, (N) component: sensitizer can also be contained.
  • a phenolic low molecular weight compound can also be contained.
  • (D ') component As an inorganic filler, the thing similar to the above-mentioned (D) component can be used.
  • the amount is preferably 1 to 70 parts by mass and preferably 3 to 65 parts by mass with respect to 100 parts by mass of the total solid content of the photosensitive composition. More preferred.
  • the average primary particle size is preferably 100 nm or less. Moreover, it is preferable that the average particle diameter of (D ') is 100 nm or less. Thereby, the thermal expansion coefficient of the cured film can be reduced according to the content of the component (D ′). From the viewpoint of suppressing light scattering in the exposure wavelength region (for example, 300 to 450 nm) of the photosensitive composition, that is, suppressing a decrease in transmittance in the exposure wavelength region, it was dispersed in the photosensitive composition (D The average particle size of the component ') is preferably 80 nm or less, more preferably 50 nm or less, and further preferably 30 nm or less.
  • the lower limit of the average particle diameter in the component (D ′) is not particularly limited, but can be, for example, 5 nm or more.
  • the inorganic filler is preferably dispersed with a maximum particle diameter of 1 ⁇ m or less when dispersed in the photosensitive composition, and is dispersed within 0.5 ⁇ m or less. More preferably, it is more preferably dispersed to 0.1 ⁇ m or less.
  • the “average particle diameter” and “maximum particle diameter” of the component (D ′) are 50% (volume basis) of the integrated value in the particle size distribution of the inorganic filler dispersed in the photosensitive composition, respectively. And the integrated value of 99.9% (volume basis).
  • a cured film of a photosensitive layer or a photosensitive composition provided on a support is diluted (or dissolved) 1000 times (volume ratio) with a solvent as described above, and then the submicron. It can be measured using a particle analyzer.
  • the resin having a phenolic hydroxyl group is not particularly limited, but is preferably a resin that is soluble in an alkaline aqueous solution, and particularly preferably a novolak resin.
  • a novolak resin can be obtained by condensing phenols and aldehydes in the presence of a catalyst.
  • phenols examples include phenol, o-cresol, m-cresol, p-cresol, o-ethylphenol, m-ethylphenol, p-ethylphenol, o-butylphenol, m-butylphenol, p-butylphenol, 2 , 3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 3,4-xylenol, 3,5-xylenol, 2,3,5-trimethylphenol, 3,4,5- Examples include trimethylphenol, catechol, resorcinol, pyrogallol, ⁇ -naphthol, ⁇ -naphthol and the like.
  • aldehydes examples include formaldehyde, paraformaldehyde, acetaldehyde, benzaldehyde, and the like.
  • novolak resins include phenol / formaldehyde condensed novolak resins, cresol / formaldehyde condensed novolak resins, phenol-naphthol / formaldehyde condensed novolak resins, and the like.
  • component (F) other than the novolak resin examples include polyhydroxystyrene and copolymers thereof, phenol-xylylene glycol condensation resin, cresol-xylylene glycol condensation resin, phenol-dicyclopentadiene condensation resin, and the like. It is done.
  • a component can be used individually by 1 type or in mixture of 2 or more types.
  • the weight average molecular weight is preferably 100,000 or less, and preferably 1,000 to 80,000 from the viewpoint of further improving the resolution, developability, thermal shock resistance, heat resistance, and the like of the obtained insulating film. Is more preferably 2000 to 50000, particularly preferably 2000 to 20000, and most preferably 4000 to 15000.
  • the content of the component (F) is 30 to 90 parts by mass with respect to 100 parts by mass of the total solid content of the photosensitive composition (excluding the component (D ′) when the component (D ′) is used). It is preferably 40 to 80 parts by mass. When the content of the component (F) is within this range, a film formed using the resulting photosensitive composition tends to be more excellent in developability with an alkaline aqueous solution.
  • the photosensitive composition of this embodiment contains (G) component: the compound which has at least 1 type chosen from the group which consists of an aromatic ring, a heterocyclic ring, and an alicyclic ring, and has a methylol group or an alkoxyalkyl group.
  • the aromatic ring means an aromatic hydrocarbon group (for example, a hydrocarbon group having 6 to 10 carbon atoms), and examples thereof include a benzene ring and a naphthalene ring.
  • the heterocyclic ring means a cyclic group having at least one nitrogen atom, oxygen atom, sulfur atom and the like (for example, a cyclic group having 3 to 10 carbon atoms), such as a pyridine ring, an imidazole ring, a pyrrolidinone ring, Examples include an oxazolidinone ring, an imidazolidinone ring, and a pyrimidinone ring.
  • the alicyclic ring means a cyclic hydrocarbon group having no aromaticity (for example, a cyclic hydrocarbon group having 3 to 10 carbon atoms), such as a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, and A cyclohexane ring is mentioned.
  • An alkoxyalkyl group means a group in which an alkyl group is bonded to an alkyl group through an oxygen atom.
  • the two alkyl groups may be different from each other, for example, an alkyl group having 1 to 10 carbon atoms.
  • the component (G) when the photosensitive layer after the resin pattern is formed is heated and cured, the component (G) reacts with the component (F) to form a bridge structure, and the resin pattern is weak. And melting can be prevented.
  • a compound having a phenolic hydroxyl group (however, the component (F) is not included) or a compound having a hydroxymethylamino group or an alkoxymethylamino group can be preferably used.
  • the “compound having a phenolic hydroxyl group” used as the component (G) has a methylol group or an alkoxymethyl group, thereby increasing the dissolution rate of the unexposed area when developing with an alkaline aqueous solution as well as a crosslinking agent. , Sensitivity can be improved.
  • the molecular weight of the compound having a phenolic hydroxyl group is preferably 94 to 2000, and preferably 108 to 2000 in terms of weight average molecular weight in consideration of the balance of solubility in alkali aqueous solution, photosensitivity, mechanical properties, and the like. More preferably, it is 108 to 1500.
  • the molecular weight can be measured by another method, and the average can be calculated.
  • Z represents a single bond or a divalent group
  • R 24 and R 25 each independently represent a hydrogen atom or a monovalent organic group
  • R 26 and R 27 each independently represent 1 A and b each independently represents an integer of 1 to 3
  • c and d each independently represents an integer of 0 to 3.
  • examples of the monovalent organic group include an alkyl group having 1 to 10 carbon atoms such as a methyl group, an ethyl group, and a propyl group; an alkenyl group having 2 to 10 carbon atoms such as a vinyl group.
  • An aryl group having 6 to 30 carbon atoms such as a phenyl group; a group in which some or all of the hydrogen atoms of these hydrocarbon groups are substituted with a halogen atom such as a fluorine atom.
  • the compound represented by the general formula (1) is preferably a compound represented by the general formula (2).
  • X 1 represents a single bond or a divalent group, and a plurality of R's each independently represents an alkyl group (for example, an alkyl group having 1 to 10 carbon atoms).
  • a plurality of R's each independently represents an alkyl group (for example, an alkyl group having 1 to 10 carbon atoms).
  • the compound in which Z is a single bond is a biphenol (dihydroxybiphenyl) derivative.
  • the divalent group represented by Z include an alkylene group having 1 to 10 carbon atoms such as a methylene group, an ethylene group and a propylene group, an alkylidene group having 2 to 10 carbon atoms such as an ethylidene group, Arylene groups having 6 to 30 carbon atoms such as phenylene groups, groups in which some or all of the hydrogen atoms of these hydrocarbon groups are substituted with halogen atoms such as fluorine atoms, sulfonyl groups, carbonyl groups, ether bonds, sulfides Examples include a bond and an amide bond.
  • Z is preferably a divalent group represented by the following general formula (4).
  • X 2 represents a single bond, an alkylene group (for example, an alkylene group having 1 to 10 carbon atoms), an alkylidene group (for example, an alkylidene group having 2 to 10 carbon atoms), these Or a sulfonyl group, a carbonyl group, an ether bond, a sulfide bond or an amide bond in which part or all of the hydrogen atoms are substituted with a halogen atom.
  • R 28 represents a hydrogen atom, a hydroxyl group, an alkyl group (for example, an alkyl group having 1 to 10 carbon atoms) or a haloalkyl group, and e represents an integer of 1 to 10.
  • the plurality of R 28 and X 2 may be the same as or different from each other.
  • the haloalkyl group means an alkyl group substituted with a halogen atom.
  • Examples of the compound having a hydroxymethylamino group or an alkoxymethylamino group include (poly) (N-hydroxymethyl) melamine, (poly) (N-hydroxymethyl) glycoluril, (poly) (N-hydroxymethyl) benzoguanamine, And (poly) (N-hydroxymethyl) urea. Moreover, you may use the nitrogen-containing compound etc. which alkyl-etherified all or one part of the hydroxymethylamino group of these compounds.
  • examples of the alkyl group of the alkyl ether include a methyl group, an ethyl group, a butyl group, or a mixture thereof, and may contain an oligomer component that is partially self-condensed.
  • the compound having an alkoxymethylamino group is preferably a compound represented by the general formula (5) or a compound represented by the general formula (6).
  • a plurality of R's each independently represents an alkyl group (for example, an alkyl group having 1 to 10 carbon atoms).
  • a plurality of R's each independently represents an alkyl group (for example, an alkyl group having 1 to 10 carbon atoms).
  • the content of component (G) is preferably 5 to 60 parts by mass, more preferably 10 to 45 parts by mass, and more preferably 10 to 35 parts by mass with respect to 100 parts by mass of component (F). More preferably.
  • the content of the component (G) is 5 parts by mass or more, the exposed part is sufficiently crosslinked, so that the resolution is further improved.
  • the photosensitive composition is placed on a desired support. It becomes easier to form a film, and the resolution is further improved.
  • the photosensitive composition of this embodiment contains an aliphatic compound having two or more functional groups selected from component (H): acryloyloxy group, methacryloyloxy group, glycidyloxy group and hydroxyl group. Also good.
  • (H) component may have 2 or more types of different functional groups one by one, and may have 2 or more of 1 type of functional groups.
  • the compound is preferably an aliphatic compound having three or more functional groups. The upper limit of the number of functional groups is not particularly limited, but is 12 for example.
  • the photosensitive composition may be required to have excellent adhesion (tackiness) to the substrate.
  • the photosensitive composition which does not have sufficient tackiness, the photosensitive layer of an exposed part is easy to be removed by development processing, and there exists a tendency for the adhesiveness of a base material and a resist pattern to deteriorate.
  • the photosensitive layer contains the component (H)
  • the adhesiveness between the photosensitive composition and the substrate that is, the tackiness tends to be improved.
  • the molecular weight is preferably 92 to 2000, more preferably 106 to 1500, and still more preferably 134 to 1300 in terms of weight average molecular weight in consideration of balance.
  • the molecular weight can be measured by another method, and the average can be calculated.
  • component (H) examples include compounds represented by general formulas (7) to (10).
  • the “aliphatic compound” refers to a compound in which the main skeleton is an aliphatic skeleton and does not contain an aromatic ring or an aromatic heterocyclic ring.
  • R 1 , R 5 , R 16 and R 19 each represent a hydrogen atom, a methyl group, an ethyl group, a hydroxyl group or a group represented by the general formula (11);
  • R 21 represents a hydroxyl group, a glycidyloxy group, an acryloyloxy group or a methacryloyloxy group, and
  • R 2 , R 3 , R 4 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 17 , R 18 and R 20 are each a hydroxyl group, a glycidyloxy group, an acryloyloxy group, a methacryloyloxy group, a group represented by the general formula (12), or the general formula (13).
  • R 22 and R 23 represents a hydroxyl group, a glycidyloxy group, acryloyloxy indicates group or methacryloyloxy group, integers der of n and m are each 1 to 10 .
  • Examples of the compound having a glycidyloxy group include ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, and 1,6-hexanediol diglycidyl.
  • Ether glycerin diglycidyl ether, pentaerythritol tetraglycidyl ether, trimethylolethane triglycidyl ether, trimethylolpropane triglycidyl ether, glycerol propoxylate triglycidyl ether, 1,4-cyclohexanedimethanol diglycidyl ether, diglycidyl-1,2 -Cyclohexane dicarboxylate and the like.
  • trimethylolethane triglycidyl ether or trimethylolpropane triglycidyl ether is preferable in terms of excellent sensitivity and resolution.
  • the compound having a glycidyloxy group includes, for example, Epolite 40E, Epolite 100E, Epolite 70P, Epolite 200P, Epolite 1500NP, Epolite 1600, Epolite 80MF, Epolite 100MF (trade name, manufactured by Kyoeisha Chemical Co., Ltd.), alkyl type epoxy resin ZX-1542 (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., trade name), Denacol EX-212L, Denacol EX-214L, Denacol EX-216L, Denacol EX-321L and Denacol EX-850L Name). These compounds having a glycidyloxy group can be used singly or in combination of two or more.
  • Examples of the compound having an acryloyloxy group include EO-modified dipentaerythritol hexaacrylate, PO-modified dipentaerythritol hexaacrylate, dipentaerythritol hexaacrylate, EO-modified ditrimethylolpropane tetraacrylate, PO-modified ditrimethylolpropane tetraacrylate, ditrile Methylolpropane tetraacrylate, EO-modified pentaerythritol tetraacrylate, PO-modified pentaerythritol tetraacrylate, pentaerythritol tetraacrylate, EO-modified pentaerythritol triacrylate, PO-modified pentaerythritol triacrylate, pentaerythritol triacrylate, EO-modified trimethylolpropane acrylate, PO modified birds Chi
  • Examples of the compound having a methacryloyloxy group include EO-modified dipentaerythritol hexamethacrylate, PO-modified dipentaerythritol hexamethacrylate, dipentaerythritol hexamethacrylate, EO-modified ditrimethylolpropane tetramethacrylate, PO-modified ditrimethylolpropane tetramethacrylate, ditriethyl.
  • Examples of the compound having a hydroxyl group include polyhydric alcohols such as dipentaerythritol, pentaerythritol, and glycerin. These compounds having a hydroxyl group can be used singly or in combination of two or more.
  • the functional group of the component (H) is preferably a glycidyloxy group, an acryloyloxy group or a methacryloyloxy group, more preferably a glycidyloxy group or an acryloyl group, and even more preferably an acryloyloxy group.
  • the component (H) is preferably an aliphatic compound having two or more glycidyloxy groups, more preferably an aliphatic compound having three or more glycidyloxy groups. More preferably, the aliphatic compound has a glycidyloxy group having a weight average molecular weight of 1000 or less.
  • the content of the component (H) is preferably 20 to 70 parts by mass, more preferably 25 to 65 parts by mass with respect to 100 parts by mass of the component (F). Preferably, the amount is 35 to 55 parts by mass.
  • the content of the component (H) is 20 parts by mass or more, sufficient tackiness can be obtained, and when the content is 70 parts by mass or less, a photosensitive composition is formed on a desired support. It becomes easy and the fall of resolution can be controlled.
  • the photosensitive composition of this embodiment may contain (I) component: a photosensitive acid generator.
  • the component (I) is a compound that generates an acid upon irradiation with actinic rays and the like, and not only the (G) component is cross-linked by the generated acid, but also reacts with the phenolic hydroxyl group of the (F) component to develop a developer.
  • the solubility of the composition with respect to is greatly reduced.
  • methylol groups or alkoxyalkyl groups in component (G) or methylol groups or alkoxyalkyl groups in component (G) react with (F) component with dealcoholization. By doing so, a negative pattern can be formed.
  • the component (I) is not particularly limited as long as it is a compound that generates an acid upon irradiation with actinic rays or the like.
  • an onium salt compound, a halogen-containing compound, a diazoketone compound, a sulfone compound, a sulfonic acid compound, a sulfonimide compound, and diazomethane for example, an onium salt compound, a halogen-containing compound, a diazoketone compound, a sulfone compound, a sulfonic acid compound, a sulfonimide compound, and diazomethane.
  • Compounds and the like Specific examples are shown below.
  • Onium salt compounds examples include iodonium salts, sulfonium salts, phosphonium salts, diazonium salts, and pyridinium salts.
  • Preferred examples of the onium salt compound include diaryl iodonium salts such as diphenyliodonium trifluoromethanesulfonate, diphenyliodonium p-toluenesulfonate, diphenyliodonium hexafluoroantimonate, diphenyliodonium hexafluorophosphate, and diphenyliodonium tetrafluoroborate; triphenylsulfonium Triarylsulfonium salts such as trifluoromethanesulfonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate; 4-t-butylpheny
  • Sulfonimide compounds Specific examples of the sulfonimide compound include N- (trifluoromethylsulfonyloxy) succinimide, N- (trifluoromethylsulfonyloxy) phthalimide, N- (trifluoromethylsulfonyloxy) diphenylmaleimide, N- (trifluoromethylsulfonyl).
  • the component (I) is preferably a compound having a trifluoromethanesulfonate group, a hexafluoroantimonate group, a hexafluorophosphate group or a tetrafluoroborate group in terms of excellent sensitivity and resolution.
  • (I) component can be used individually by 1 type or in mixture of 2 or more types.
  • component (I) When component (I) is contained, the content of component (I) is based on 100 parts by mass of component (F) from the viewpoint of further improving the sensitivity, resolution, pattern shape, and the like of the photosensitive composition of the present embodiment. 0.1 to 15 parts by mass, and more preferably 0.3 to 10 parts by mass.
  • a solvent may be added to the photosensitive composition of this embodiment.
  • the solvent is preferably an organic solvent.
  • Such an organic solvent is not particularly limited.
  • ethylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate and ethylene glycol monoethyl ether acetate; propylene glycol monomethyl ether, propylene glycol monoethyl Propylene glycol monoalkyl ethers such as ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether; Propylene glycol dialkyl ethers such as propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol dipropyl ether, propylene glycol dibutyl ether; Propylene glycol Monomethyl ether acete Propylene glycol monoalkyl ether acetate
  • the content of the solvent is preferably 30 to 200 parts by mass, and more preferably 60 to 120 parts by mass with respect to 100 parts by mass of the total amount of the photosensitive composition excluding the solvent.
  • a dry film comprising the above-mentioned non-photosensitive layer and photosensitive layer is prepared. Lamination is performed so that the photosensitive layer is in contact with the substrate.
  • a base material and a laminate in which a photosensitive layer and a non-photosensitive layer are formed in this order on the base material can be formed.
  • the photosensitive layer is exposed to a predetermined pattern through a predetermined mask pattern.
  • radiation used for exposure include low-pressure mercury lamps, high-pressure mercury lamps, metal halide lamps, g-ray steppers, i-line steppers and other ultraviolet rays or electron beams, laser beams, and the like.
  • the thickness is selected as appropriate depending on the thickness, the thickness of the non-photosensitive layer, the transmittance of the non-photosensitive layer, etc. For example, in the case of UV irradiation from a high-pressure mercury lamp, when the photosensitive layer thickness is 10-50 ⁇ m, 100-5000 mJ / cm. It is about 2 .
  • the photosensitive layer is exposed by irradiating the non-photosensitive layer with radiation.
  • a support body shows a light-shielding property with respect to actinic light, after removing a support body, actinic light is irradiated.
  • post-exposure baking heat treatment
  • the curing reaction of the (F) component and the (G) component by the generated acid can be promoted.
  • the preferable range varies depending on the composition of the photosensitive composition, the thickness of the photosensitive layer, and the like, but it is usually preferable to heat at 60 to 150 ° C. for about 1 to 60 minutes, and at 1 to 60 at 70 to 100 ° C. It is more preferable to heat for about a minute.
  • the photosensitive layer that has been baked after exposure is developed with an alkaline developer to dissolve and remove the region other than the photocured portion (unexposed portion) of the photosensitive layer.
  • Examples of the developing method in this case include a shower method, a high-pressure spray method, a dipping method, a paddle method, and the like, and a high-pressure spray method is preferable.
  • the non-photosensitive layer has a lower solubility in a developer than the photosensitive layer, and the solubility change in the exposed area is poor. Therefore, a clear resin pattern of the non-photosensitive layer like the photosensitive layer is not formed, or no resin pattern is formed at all.
  • the development conditions are usually 20 to 40 ° C. for about 1 to 10 minutes.
  • the unexposed portion of the photosensitive layer is eluted, the non-photosensitive layer on the unexposed portion is broken, and penetrates the photosensitive layer and the non-photosensitive layer. A hole is formed.
  • the alkaline developer examples include an alkaline aqueous solution in which an alkaline compound such as sodium hydroxide, potassium hydroxide, ammonia water, tetramethylammonium hydroxide, and choline is dissolved in water so as to have a concentration of about 1 to 10% by mass. Is mentioned.
  • An appropriate amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant can be added to the alkaline aqueous solution.
  • the alkaline developer is preferably tetramethylammonium hydroxide in terms of excellent resolution.
  • a cured film (resist pattern) is obtained by performing a heat treatment in order to develop the insulating film characteristics and improve the resolution.
  • the curing conditions at this time are not particularly limited, but the photosensitive composition can be cured by heating at 50 to 250 ° C. for about 30 minutes to 10 hours depending on the use of the cured product.
  • heating can be performed in two stages in order to sufficiently advance the curing or to prevent deformation of the obtained pattern shape.
  • it can be cured by heating at 50 to 120 ° C. for about 5 minutes to 2 hours in the first stage and further heating at 80 to 200 ° C. for about 10 minutes to 10 hours in the second stage.
  • a general oven, infrared furnace, or the like can be used as a heating facility.
  • the laminated body of the present embodiment is heat-treated after development, whereby the non-photosensitive layer torn as shown in FIG. 4 is fused to the wall surface of the hole to form a via.
  • the non-photosensitive layer is torn in a shape similar to the shape of the hole, the non-photosensitive layer does not necessarily have to be fused to the wall surface of the hole.
  • the method for forming the circuit is not particularly limited, and a photosensitive layer and a non-photosensitive layer are formed on the inner layer circuit, and an outer layer circuit is formed on the non-photosensitive layer by a plating method.
  • an oxidizing roughening liquid such as a chromium / sulfuric acid roughening liquid, an alkaline permanganic acid roughening liquid, a sodium fluoride / chromium / sulfuric acid roughening liquid, or a borofluoric acid roughening liquid can be used.
  • an aqueous solution of diethylene glycol monobutyl ether and NaOH is first heated as a swelling solution to 80 ° C., and the laminate or multilayer wiring board is immersed for 5 minutes.
  • an aqueous solution of KMnO 4 and NaOH is heated to 80 ° C. and immersed for 10 minutes.
  • KMnO 4 is reduced by immersing in a neutralizing solution, for example, an aqueous hydrochloric acid solution of stannous chloride (SnCl 2 ) at room temperature for 5 minutes.
  • a plating catalyst applying treatment for adhering palladium is performed.
  • the plating catalyst treatment is performed by immersing in a palladium chloride plating catalyst solution.
  • an electroless plating solution to deposit an electroless plating layer (conductor layer) having a thickness of 0.1 to 1.5 ⁇ m on the entire surface of the non-photosensitive layer. If necessary, further electroplating is performed to obtain a necessary thickness.
  • the electroless plating solution used for electroless plating a known electroless plating solution can be used, and there is no particular limitation.
  • electroplating can be performed by a known method and is not particularly limited. These platings are preferably copper platings. Furthermore, unnecessary portions can be removed by etching to form a circuit layer. Furthermore, a multilayer wiring board with many layers can be manufactured by repeating the same process.
  • the roughening treatment can also be performed to remove via smear.
  • an interlayer insulating layer 103 is formed on both surfaces of a base material 101 having a wiring pattern 102 formed on the surface (see FIG. 2A).
  • the interlayer insulating layer 103 can be formed by preparing the above-described dry film in advance and using a laminator to attach the photosensitive layer and the non-photosensitive layer of the dry film so that the photosensitive layer is in contact with the printed wiring board. .
  • the photosensitive composition is applied to the substrate to form a photosensitive layer, and then the resin composition is applied onto the photosensitive layer to form a non-photosensitive layer.
  • the interlayer insulating layer 103 may be formed.
  • the interlayer insulating layer 103 is expressed as a single layer for simplification, but is actually divided into a photosensitive layer and a non-photosensitive layer.
  • an opening 104 is formed by exposing a region other than a portion that needs to be electrically connected to the outside, developing, and then performing heat treatment (see FIG. 2B). Smear (residue) around the opening 104 is removed by desmear treatment.
  • a seed layer 105 is formed by an electroless plating method (see FIG. 2C). A photosensitive layer of the semi-additive photosensitive element is formed on the seed layer 105, and a predetermined portion is exposed and developed to form a resin pattern 106 (see FIG. 2D).
  • a wiring pattern 107 is formed on the portion of the seed layer 105 where the resin pattern 106 is not formed by electrolytic plating, and the resin pattern 106 is removed using a stripping solution, and then the wiring pattern 107 of the seed layer 105 is formed. Unexposed portions are removed by etching (see FIG. 2E).
  • the multilayer printed wiring board 100A can be manufactured by repeating the above operation and forming the solder resist 108 on the outermost surface (see FIG. 2F).
  • the dry film according to the second embodiment is a dry film including a photosensitive layer and a non-photosensitive layer, and a photosensitive layer and a non-photosensitive layer are formed on a substrate in this order, and the photosensitive layer is exposed to dry By developing the film, the unexposed portion of the photosensitive layer is eluted and the non-photosensitive layer on the unexposed portion is broken, and a via can be formed at a location where the non-photosensitive layer is broken by the heat treatment after development. Is.
  • the dry film according to the present embodiment includes, for example, a photosensitive layer and a non-photosensitive layer formed in this order on a substrate, and after exposing the photosensitive layer in a predetermined pattern by the above-described method, the non-photosensitive layer And by spraying the photosensitive layer with an aqueous 2.38 mass% tetramethylammonium hydroxide solution for a time corresponding to twice the shortest development time (the shortest time for removing the unexposed portion of the photosensitive layer). As shown in FIG. 3, the unexposed portion of the photosensitive layer is eluted and the non-photosensitive layer on the unexposed portion is broken. In the developed dry film, a hole penetrating the photosensitive layer and the non-photosensitive layer is formed.
  • the development here can also be performed by a method other than the spray method described above. Moreover, you may heat-process the photosensitive layer exposed before developing a dry film.
  • the post-exposure heat treatment is preferably performed under the same conditions as the post-exposure heat treatment in the first embodiment described above.
  • the developed dry film is heat-treated, so that the torn non-photosensitive layer is fused to the wall surface of the hole as shown in FIG. 4 to form a via.
  • the heat treatment can be performed, for example, at 50 to 250 ° C. for about 30 minutes to 10 hours in one stage. In the first stage, heating is performed at 50 to 120 ° C. for about 5 minutes to 2 hours, and then the second treatment. The heating may be performed in two steps at 80 to 200 ° C. for about 10 minutes to 10 hours.
  • the non-photosensitive layer and the photosensitive layer in the dry film of the present embodiment are not particularly limited as long as they have the functions described above, and examples thereof include the photosensitive layer and the non-photosensitive layer described in the first embodiment. It is done. Moreover, a resist pattern and a multilayer printed wiring board can be formed by the above-mentioned method by using the dry film of this embodiment.
  • the photosensitive layer is a positive type, the exposed portion of the photosensitive layer elutes and the non-photosensitive layer on the exposed portion is broken, but vias can be formed at locations where the non-photosensitive layer is broken by the heat treatment after development.
  • Varnish a-II was obtained in the same manner as varnish a-I except that the component (D) of varnish a-I was removed.
  • varnish a-III solid content concentration: about 25 mass%) was obtained using a disperser (Nanomizer, trade name, manufactured by Yoshida Kikai Kogyo Co., Ltd.).
  • F-1 Cresol novolak resin (Asahi Organic Materials Co., Ltd., trade name: TR4020G)
  • F-2 Cresol novolac resin (Asahi Organic Materials Co., Ltd., trade name: TR4080G)
  • G-1 1,3,4,6-tetrakis (methoxymethyl) glycoluril (manufactured by Sanwa Chemical Co., Ltd., trade name “MX-270”)
  • H-1 Trimethylolpropane triglycidyl ether (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., trade name: ZX-1542, see formula (3) below)
  • H-2 Trimethylolpropane triacrylate (manufactured by Nippon Kayaku Co., Ltd., trade name: TMPTA)
  • H-3 Pentaerythritol triacrylate (manufactured by Nippon Kayaku Co., Ltd., trade name: PET-30)
  • I-1 Triarylsulfonium salt (manufactured by San Apro Co., Ltd., trade name: CPI-310B)
  • Solvent methyl ethyl ketone (manufactured by Wako Pure Chemical Industries, Ltd.)
  • Sol-gel silica having an average primary particle size of 15 nm, which is coupled with D′-1: 3-methacryloyloxypropyltrimethoxysilane
  • the solution of the resin composition used for forming the non-photosensitive layer obtained above becomes uniform in thickness on a polyethylene terephthalate film (product name “Purex A53” manufactured by Teijin DuPont Films Ltd.) (support). And dried for 10 minutes with a hot air convection dryer at 100 to 140 ° C. to form a non-photosensitive layer so that the film thickness after drying was as shown in Tables 2 and 3.
  • the solution of the photosensitive composition obtained above is applied onto the non-photosensitive layer so that the thickness is uniform, and dried for 10 minutes in a hot air convection dryer at 90 ° C., and the film thickness after drying
  • the photosensitive layer was formed so as to have the thicknesses shown in Tables 2 and 3.
  • a polypropylene film (manufactured by Tamapoly Co., Ltd., product name “NF-15”) (protective layer) was bonded onto the photosensitive layer to obtain dry films.
  • the composition of the produced dry film is shown in Tables 2 and 3.
  • Example A1 a non-photosensitive layer (thickness: 0.5 ⁇ m) formed using varnish a-I and a photosensitive layer (thickness) formed using varnish b-I on the support. : 10 ⁇ m) and a dry film comprising a protective layer in this order.
  • dry films were prepared using solutions of the corresponding resin compositions.
  • MVLP-500 manufactured by Meiki Seisakusho Co., Ltd.
  • the exposed photosensitive layer is then heated at 65 ° C. for 1 minute and then at 75 ° C. for 8 minutes (post-exposure bake), using a 2.38% by weight aqueous tetramethylammonium hydroxide solution to develop the shortest development time (the photosensitive layer).
  • the unexposed portion of the photosensitive layer was removed (development process) by spraying for a time corresponding to twice the shortest time for removing the exposed portion).
  • heat treatment was performed at 180 ° C. for 60 minutes. After the heat treatment, the via pattern formed using a metal microscope was observed, and the resolution was evaluated with the minimum via pattern size. The evaluation results are shown in Tables 2 and 3.
  • FIG.3 and FIG.4 respectively.
  • SEM scanning electron microscope
  • the evaluation laminated body produced by the above-mentioned method was exposed.
  • the non-photosensitive layer or the photosensitive layer was exposed using an exposure machine having a high-pressure mercury lamp (trade name “EXM-1201” manufactured by Oak Manufacturing Co., Ltd.) so that the irradiation energy amount was 3000 mJ / cm 2 .
  • the exposed evaluation laminate was heated on a hot plate at 65 ° C. for 2 minutes and then at 95 ° C. for 8 minutes (post exposure bake). Furthermore, it heat-processed for 60 minutes at 180 degreeC with the hot air convection type dryer, and obtained the cured film.
  • an aqueous solution of diethylene glycol monobutyl ether: 200 ml / L, sodium hydroxide: 5 g / L was prepared as a swelling liquid, heated to 80 ° C. and immersed for 10 minutes.
  • an aqueous solution of potassium permanganate: 60 g / L and sodium hydroxide: 40 g / L was prepared as a roughening solution, heated to 80 ° C. and immersed for 15 minutes.
  • an aqueous solution of a neutralizing solution tin chloride (SnCl 2 ): 30 g / L, hydrogen chloride: 300 ml / L
  • the surface roughness Ra of the surface of the insulating resin (non-photosensitive layer (photosensitive layer when no non-photosensitive layer is present) after the heat treatment) after chemical roughening is measured using a micromap MN5000 model manufactured by Ryoka System Co., Ltd. And measured. The evaluation results are shown in Tables 2 and 3.
  • an electroless plating catalyst activator Neogant 834 (Atotech Japan Co., Ltd., trade name) containing lead chloride (PdCl 2 ) is set to 35 ° C. Heat and immerse for 5 minutes, immerse in plating solution Print Gantt MSK-DK (trade name, manufactured by Atotech Japan Co., Ltd.) for electroless copper plating for 15 minutes at room temperature, and perform copper sulfate electrolytic plating It was. Thereafter, annealing was performed at 180 ° C. for 60 minutes to form a conductor layer having a thickness of 20 ⁇ m.
  • a region having a width of 10 mm and a length of 50 mm was formed on the conductor layer by etching, and one end of this region was peeled off by 10 mm at the interface between the conductor layer (copper layer) and the cured insulating resin.
  • the peeled conductor layer was pinched with a gripper, and the load (peel strength) when peeled at room temperature at a pulling speed of 50 mm / min in the thickness direction (vertical direction) of the silicon wafer was measured.
  • the evaluation results are shown in Tables 2 and 3. In this specification, room temperature means 25 ° C.
  • Examples A1 to A13 had good resolution and high adhesive strength with a peel strength of 0.3 kN / m or more.
  • Comparative Examples A1 to A5 had lower peel strength and Comparative Examples A6 to A15 had inferior resolution as compared with the Examples.
  • a photosensitive layer having a thickness of 10 ⁇ m after drying was formed.
  • a polypropylene film manufactured by Tamapoly Co., Ltd., product name “NF-15”) (protective layer) was bonded onto the photosensitive layer to obtain dry films.
  • Table 5 shows the configuration of the produced dry film.
  • a non-photosensitive layer (thickness: 1 ⁇ m) formed using varnish c-I and a photosensitive layer (thickness: formed using varnish d-I) on the support. 10 ⁇ m) and a dry film provided with a protective layer in this order.
  • dry films were prepared using the corresponding resin composition solution and / or the photosensitive composition solution, respectively.
  • MVLP-500 manufactured by Meiki Seisakusho Co., Ltd.
  • the exposed photosensitive layer is heated at 75 ° C. for 8 minutes (post-exposure baking), and the shortest development time using the 2.38 mass% tetramethylammonium hydroxide aqueous solution (the shortest time at which the unexposed portion of the photosensitive layer is removed)
  • the unexposed portion of the photosensitive layer was removed (development processing) by spraying for a time corresponding to four times the (time).
  • the film was heat-treated at 180 ° C. for 60 minutes in a hot air convection dryer. After the heat treatment, the via pattern formed using a metal microscope was observed.
  • an aqueous solution of a neutralizing solution (tin chloride (SnCl 2 ): 30 g / L, hydrogen chloride: 300 ml / L) was prepared, heated to 40 ° C. and immersed for 5 minutes to reduce potassium permanganate. .
  • HS-202B (trade name, manufactured by Hitachi Chemical Co., Ltd.), a catalyst for electroless plating containing lead chloride (PdCl 2 ), at room temperature for 10 minutes, washed with water, and electroless copper
  • CUST-201 plating solution (trade name, manufactured by Hitachi Chemical Co., Ltd.) for 15 minutes at room temperature, and further subjected to copper sulfate electrolytic plating. Thereafter, annealing was performed at 180 ° C. for 60 minutes to form a conductor layer having a thickness of 20 ⁇ m.
  • a region having a width of 10 mm and a length of 50 mm was formed on the conductor layer by etching, and one end of this region was peeled off by 10 mm at the interface between the conductor layer (copper layer) and the cured insulating resin.
  • the peeled conductor layer was pinched with a gripper, and the load (peel strength) when peeled at room temperature at a pulling speed of 50 mm / min in the thickness direction (vertical direction) of the silicon wafer was measured.
  • the evaluation results are shown in Table 5. In this specification, room temperature means 25 ° C.
  • the cured film produced by the above method was irradiated with ultraviolet rays.
  • the ultraviolet irradiation was performed using a conveyor type ultraviolet irradiation apparatus with a metal halide lamp (maximum wavelength 350 to 380 nm) at an exposure amount of 3000 mJ / cm 2 .
  • an aqueous solution of diethylene glycol monobutyl ether: 200 ml / L, sodium hydroxide: 5 g / L was prepared, heated to 70 ° C. and immersed for 10 minutes. Thereafter, it is washed with water, and immersed in a conditioner solution “CLC-601” (trade name, manufactured by Hitachi Chemical Co., Ltd.) for 5 minutes at 60 ° C. as a pretreatment for electroless plating, then washed with water, and pre-dip solution “PD- 201 "(trade name, manufactured by Hitachi Chemical Co., Ltd.) for 2 minutes at room temperature.
  • a conditioner solution “CLC-601” trade name, manufactured by Hitachi Chemical Co., Ltd.
  • HS-202B (trade name, manufactured by Hitachi Chemical Co., Ltd.), a catalyst for electroless plating containing lead chloride (PdCl 2 ), at room temperature for 10 minutes, washed with water, and electroless copper
  • CUST-201 plating solution (trade name, manufactured by Hitachi Chemical Co., Ltd.) for 15 minutes at room temperature, and further subjected to copper sulfate electrolytic plating. Thereafter, annealing was performed at 180 ° C. for 60 minutes to form a conductor layer having a thickness of 20 ⁇ m.
  • a region having a width of 10 mm and a length of 50 mm was formed on the conductor layer by etching, and one end of this region was peeled off by 10 mm at the interface between the conductor layer (copper layer) and the cured resin film.
  • the peeled conductor layer was pinched with a gripper, and the load (peel strength) when peeled at room temperature at a pulling speed of 50 mm / min in the thickness direction (vertical direction) of the silicon wafer was measured.
  • the evaluation results are shown in Table 5.
  • room temperature shows 25 degreeC.
  • Example B8 and Comparative Example B7> The solution of the resin composition obtained above was applied on a polyethylene terephthalate film (manufactured by Unitika Co., Ltd.) product name “TR-1”) (support) so as to have a uniform thickness, and was heated at 100 to 140 ° C. It dried for 10 minutes with the hot air convection type dryer, and formed the non-photosensitive layer so that the film thickness after drying might be set to 1 micrometer. Next, a photosensitive composition (manufactured by Hitachi Chemical Co., Ltd., trade name: Raytec (registered trademark) FZ-2700GA) (d-IV) is laminated on the non-photosensitive layer under the conditions of 100 ° C.
  • a photosensitive composition manufactured by Hitachi Chemical Co., Ltd., trade name: Raytec (registered trademark) FZ-2700GA
  • Example B8 a non-photosensitive layer (thickness: 1 ⁇ m) formed using varnish c-I and a photosensitive composition (d-IV) formed on the support were used. It means that a dry film comprising a layer (thickness: 10 ⁇ m) and a protective layer in this order was produced.
  • a photosensitive composition manufactured by Hitachi Chemical Co., Ltd., trade name: Raytec (registered trademark) FZ-2700GA
  • d-IV was used as it was.
  • the resolution, surface roughness and peel strength were evaluated by the methods described above. The evaluation results are shown in Table 6.
  • Examples B1 to B8 have good resolution, and have high peel strength of 0.4 kN / m or more after both chemical roughening and ultraviolet irradiation. showed that.
  • the surface roughness (Ra) of the base resin was as smooth as 0.1 ⁇ m in the ultraviolet irradiation process.
  • Comparative Examples B1 to B3 were inferior in resolution, and the vias could not be opened. Further, Comparative Examples B4 to B7 resulted in poor peel strength.
  • the dry film of the present disclosure is applied as a member used for an interlayer insulating film of a wiring board material or an interlayer insulating film (passivation film) of a semiconductor element or the like.
  • the above-mentioned dry film is suitable for high-density package substrates and the like that are thinned and densified because both the adhesiveness and resolution with the plated copper are good.

Abstract

L'invention concerne un film sec comprenant une couche photosensible et une couche non photosensible, ladite couche non photosensible contenant une résine thermodurcissable.
PCT/JP2016/058045 2015-03-27 2016-03-14 Film sec, produit durci, stratifié et procédé de formation de motif de réserve WO2016158362A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP2015-066538 2015-03-27
JP2015066538A JP2018087832A (ja) 2015-03-27 2015-03-27 ドライフィルム、硬化物、積層体及びレジストパターンの形成方法
JP2015087885A JP2018087835A (ja) 2015-04-22 2015-04-22 ドライフィルム、硬化物、積層体及びレジストパターンの形成方法
JP2015-087885 2015-04-22

Publications (1)

Publication Number Publication Date
WO2016158362A1 true WO2016158362A1 (fr) 2016-10-06

Family

ID=57006763

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2016/058045 WO2016158362A1 (fr) 2015-03-27 2016-03-14 Film sec, produit durci, stratifié et procédé de formation de motif de réserve

Country Status (2)

Country Link
TW (1) TW201641276A (fr)
WO (1) WO2016158362A1 (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018163602A1 (fr) * 2017-03-09 2018-09-13 Jsr株式会社 Procédé de production d'une structure façonnée plaquée et composition de résine photosensible pour la production de structures façonnées plaquées
US11140768B2 (en) 2019-04-10 2021-10-05 At&S Austria Technologie & Systemtechnik Aktiengesellschaft Component carrier with high passive intermodulation performance
WO2022075432A1 (fr) * 2020-10-08 2022-04-14 太陽インキ製造株式会社 Composition de résine multicouche photosensible, film sec, produit durci et composant électronique
WO2023145973A1 (fr) * 2022-01-31 2023-08-03 太陽ホールディングス株式会社 Film sec, produit durci, couche d'isolation intercouche comprenant le produit durci, et carte de câblage

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109644555B (zh) 2016-08-12 2022-03-01 昭和电工材料株式会社 层间绝缘膜及其制造方法
KR102225796B1 (ko) * 2017-03-21 2021-03-11 미쓰이금속광업주식회사 배선판의 제조 방법

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003330178A (ja) * 2002-05-10 2003-11-19 Kanegafuchi Chem Ind Co Ltd エポキシ樹脂層を有する感光性ドライフィルムレジスト及びその作製方法
JP2004145013A (ja) * 2002-10-24 2004-05-20 Kanegafuchi Chem Ind Co Ltd 接着剤層を有する感光性ドライフィルムレジストおよびその製造方法
JP2008241741A (ja) * 2007-03-23 2008-10-09 Jsr Corp ソルダーレジスト用ポジ型ドライフィルム及びその硬化物並びにそれを備える回路基板及び電子部品
JP2009210972A (ja) * 2008-03-06 2009-09-17 Jsr Corp 転写フィルムおよびパターンの形成方法
JP2010197996A (ja) * 2009-01-30 2010-09-09 Jsr Corp 感光性絶縁樹脂組成物及びその硬化物並びに絶縁膜の製造方法
JP2010238704A (ja) * 2009-03-30 2010-10-21 Sanyo Chem Ind Ltd プリント配線板用層間絶縁樹脂フィルム
WO2013094606A1 (fr) * 2011-12-22 2013-06-27 太陽インキ製造株式会社 Film sec, carte à câblage imprimé utilisant ledit film sec, procédé de production de carte à câblage imprimé et substrat de montage de puces à protubérances
WO2013099885A1 (fr) * 2011-12-27 2013-07-04 太陽インキ製造株式会社 Film sec, structure stratifiée, carte à câblage imprimé et processus de production d'une structure stratifiée

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003330178A (ja) * 2002-05-10 2003-11-19 Kanegafuchi Chem Ind Co Ltd エポキシ樹脂層を有する感光性ドライフィルムレジスト及びその作製方法
JP2004145013A (ja) * 2002-10-24 2004-05-20 Kanegafuchi Chem Ind Co Ltd 接着剤層を有する感光性ドライフィルムレジストおよびその製造方法
JP2008241741A (ja) * 2007-03-23 2008-10-09 Jsr Corp ソルダーレジスト用ポジ型ドライフィルム及びその硬化物並びにそれを備える回路基板及び電子部品
JP2009210972A (ja) * 2008-03-06 2009-09-17 Jsr Corp 転写フィルムおよびパターンの形成方法
JP2010197996A (ja) * 2009-01-30 2010-09-09 Jsr Corp 感光性絶縁樹脂組成物及びその硬化物並びに絶縁膜の製造方法
JP2010238704A (ja) * 2009-03-30 2010-10-21 Sanyo Chem Ind Ltd プリント配線板用層間絶縁樹脂フィルム
WO2013094606A1 (fr) * 2011-12-22 2013-06-27 太陽インキ製造株式会社 Film sec, carte à câblage imprimé utilisant ledit film sec, procédé de production de carte à câblage imprimé et substrat de montage de puces à protubérances
WO2013099885A1 (fr) * 2011-12-27 2013-07-04 太陽インキ製造株式会社 Film sec, structure stratifiée, carte à câblage imprimé et processus de production d'une structure stratifiée

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018163602A1 (fr) * 2017-03-09 2018-09-13 Jsr株式会社 Procédé de production d'une structure façonnée plaquée et composition de résine photosensible pour la production de structures façonnées plaquées
JPWO2018163602A1 (ja) * 2017-03-09 2019-12-26 Jsr株式会社 メッキ造形物の製造方法、及びメッキ造形物製造用感光性樹脂組成物
US11249398B2 (en) 2017-03-09 2022-02-15 Jsr Corporation Method for producing plated shaped structure and photosensitive resin composition for production of plated shaped structures
JP7147741B2 (ja) 2017-03-09 2022-10-05 Jsr株式会社 メッキ造形物の製造方法
US11140768B2 (en) 2019-04-10 2021-10-05 At&S Austria Technologie & Systemtechnik Aktiengesellschaft Component carrier with high passive intermodulation performance
WO2022075432A1 (fr) * 2020-10-08 2022-04-14 太陽インキ製造株式会社 Composition de résine multicouche photosensible, film sec, produit durci et composant électronique
WO2023145973A1 (fr) * 2022-01-31 2023-08-03 太陽ホールディングス株式会社 Film sec, produit durci, couche d'isolation intercouche comprenant le produit durci, et carte de câblage

Also Published As

Publication number Publication date
TW201641276A (zh) 2016-12-01

Similar Documents

Publication Publication Date Title
WO2016158362A1 (fr) Film sec, produit durci, stratifié et procédé de formation de motif de réserve
TWI667536B (zh) 半導體裝置
JP2017211555A (ja) ドライフィルム及びレジストパターンの形成方法
EP2940527B1 (fr) Composition de résine photosensible, film photosensible, et procédé permettant de former un motif de résine
KR20040004392A (ko) 포지티브형 감광성 에폭시 수지 조성물 및 그를 사용한인쇄회로판
US10656521B2 (en) Photosensitive resin composition, photosensitive element, cured product, semiconductor device, method for forming resist pattern, and method for producing circuit substrate
US9829791B2 (en) Photosensitive resin composition, photosensitive element, semiconductor device and method for forming resist pattern
WO2016157622A1 (fr) Film sec, produit durci, dispositif à semi-conducteurs, et procédé de formation de motif de produit de réserve
JP6600962B2 (ja) 感光性樹脂組成物、感光性エレメント、半導体装置及びレジストパターンの形成方法
JP2018087832A (ja) ドライフィルム、硬化物、積層体及びレジストパターンの形成方法
WO2016159133A1 (fr) Film sec, produit durci, dispositif à semi-conducteur et procédé de formation de motif de réserve
JP2018084683A (ja) 感光性樹脂組成物、感光性エレメント、硬化物、半導体装置及びレジストパターンの形成方法
WO2018164233A1 (fr) Élément photosensible, dispositif à semi-conducteurs, et procédé de formation d'un motif de réserve
JP2018087835A (ja) ドライフィルム、硬化物、積層体及びレジストパターンの形成方法
WO2018070489A1 (fr) Élément photosensible, dispositif à semi-conducteur et procédé de formation de motif de réserve
JP2014204023A (ja) 導体配線を有する構造体の製造方法、その方法により製造された導体配線を有する構造体、熱硬化性樹脂組成物、樹脂フィルム、感光性樹脂組成物及びドライフィルムレジスト
WO2016159160A1 (fr) Composition de résine photosensible, élément photosensible, produit durci, et procédé de formation d'un motif de réserve
WO2016157605A1 (fr) Composition de résine photosensible, élément photosensible, produit durci et procédé de formation de motif de produit de réserve
JP6790461B2 (ja) 感光性樹脂組成物、感光性エレメント、半導体装置及びレジストパターンの形成方法
JP2018084684A (ja) 感光性樹脂組成物、感光性エレメント、硬化物、半導体装置及びレジストパターンの形成方法
JP2018169548A (ja) 感光性樹脂積層体、及びレジストパターンの形成方法
JP2018091879A (ja) ドライフィルム、硬化物、及びレジストパターンの形成方法
JP2018091877A (ja) 感光性樹脂組成物、感光性エレメント、硬化物及びレジストパターンの形成方法

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 16772245

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 16772245

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: JP